JP4553373B2 - Polyhydroxyalkanoic acid having vinyl group, ester group, carboxyl group and sulfonic acid group and method for producing the same - Google Patents

Description

  The present invention relates to a novel polyhydroxyalkanoate and a method for producing the same.

  Biodegradable polymer materials are widely applied to medical materials, drug delivery systems, and environmentally compatible materials. In recent years, in addition to these, new functions have been required, and various studies have been conducted. In particular, for polyhydroxyalkanoates typified by polylactic acid, it has been studied to introduce functional groups that can be chemically modified into the molecule, and there have been reports on compounds having a carboxyl group or a vinyl group introduced therein. For example, polymalic acid is known as a polyhydroxyalkanoate having a carboxyl group in the side chain. This polymalic acid polymer has chemical formula (22),

Α type represented by the chemical formula (23),

The β type represented by is known. Of these, β-type polymalic acid and copolymers thereof are described in US Pat. No. 4,265,247 (Patent Document 1), which has chemical formula (24),

(R _24: a benzyl group)
A polymer obtained by ring-opening polymerization of a benzyl ester of β-malolactone represented by the formula: In addition, an α-type polymalic acid-glycolic acid copolymer and a copolymer containing other hydroxyalkanoic acids such as glycolic acid are disclosed in JP-A-2-41515 (Patent Document 2). twenty five)

(R ₂₅ is a lower alkyl group such as methyl group, ethyl group, n-propyl group, isopropyl group, t-butyl group, and benzyl group)
A copolymer obtained by copolymerizing a cyclic diester with glycolide and lactide, and a lactone that is an intramolecular ring-closing ester of ω-hydroxycarboxylic acid is disclosed.

  As polyhydroxyalkanoates having a carboxyl group in the side chain, 7-oxo-4-oxepanone carboxylic acid ester is ring-opening polymerized in Macromolecules 2000, 33 (13), 4619-4627 (Non-patent Document 1). Thus, it is disclosed that a polymer having an ester group in a side chain is produced, and a polymer having a carboxylic acid in a side chain is produced by hydrogenolysis of the polymer. Biomacromolecules 2000, 1, 275 (Non-patent Document 2) discloses a main chain of poly (ε-caprolactone) by reacting poly (ε-caprolactone) with lithium diisopropylamide and further reacting with benzyl chloroformate. A polymer in which a benzyloxycarbonyl group is introduced into a methylene group at the α-position of a carbonyl group therein is disclosed. In Macromolecular Bioscience 2004, 4, 232 (Non-patent Document 3), by reacting polylactic acid with lithium diisopropylamide and further reacting with benzyl bromoacetate, α of the carbonyl group in the main chain of polylactic acid is obtained. Polymers in which a (benzyloxycarbonyl) methyl group is introduced into the methylene group at the position are disclosed.

  As a polyhydroxyalkanoate having a vinyl group in the side chain, a polymer obtained by ring-opening polymerization of α-allyl (δ-valerolactone) is disclosed in Polymer Materials Science & Engineering 2002, 87, 254 (Non-patent Document 4). Yes. Similarly, as a polyhydroxyalkanoate having a vinyl group in the side chain, Polymer Preprints 2002, 43 (2), 727 (Non-patent Document 5), 6,6-diallyl-1, which is a 6-membered diester monomer, A polymer obtained by ring-opening polymerization of 4-dioxane-2,5-dione is disclosed.

There has been a report on a polymer having a new function by introducing a structure imparting functionality to a polyhydroxyalkanoate into which a functional group that can be chemically modified is introduced as described above. International Journal of Biological Macromolecules 25 (1999) 265 (Non-patent Document 6) obtained a copolymer of α-type malic acid and glycolic acid by ring-opening polymerization of a cyclic dimer of α-malic acid and glycolic acid. The resulting polymer is deprotected to obtain a polyester having a carboxyl group in the side chain. When the tripeptide was chemically modified to the carboxyl group of this side chain and the resulting polymer was evaluated for cell adhesiveness, good results were obtained.
U.S. Pat.No. 4,265,247 Japanese Patent Laid-Open No. 2-3415 Macromolecules 2000, 33 (13), 4619-4627 Biomacromolecules 2000, 1, 275 Macromolecular Bioscience 2004, 4, 232 Polymeric Materials Science & Engineering 2002, 87, 254 Polymer Preprints 2002, 43 (2), 727 International Journal of Biological Macromolecules 25 (1999) 265

  As described above, it is not possible to add new functionality by introducing a unit having a carboxyl group that is a reactive functional group or a unit having a vinyl group into the molecule and chemically modifying the reactive functional group. There are few reported cases. Therefore, the present invention provides a novel polyhydroxyalkanoate having a reactive functional group in the molecule and a method for producing the same, and a novel polyhydroxyalkanoate having a new function by chemically modifying the polyhydroxyalkanoate having the reactive functional group. A polyhydroxyalkanoate and a method for producing the same are provided.

  Therefore, the present inventors have developed a novel polyhydroxyalkanoate having a reactive functional group in the molecule and a novel polyhydroxyalkanoate having a new function by chemically modifying the polyhydroxyalkanoate having the reactive functional group. As a result of intensive research aimed at the development of alkanoates, the inventors have reached the following inventions.

  The polyhydroxyalkanoate according to the present invention includes the following.

  (1) A polyhydroxyalkanoate containing at least one unit represented by the chemical formula (1) in the molecule.

(Wherein, R .R ₁ representing a -A ₁ -SO ₂ R ₁ represents OH, a halogen atom, ONa, .R _1a and A ₁ is OK or OR _1a are each independently substituted or unsubstituted Represents a group having an aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure, and n is an integer selected from 0 to 4. n is 0. M is an integer selected from 0 to 8, when m is an integer selected from 2, 3, and 4. When n is 1, m is 0. When there are a plurality of units, R, R ₁ , R _1a , A ₁ , m, and n represent the above meanings independently for each unit.)
(2) A polyhydroxyalkanoate containing at least one unit represented by the chemical formula (5).

(Wherein R ₅ is hydrogen, a group forming a salt, or R _5a . In the formula, R _5a is a linear or branched alkyl group having 1 to 12 carbon atoms, an aralkyl group, or And n is an integer selected from 0, 2, 3, and 4. When n is 0, m is an integer selected from 2 to 8, provided that m is 2. In this case, R ₅ is only R _5a , and when n is an integer selected from 2 to 4, m is an integer selected from 0 to 8. When there are a plurality of units , R ₅ , R _5a , m and n have the above meanings independently for each unit.)
(3) A polyhydroxyalkanoate containing at least one unit represented by the chemical formula (6).

(In the formula, n is an integer selected from 0, 2, 3, and 4. When n is 0, m is an integer selected from 2 to 8. n is an integer selected from 2 to 3) M is an integer selected from 0 to 8. When n is an integer selected from 4, m is an integer selected from 0, 2 to 8. There are a plurality of units. M and n represent the above meanings independently for each unit.)

On the other hand, the polyhydroxyalkanoate production method according to the present invention includes the following methods.

  (A) A method for producing a polyhydroxyalkanoate represented by the chemical formula (14), which comprises polymerizing a compound represented by the chemical formula (8) in the presence of a catalyst.

(R ₈ is a linear or branched alkylene group having 1 to 11 carbon atoms, an alkyleneoxyalkylene group (each alkylene group is independently an alkylene group having 1 to 2 carbon atoms), 11 is a linear or branched alkenyl group, or an alkylidene group having 1 to 5 carbon atoms which may be substituted with aryl, and m is an integer selected from 2 to 8.)

(R ₉ is an alkylene group having a linear or branched alkylene group having 1 to 11 carbon atoms, alkylene oxyalkylene group (each alkylene group are each independently a carbon number 1-2), 1 carbon atoms 11 is a linear or branched alkenyl group or an alkylidene group having 1 to 5 carbon atoms which may be substituted with aryl, m is an integer selected from 2 to 8. There are a plurality of units. In this case, R ₉ and m represent the above meanings independently for each unit.)

(B) A method for producing a polyhydroxyalkanoate represented by the chemical formula (13), which comprises a step of polymerizing the compound represented by the chemical formula (12) in the presence of a catalyst.

(n is an integer selected from 2 to 4, and when n is an integer selected from 2 to 3, m is an integer selected from 0 to 8. When n is 4, m is 0, (It is an integer selected from 2 to 8.)

(n is an integer selected from 2 to 4. When n is an integer selected from 2 to 3, m is an integer selected from 0 to 8. When n is 4, m is 0, (It is an integer selected from 2 to 8. When there are a plurality of units, m and n represent the above meanings independently for each unit.)
(C) A method for producing a polyhydroxyalkanoate represented by the chemical formula (15), which comprises a step of polymerizing the compound represented by the chemical formula (14) in the presence of a catalyst.

(Wherein R _14a is a linear or branched alkylene group having 1 to 11 carbon atoms, an alkyleneoxyalkylene group (each alkylene group is independently an alkylene group having 1 to 2 carbon atoms), carbon A linear or branched alkenyl group having 1 to 11 carbon atoms, or an alkylidene group having 1 to 5 carbon atoms which may be substituted with aryl, and R _14b is a linear or branched chain having 1 to 12 carbon atoms N is an integer selected from 0, 2, 3, and 4. When n is 0, m is an integer selected from 2 to 8. n is In the case of 2-4, m is an integer selected from 0-8.)

(Wherein R _15a is a linear or branched alkylene group having 1 to 11 carbon atoms, an alkyleneoxyalkylene group (each alkylene group is independently an alkylene group having 1 to 2 carbon atoms), carbon A linear or branched alkenyl group having 1 to 11 carbon atoms, or an alkylidene group having 1 to 5 carbon atoms which may be substituted with aryl, and R _15b is a linear or branched chain having 1 to 12 carbon atoms N is an integer selected from 0, 2, 3, and 4. When n is 0, m is an integer selected from 2 to 8. n is 2 to 2. In the case of 4, m is an integer selected from 0 to 8. When there are a plurality of units, R _15b , m and n have the above meanings independently for each unit.)
(D) A method for producing a polyhydroxyalkanoate containing a unit represented by the chemical formula (17), wherein a double bond portion of the polyhydroxyalkanoate containing a unit represented by the chemical formula (16) is subjected to an oxidation reaction.

(In the formula, m is an integer selected from 0 to 8, and n is an integer selected from 0, 2, 3, and 4. When there are a plurality of units, m and n are for each unit. Independently represents the above meaning.)

(In the formula, m is an integer selected from 0 to 8, and R ₁₇ is hydrogen or a group that forms a salt. N is an integer selected from 0, 2, 3, and 4. When there are a plurality of units, m and R ₁₇ independently represent the above meanings for each unit.)
(E) Hydrolyzing the polyhydroxyalkanoate represented by the unit represented by the chemical formula (18) in the presence of an acid or an alkali, or performing a hydrogenolysis including catalytic reduction, 19) A method for producing a polyhydroxyalkanoate comprising the unit represented by

(In the formula, R ₁₈ is a linear or branched alkyl group having 1 to 12 carbon atoms or an aralkyl group. N is an integer selected from 0, 2, 3, and 4. When n is 0, , M is an integer selected from 2 to 8. When n is 2, 3, or 4, m is an integer selected from 0 to 8. When a plurality of units are present, R ₁₈ , m and n represents the above meaning independently for each unit.)

(In the formula, R ₁₉ is hydrogen or a group that forms a salt. N is an integer selected from 0, 2, 3, and 4. When n is 0, m is selected from 2 to 8. When n is 2, 3, or 4, m is an integer selected from 0 to 8. When there are a plurality of units, R ₁₉ , m and n are independent for each unit. The above meanings.)
(F) A polyhydroxyalkanoate containing a unit represented by the chemical formula (20) and at least one amine compound represented by the chemical formula (21) are subjected to a condensation reaction, and the unit represented by the chemical formula (1) is included. Process for producing polyhydroxyalkanoate.

(In the formula, R ₂₀ is hydrogen or a group that forms a salt. N is an integer selected from 0 to 4. When n is 0, 2, 3, or 4, m is 0. It is an integer selected from ~ 8. When n is 1, m is 0. When there are a plurality of units, m, n and R ₂₀ independently represent the above meaning for each unit. .)

(Wherein R ₂₁ is OH, a halogen atom, ONa, OK or OR _21a . R _21a and A ₃ are each independently a substituted or unsubstituted aliphatic hydrocarbon structure, substituted or unsubstituted. When a plurality of units are present, R ₂₁ , R _21a and A ₃ are independently selected from the above meanings when selected from the group having an aromatic ring structure or a substituted or unsubstituted heterocyclic structure. Represents.)

(Wherein, R .R ₁ representing a -A ₁ -SO ₂ R ₁ represents OH, a halogen atom, ONa, .R _1a and A ₁ is OK or OR _1a are each independently substituted or unsubstituted Represents a group having an aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure, and n is an integer selected from 0 to 4. n is 0. In the case of 2, 3, 4, m is an integer selected from 0 to 8. When n is 1, m is 0. When a plurality of units are present, R, R ₁ , R _1a , A ₁ , m and n represent the above meanings independently for each unit.)
(G) a step of reacting a polyhydroxyalkanoate containing a unit represented by the chemical formula (168) with a base, and a step of reacting the compound obtained in the above step with the compound represented by the chemical formula (169). And a method for producing a polyhydroxyalkanoate comprising a unit represented by the chemical formula (170).

(In the formula, m is an integer selected from 0 to 8. X is a halogen atom. R ₁₆₉ is a linear or branched alkyl group having 1 to 12 carbon atoms or an aralkyl group. .)

(In the formula, m is an integer selected from 0 to 8. R ₁₇₀ is a linear or branched alkyl group having 1 to 12 carbon atoms or an aralkyl group. When there are a plurality of units. , R ₁₇₀ and m represent the above meanings independently for each unit.)
(H) a step of reacting a polyhydroxyalkanoate containing a unit represented by the chemical formula (168) with a base, and a step of reacting the compound obtained in the above step with the compound represented by the chemical formula (171). A method for producing a polyhydroxyalkanoate comprising a unit represented by the chemical formula (172) as a feature.

(Wherein R ₁₇₁ represents -A ₁₇₁ -SO ₂ R _171a . R _171a is OH, a halogen atom, ONa, OK or OR _171b . R _171b and A ₁₇₁ are each independently substituted or substituted. Selected from a group having an unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure, and when there are a plurality of units, R ₁₇₁ , R _171a , R _171b and A ₁₇₁ have the above meanings independently for each unit.)

(Wherein, R ₁₇₂ is .R _172a representing the -A ₁₇₂ -SO ₂ R _172a OH, a halogen atom, ONa, .R _{172 b} and A ₁₇₂ is OK or OR _{172 b} are each independently a substituted or unsubstituted When a plurality of units are present, R ₁₇₂ , R _172a , R _172b and R ₁₇₂ , R _172a , R _172b and A ₁₇₂ represents the above meaning independently for each unit.)
In addition, the present invention includes the following compounds.

  (I) A compound represented by the chemical formula (8).

(R ₈ is a linear or branched alkylene group having 1 to 11 carbon atoms, an alkyleneoxyalkylene group (each alkylene group is independently an alkylene group having 1 to 2 carbon atoms), 11 is a linear or branched alkenyl group, or an alkylidene group having 1 to 5 carbon atoms which may be substituted with aryl, and m is an integer selected from 2 to 8.)
(II) A compound represented by the chemical formula (14).

(Wherein R _14a is a linear or branched alkylene group having 1 to 11 carbon atoms, an alkyleneoxyalkylene group (each alkylene group is independently an alkylene group having 1 to 2 carbon atoms), carbon A linear or branched alkenyl group having 1 to 11 carbon atoms, or an alkylidene group having 1 to 5 carbon atoms which may be substituted with aryl, and R _14b is a linear or branched chain having 1 to 12 carbon atoms And n is an integer selected from 0, 2, 3, and 4, n is 0, m is an integer selected from 2 to 8, and n is 2 In the case of .about.4, m is an integer selected from 0 to 8.)

  The contents of the present invention will be described below. The target polyhydroxyalkanoate represented by the chemical formula (1) in the present invention is a polyhydroxyalkanoate containing a unit represented by the chemical formula (20) used as a starting material and an aminosulfonic acid compound represented by the chemical formula (21). It can be produced by reaction with one species.

(In the formula, R ₂₀ is hydrogen or a group that forms a salt. N is an integer selected from 0 to 4, and when n is 0, 2, 3, or 4, m is 0. Is an integer selected from -8, and when n is 1, m is 0. When there are a plurality of units, m, n, and R ₂₀ independently represent the above meanings for each unit. .)

(Wherein R ₂₁ is OH, a halogen atom, ONa, OK or OR _21a . R _21a and A ₃ are each independently a substituted or unsubstituted aliphatic hydrocarbon structure, substituted or unsubstituted. When a plurality of units are present, R ₂₁ , R _21a and A ₃ are independently selected from the above meanings when selected from the group having an aromatic ring structure or a substituted or unsubstituted heterocyclic structure. Represents.)
More specifically, R ₂₁ is OH, a halogen atom, ONa, OK or OR _21a . R _21a is a linear or branched alkyl group having 1 to 8 carbon atoms and a substituted or unsubstituted phenyl group.

A ₃ is preferably a C _{1 to} C ₈ linear or branched substituted or unsubstituted alkylene group, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthalene group, or a substituted or unsubstituted group. A group having a heterocyclic structure containing one or more of N, S, and O is represented. When A ₃ is a ring structure, the unsubstituted ring may be further condensed. Further, when there are a plurality of units, R ₂₁ , R _21a and A ₃ represent the above meanings independently for each unit.

When A ₃ is a linear substituted or unsubstituted alkylene group, an aminosulfonic acid compound represented by the following chemical formula (26) is exemplified.

(Wherein R ₂₆ is OH, halogen atom, ONa, OK or OR _26a . R _26a is a linear or branched alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted phenyl group. A ₄ is a C _{1 to} C ₈ linear or branched substituted or unsubstituted alkylene group, and when substituted, an alkyl group having 1 to 20 carbon atoms, (Alkoxy groups may be substituted.)
Examples of the compound represented by the chemical formula (26) include 2-aminoethanesulfonic acid (taurine), 3-aminopropanesulfonic acid, 4-aminobutanesulfonic acid, 2-amino-2-methylpropanesulfonic acid, and alkali metals thereof. Examples include salts and esterified products.

When A ₃ is a substituted or unsubstituted phenylene group, examples thereof include aminosulfonic acid compounds represented by the following chemical formula (27).

(Wherein R _3a , R _3b , R _3c , R _3d and R _3e are each independently SO ₂ R _3f (R _3f is OH, a halogen atom, ONa, OK or OR _3f1 (R _3f1 Is a linear or branched alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted phenyl group.)), Hydrogen atom, halogen atom, alkyl group having 1 to 20 carbon atoms, 1 to 20 carbon atoms Alkoxy group, OH group, NH ₂ group, NO ₂ group, COOR _3g (R _3g represents any of H atom, Na atom and K atom), acetamide group, OPh group, NHPh group, CF ₃ group, C Represents a ₂ F ₅ group or a C ₃ F ₇ group (Ph represents a phenyl group), and at least one of these groups is SO ₂ R _3f .)
By using the compound represented by the chemical formula (27), a polyhydroxyalkanoate having one or more units represented by the chemical formula (3) can be obtained.

(In the formula, R _3a , R _3b , R _3c , R _3d , R _3e , and R _3f , R _3f1, and R _3g defined in formula (27) represent the above-mentioned meanings, and n is 0 It is an integer selected from -4 When m is an integer selected from 0, 2, 3, 4, m is an integer selected from 0 to 8. When n is 1, m is 0 is a. when multiple units _{exist, R 3a, R 3b, R} 3c, R 3d, R 3e, R 3f, R 3f1, R 3g, m and n are, above independently for each unit Represents meaning.)
Examples of the compound represented by the chemical formula (27) include p-aminobenzenesulfonic acid (sulfanilic acid), m-aminobenzenesulfonic acid, o-aminobenzenesulfonic acid, m-toluidine-4-sulfonic acid, and o-toluidine-4. -Sulphonic acid sodium salt, p-toluidine-2-sulfonic acid, 4-methoxyaniline-2-sulfonic acid, o-anisidine-5-sulfonic acid, p-anisidine-3-sulfonic acid, 3-nitroaniline-4- Sulfonic acid, 2-nitroaniline-4-sulfonic acid sodium salt, 4-nitroaniline-2-sulfonic acid sodium salt, 1,5-dinitroaniline-4-sulfonic acid, 2-aminophenol-4-hydroxy-5- Nitrobenzenesulfonic acid, 2,4-dimethylaniline-5-sulfonic acid sodium salt, 2,4-dimethylaniline-6-sulfonic acid, 3,4-dimethylaniline-5-sulfonic acid, 4-isopropyl Ruaniline-6-sulfonic acid, 4-trifluoromethylaniline-6-sulfonic acid, 3-carboxy-4-hydroxyaniline-5-sulfonic acid, 4-carboxyaniline-6-sulfonic acid, and alkali metal salts and esters thereof And the like.

When A ₃ is a substituted or unsubstituted naphthalene group, an aminosulfonic acid compound represented by the following chemical formula (28A) or chemical formula (28B) is exemplified.

(Wherein R _4a , R _4b , R _4c , R _4d , R _4e , R _4f and R _4g are each independently SO ₂ R _4o (R _4o is OH, halogen atom, ONa, OK or OR _4o1 (R _4o1 is a linear or branched alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted phenyl group)), a hydrogen atom, a halogen atom, or an alkyl group having 1 to 20 carbon atoms , An alkoxy group having 1 to 20 carbon atoms, OH group, NH ₂ group, NO ₂ group, COOR _4p (R _4p represents any one of H atom, Na atom and K atom), acetamide group, OPh group, NHPh group CF ₃ group, C ₂ F ₅ group or C ₃ F ₇ group (Ph represents a phenyl group), and at least one of these groups is SO ₂ R _4o .)

Wherein R _4h , R _4i , R _4j , R _4k , R _4l , R _4m and R _4n are each independently SO ₂ R _4o (R _4o is OH, halogen atom, ONa, OK or OR _4o1 (R _4o1 is a linear or branched alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted phenyl group)), a hydrogen atom, a halogen atom, or an alkyl group having 1 to 20 carbon atoms , An alkoxy group having 1 to 20 carbon atoms, OH group, NH ₂ group, NO ₂ group, COOR _4p (R _4p represents any one of H atom, Na atom and K atom), acetamide group, OPh group, NHPh group CF ₃ group, C ₂ F ₅ group or C ₃ F ₇ group (Ph represents a phenyl group), and at least one of these groups is SO ₂ R _4o .)
By using the compound represented by the chemical formula (28A) or (28B), a polyhydroxyalkanoate containing at least one unit represented by the chemical formula (4A) or (4B) in the molecule can be obtained.

(Wherein R _4a , R _4b , R _4c , R _4d , R _4e , R _4f , R _4g , and R _4o , R _4o1, and R _4p defined in formula (28A) have the above-mentioned meanings. N is an integer selected from 0 to 4. When n is an integer selected from 0, 2, 3, and 4, m is an integer selected from 0 to 8. n is 1 If it is, m is 0. when multiple units _{exist, R 4a, R 4b, R} 4c, R 4d, R 4e, R 4f, R 4g, R 4o, R 4o1, R 4p, m and n represents the above meaning independently for each unit.)

(In the formula, R _4h , R _4i , R _4j , R _4k , R _4l , R _4m , R _4n , and R _4o , R _4o1, and R _4p defined by the formula (28B) represent the above-mentioned meanings. N is an integer selected from 0 to 4. When n is an integer selected from 0, 2, 3, and 4, m is an integer selected from 0 to 8. n is 1 If it is, m is 0. when multiple units _{exist, R 4h, R 4i, R} 4j, R 4k, R 4l, R 4m, R 4n, R 4o, R 4o1, R 4p, m and n represents the above meaning independently for each unit.)
Examples of the compound represented by the chemical formula (28A) or (28B) include 1-naphthylamine-5-sulfonic acid, 1-naphthylamine-4-sulfonic acid, 1-naphthylamine-8-sulfonic acid, 2-naphthylamine-5-sulfonic acid. 1-naphthylamine-6-sulfonic acid, 1-naphthylamine-7-sulfonic acid, 1-naphthylamine-2-ethoxy-6-sulfonic acid, 1-amino-2-naphthol-4-sulfonic acid, 6-amino-1 1-amino-8-naphthol-2,4-sulfonic acid monosodium salt, 1-amino-8-naphthol-3,6-sulfonic acid monosodium salt, sulfonic acid, or the like Examples include alkali metal salts and esterified products.

When A ₃ is a group having a heterocyclic structure containing any one or more of substituted or unsubstituted N, S, and O, any of a pyridine ring, a piperazine ring, a furan ring, a thiol ring, etc. as a heterocyclic ring Good. Examples of the compound include 2-aminopyridine-6-sulfonic acid, 2-aminopiperazine-6-sulfonic acid and the like, sulfonic acid, an alkali metal salt thereof, an esterified product, and the like.

In the case of the sulfonate ester, the group having an ester bond with the sulfonic acid includes, as described above, a substituted or unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, a substituted or unsubstituted heterocyclic ring. Examples thereof include a group having a structure. Furthermore, a linear or branched alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted phenyl group and the like are preferable. From the point of easiness of esterification, OCH ₃ , OC ₂ H ₅ , OC ₆ H ₅ , OC ₃ H ₇ , OC ₄ H ₉ , OCH (CH ₃ ) ₂ , OCH ₂ C (CH ₃ ) ₃ , OC (CH ₃ ) _{3 and the} like are more preferable.

(Method for producing polyhydroxyalkanoate represented by chemical formula (1))
The reaction of the polyhydroxyalkanoate containing a unit represented by the chemical formula (20) and the aminosulfonic acid compound represented by the chemical formula (21) in the present invention will be described in detail. The amount of the compound represented by the chemical formula (21) used in the present invention is 0.1 to 50.0 times mol, preferably 1.0 to 20.0 times mol, with respect to the unit represented by the chemical formula (20) used as the starting material. .

  As a method for producing an amide bond from a carboxylic acid and an amine of the present invention, there is a condensation reaction by heat dehydration. In particular, from the viewpoint of mild reaction conditions in which the ester bond of the polymer main chain is not cleaved, it is effective to activate the carboxylic acid moiety with an activator to produce an active acyl intermediate and then react with the amine. It is. Examples of the active acyl intermediate include an acid halide, an acid anhydride, and an active ester. In particular, a method of forming an amide bond in the same reaction field using a condensing agent is preferable from the viewpoint of simplifying the production process.

  If necessary, it can be isolated as an acid halide and then subjected to a condensation reaction with an amine.

  Examples of the condensing agent to be used include a phosphoric acid condensing agent used for polycondensation of aromatic polyamide, a carbodiimide condensing agent used for peptide synthesis, an acid chloride condensing agent, etc. It can be appropriately selected depending on the combination with the polyhydroxyalkanoate having a unit represented by the chemical formula (20).

Examples of the phosphoric acid-based condensing agent include a phosphite-based condensing agent, a phosphoric chloride-based condensing agent, a phosphoric anhydride-based condensing agent, a phosphoric ester-based condensing agent, and a phosphoric acid amide-based condensing agent.
In the reaction of the present invention, a condensing agent such as phosphite can be used. The phosphites used here include triphenyl phosphite, diphenyl phosphite, tri-o-tolyl phosphite, di-o-tolyl phosphite, tri-m-tolyl phosphite. , Di-m-tolyl phosphite, tri-p-tolyl phosphite, di-p-tolyl phosphite, di-o-chlorophenyl phosphite, tri-p-chlorophenyl phosphite, diphosphite -p-chlorophenyl, trimethyl phosphite, triethyl phosphite and the like. Of these, triphenyl phosphite is preferably used. In order to improve the solubility and reactivity of the polymer, a metal salt such as lithium chloride or calcium chloride may be added.

  Examples of the carbodiimide condensing agent include dicyclohexylcarbodiimide (DCC), N-ethyl-N′-3-dimethylaminopropylcarbodiimide (EDC = WSCI), diisopropylcarbodiimide (DIPC), and the like. DCC or WSCI, N-hydroxysuccinimide (HONSu), 1-hydroxybenzotriazole (HOBt), 3-hydroxy-4-oxo-3,4-dihydro-1,2,3-benzotriazine (HOObt), etc. And may be used in combination.

  The amount of the condensing agent used is in the range of 0.1 to 50 times mol, preferably 1 to 20 times mol for the unit represented by chemical formula (20).

  In the reaction of the present invention, a solvent can be used as necessary. Solvents used include hydrocarbons such as hexane, cyclohexane and heptane, ketones such as acetone and methyl ethyl ketone, ethers such as dimethyl ether, diethyl ether and tetrahydrofuran, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane and the like. Halogenated hydrocarbons, aromatic hydrocarbons such as benzene and toluene, aprotic polar solvents such as N, N-dimethylformamide, dimethyl sulfoxide, dimethylacetamide and hexamethylphosphoramide, and pyridine derivatives such as pyridine and picoline , N-methylpyrrolidone and the like. Particularly preferably, pyridine, N-methylpyrrolidone or the like is used. The amount of the solvent used can be appropriately determined according to the starting material, the type of base, reaction conditions and the like. In the method of the present invention, the reaction temperature is not particularly limited, but is usually in the range of −20 ° C. to the boiling point of the solvent. However, it is desirable to carry out the reaction at an optimum temperature according to the condensing agent used.

  In the method of the present invention, the reaction time is usually in the range of 1 to 48 hours. In particular, 1 to 10 hours are preferable.

  In the present invention, recovery and purification of the desired polyhydroxyalkanoate from the reaction solution containing the polyhydroxyalkanoate having the unit represented by the chemical formula (1) thus produced can be performed by distillation, which is a conventional method. It is. Alternatively, water, alcohols such as methanol and ethanol, and solvents such as dimethyl ether, diethyl ether, tetrahydrofuran and other ethers are uniformly mixed in the reaction solution to precipitate the desired polyhydroxyalkanoate represented by chemical formula (1). This can be recovered. The polyhydroxyalkanoate having a unit represented by the chemical formula (1) obtained here can be isolated and purified if necessary. The isolation and purification method is not particularly limited, and a precipitation method using a solvent insoluble in the polyhydroxyalkanoate represented by the chemical formula (1), a column chromatography method, a dialysis method, and the like can be used.

As another production method of the present invention, when the R moiety in the chemical formula (1) is —A ₁ —SO ₃ H, a methyl esterifying agent is used after the condensation reaction with the amine to form the R moiety in the chemical formula (1). There is a method of carrying out methyl esterification in which -A ₁ -SO ₃ CH ₃ is used. As the methyl esterifying agent, those used for methyl esterification of fatty acids in gas chromatography analysis can be used. As the methyl esterification method, acid catalyst methods such as hydrochloric acid-methanol method, boron trifluoride-methanol method, sulfuric acid-methanol method, sodium methoxide method, tetramethylguanidine method, base catalyst method such as trimethylsilyldiazomethane method, etc. Is given. Among them, the trimethylsilyldiazomethane method is preferable because methylation can be performed under mild conditions.

  Solvents used in the reaction of the present invention are hydrocarbons such as hexane, cyclohexane and heptane, alcohols such as methanol and ethanol, halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, dichloroethane and trichloroethane, Examples thereof include aromatic hydrocarbons such as benzene and toluene. Particularly preferably, halogenated hydrocarbons are used. The amount of the solvent used can be appropriately determined according to the starting materials, reaction conditions and the like. In the method of the present invention, the reaction temperature is not particularly limited, but is usually in the range of −20 to 30 ° C. However, it is desirable to carry out the reaction at an optimum temperature according to the condensing agent and reagent to be used.

  A step of reacting a polyhydroxyalkanoate having a unit represented by the chemical formula (172) included in the chemical formula (1) of the present invention with a base using the polyhydroxyalkanoate having a unit represented by the chemical formula (168) as a starting material And the step of reacting the compound obtained in the above step with the compound represented by the chemical formula (171).

(Wherein, R ₁₇₂ is .R _172a representing the -A ₁₇₂ -SO ₂ R _172a OH, a halogen atom, ONa, .R _{172 b} and A ₁₇₂ is OK or OR _{172 b} are each independently a substituted or unsubstituted When a plurality of units are present, R ₁₇₂ , R _172a , R _172b and R ₁₇₂ , R _172a , R _172b and A ₁₇₂ represents the above meaning independently for each unit.)

(Wherein R ₁₇₁ represents -A ₁₇₁ -SO ₂ R _171a . R _171a is OH, a halogen atom, ONa, OK or OR _171b . R _171b and A ₁₇₁ are each independently substituted or substituted. Selected from a group having an unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure, and when there are a plurality of units, R ₁₇₁ , R _171a , R _171b and A ₁₇₁ have the above meanings independently for each unit.)
Examples of the compound represented by the chemical formula (171) include 2-acrylamido-2-methylpropanesulfonic acid, alkali metal salts thereof, and esterified products thereof.

  The reaction of the polyhydroxyalkanoate containing a unit represented by the chemical formula (168) and the compound represented by the chemical formula (171) in the present invention will be described in detail.

  The present invention can be achieved by Michael addition reaction of the compound represented by the chemical formula (171) to the α-methylene group adjacent to the carbonyl group in the polymer main chain. Specifically, under the reaction conditions of Michael addition, a polyhydroxyalkanoate containing a unit represented by the chemical formula (168) and a carbonyl group in the polymer main chain of the polyhydroxyalkanoate containing a unit represented by the chemical formula (168) This is achieved by reacting the adjacent α-methylene group with a base capable of anion formation, and subsequently reacting with the compound represented by the chemical formula (171). In the present invention, the amount of the compound represented by the chemical formula (171) to be used is 0.001 to 100-fold mol amount, preferably 0.01 to 10-fold mol amount based on the unit represented by the chemical formula (168).

  The solvent used in the reaction of the present invention is not particularly limited as long as it is an inert solvent for the reaction and can dissolve the starting material to some extent. For example, hexane, cyclohexane, heptane, ligroin or petroleum ether is used. Aliphatic hydrocarbons; aromatic hydrocarbons such as benzene, toluene or xylene; ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane or diethylene glycol dimethyl ether; or formamide, N, N- Amides such as dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylpyrrolidinone or hexamethylphosphorotriamide are preferred, and tetrahydrofuran is preferred.

  The reaction is carried out in the presence of a base. Bases used include alkyllithiums such as methyllithium and butyllithium; alkali metal disilazides such as lithium hexamethyldisilazide, sodium hexamethyldisilazide and potassium hexamethyldisilazide; lithium diisopropylamide Lithium amides such as lithium dicyclohexylamide, preferably lithium diisopropylamide. Moreover, the usage-amount of the base in this invention is 0.001-100 times mole amount with respect to the unit shown in Chemical formula (168), Preferably, it is 0.01-10 times mole amount.

  In the method of the present invention, the reaction temperature is usually −78 ° C. to 40 ° C., preferably −78 ° C. to 30 ° C.

  In the method of the present invention, the reaction time is usually in the range of 10 minutes to 24 hours. In particular, 10 minutes to 4 hours are preferable.

  On the other hand, in the polyhydroxyalkanoate having a unit represented by the chemical formula (5) of the present invention, the polyhydroxyalkanoate having a unit represented by the chemical formula (29) is a polyhydroxyalkanoate having a unit represented by the chemical formula (30) as a starting material. A method of oxidizing the side chain double bond portion of the polyhydroxyalkanoate using alkanoate, or a polyhydroxyalkanoate having a unit represented by the chemical formula (31), and converting the side chain ester portion to acid or alkali It can be produced by a method of hydrolyzing in the presence of water or a method of hydrocracking including catalytic reduction.

(In the formula, R ₂₉ is hydrogen or a group forming a salt. M is an integer selected from 3 to 8, and n is 0. When a plurality of units are present, R ₂₉ , m, and n represent the above meanings independently for each unit.)

(In the formula, m is an integer selected from 3 to 8, and n is 0. When a plurality of units are present, m and n represent the above meanings independently for each unit. )

(In the formula, R ₃₁ is a linear or branched alkyl group having 1 to 12 carbon atoms or an aralkyl group. M is an integer selected from 3 to 8, and n is 0. When there are a plurality of units, R ₃₁ , m, and n represent the above meanings independently for each unit.)
Further, in the polyhydroxyalkanoate having a unit represented by the chemical formula (5) of the present invention, the polyhydroxyalkanoate having a unit represented by the chemical formula (32) is a polyhydroxyalkanoate having a unit represented by the chemical formula (33) as a starting material. A method of oxidizing the side chain double bond moiety using alkanoate or a polyhydroxyalkanoate having a unit represented by the chemical formula (34), and hydrolyzing the side chain ester moiety in the presence of an acid or alkali. It can be produced by a method of decomposing or a method of hydrocracking including catalytic reduction.

(In the formula, R ₃₂ is hydrogen or a group forming a salt, m is an integer selected from 0 to 8, and n is an integer selected from 2 to 4. R ₃₂ , m, and n represent the above meanings independently for each unit.

(In the formula, m is an integer selected from 0 to 8, and n is an integer selected from 2 to 4. When there are a plurality of units, m and n are independent for each unit. Represents the above meaning.)

(In the formula, R ₃₄ is a linear or branched alkyl group having 1 to 12 carbon atoms or an aralkyl group. M is an integer selected from 0 to 8, and n is 2 to 4. (When there are a plurality of units, R ₃₄ , m and n represent the above meanings independently for each unit.)
(Method for producing polyhydroxyalkanoate represented by chemical formula (29) and chemical formula (32))
A method for producing a polyhydroxyalkanoate containing a unit represented by chemical formula (29) by oxidation reaction from a polyhydroxyalkanoate containing a unit represented by chemical formula (30) in the present invention, and a polyhydroxy containing a unit represented by chemical formula (33) A method for producing a polyhydroxyalkanoate containing a unit represented by the chemical formula (32) from an alkanoate by an oxidation reaction will be described in detail.

  As a method for obtaining a carboxylic acid by oxidative cleavage of the above carbon-carbon double bond with an oxidizing agent, for example, a method using permanganate (J. Chem. Soc., Perkin. Trans. 1, 806 (1973)), a method using dichromate (Org. Synth., 4, 698 (1963)), a method using periodate (J. Org. Chem., 46, 19 (1981) ) A method using nitric acid (Japanese Patent Application Laid-Open No. 59-190945), a method using ozone (J. Am. Chem. Soc., 81, 4273 (1959)) and the like are known, and Macromolecular Chemistry, 4 , 289-293 (2001), the reaction was carried out under acidic conditions using potassium permanganate with the carbon-carbon double bond at the end of the side chain of the polyhydroxyalkanoate produced by the microorganism as the oxidizing agent. How to get it has been reported. A similar method can be used in the present invention.

  As the permanganate used as the oxidizing agent, potassium permanganate is common. Since the oxidative cleavage reaction is a stoichiometric reaction, the amount of permanganate is usually 1 mole equivalent or more, preferably 2 moles per 1 mole of the unit represented by the chemical formula (30) or the chemical formula (33). ~ 10 molar equivalents should be used.

  In order to bring the reaction system to acidic conditions, various inorganic acids and organic acids such as sulfuric acid, hydrochloric acid, acetic acid and nitric acid are usually used. However, when an acid such as sulfuric acid, nitric acid or hydrochloric acid is used, the ester bond in the main chain is cleaved, which may cause a decrease in molecular weight. Therefore, it is preferable to use acetic acid. The amount of the acid used is usually 0.2 to 2000 molar equivalents, preferably 0.4 to 1000 molar equivalents per 1 mol of the unit represented by the chemical formula (30) or (33). If it is 0.2 molar equivalent or more, it becomes a preferable yield, and if it is 2000 molar equivalent or less, it is possible to reduce the by-product of the decomposition product due to the acid. In addition, crown-ether can be used for the purpose of promoting the reaction. In this case, the crown-ether and permanganate form a complex, and the effect of increasing the reaction activity is obtained. As the crown-ether, dibenzo-18-crown-6-ether, dicyclo-18-crown-6-ether, or 18-crown-6-ether is generally used. The amount of crown-ether used is usually 0.005 to 2.0 molar equivalents, preferably 0.01 to 1.5 molar equivalents per mole of permanganate.

  In addition, the solvent in the oxidation reaction of the present invention is not particularly limited as long as it is an inert solvent. For example, water, acetone; ethers such as tetrahydrofuran and dioxane; aromatic hydrocarbons such as benzene; hexane And aliphatic hydrocarbons such as heptane; halogenated hydrocarbons such as methyl chloride, dichloromethane, and chloroform. Among these solvents, halogenated hydrocarbons such as methyl chloride, dichloromethane, chloroform, and acetone are preferable in consideration of the solubility of polyhydroxyalkanoate.

  In the oxidation reaction of the present invention, the polyhydroxyalkanoate, permanganate and acid containing a unit represented by the chemical formula (30) or (33) may be charged together with a solvent from the beginning and reacted. You may make it react, adding continuously or intermittently in a system. Alternatively, only permanganate may be dissolved or suspended in a solvent first, and then polyhydroxyalkanoate and acid may be continuously or intermittently added to the system to react. Alternatively, only permanganate and an acid may be added to the system continuously or intermittently and reacted in advance. Furthermore, polyhydroxyalkanoate and acid may be charged first, and then permanganate may be added to the system continuously or intermittently to react, and the permanganate and acid are charged first. The polyhydroxyalkanoate may be continuously or intermittently added to the system and allowed to react, and the polyhydroxyalkanoate and permanganate are charged first, followed by the acid continuously or intermittently. The reaction may be carried out in addition to the system.

  The reaction temperature is usually −40 to 40 ° C., preferably −10 to 30 ° C. The reaction time depends on the stoichiometric ratio between the unit represented by the chemical formula (30) or the chemical formula (33) and the permanganate and the reaction temperature, but it is usually preferably 2 to 48 hours.

  The method for producing a polyhydroxyalkanoate containing a unit represented by the chemical formula (36) from a polyhydroxyalkanoate containing a unit represented by the chemical formula (35) shown in the present invention by an oxidation reaction applies the oxidation reaction described above. This is the novel production method of the present invention.

(In the formula, m is either 1 or 2, and n is 0.)

(In the formula, R ₃₆ is hydrogen or a group forming a salt, and m is 1 or 2 and n is 0.)
The method of hydrolyzing the side chain ester moiety from the polyhydroxyalkanoate containing the unit represented by the chemical formula (31) in the present invention in the presence of an acid or alkali, or the method of hydrocracking including catalytic reduction (29) A method for producing a polyhydroxyalkanoate containing a unit represented by formula (34), a method for hydrolyzing the side chain ester moiety from a polyhydroxyalkanoate containing a unit represented by chemical formula (34) in the presence of an acid or an alkali, or catalytic reduction A method for producing a polyhydroxyalkanoate containing a unit represented by the chemical formula (32) by a hydrocracking method containing

  When using the method of hydrolysis in the presence of an acid or an alkali, hydrochloric acid, sulfuric acid, nitric acid in an aqueous solution as a solvent or in an aqueous organic solvent such as methanol, ethanol, tetrahydrofuran, dioxane, dimethylformamide, dimethylsulfoxide, etc. Or an aqueous solution of an inorganic acid such as phosphoric acid or an organic acid such as trifluoroacetic acid, trichloroacetic acid, p-toluenesulfonic acid, methanesulfonic acid, or an aqueous caustic alkali such as sodium hydroxide or potassium hydroxide, It can be carried out using an aqueous solution of an alkali carbonate such as sodium carbonate or potassium carbonate, or an alcohol solution of a metal alkoxide such as sodium methoxide or sodium ethoxide. The reaction temperature is usually 0 to 40 ° C, preferably 0 to 30 ° C. The reaction time is usually 0.5 to 48 hours. However, when hydrolyzed with an acid or alkali, the ester bond of the main chain may be cleaved in any case, and a decrease in molecular weight may be observed.

  When using the method of obtaining carboxylic acid using the method of hydrocracking including catalytic reduction, it is performed as follows. That is, in an appropriate solvent, catalytic reduction is carried out by allowing hydrogen to act at normal pressure or under pressure in the presence of a reduction catalyst at a temperature in the range of -20 ° C to the boiling point of the solvent used, preferably 0 to 50 ° C. Do it. Examples of the solvent used include water, methanol, ethanol, propanol, hexafluoroisopropanol, ethyl acetate, diethyl ether, tetrahydrofuran, dioxane, benzene, toluene, dimethylformamide, pyridine, and N-methylpyrrolidone. Moreover, it can also be used as said mixed solvent. As the reduction catalyst, a catalyst such as palladium, platinum, rhodium or the like supported on a carrier or Raney nickel is used. The reaction time is usually preferably 0.5 to 72 hours. The reaction solution containing the polyhydroxyalkanoate having the unit represented by the chemical formula (29) or the chemical formula (32) thus produced is removed as a crude polymer by removing the catalyst by filtration and removing the solvent by distillation or the like. To be recovered. The polyhydroxyalkanoate having a unit represented by the chemical formula (29) or (32) obtained here can be isolated and purified if necessary. This isolation and purification method is not particularly limited, and a method of reprecipitation using a solvent insoluble in polyhydroxyalkanoate having a unit represented by chemical formula (29) or (32), a method by column chromatography, dialysis The method etc. can be used. However, even when catalytic reduction is used, the ester bond of the main chain is also cleaved, and a decrease in molecular weight may be observed.

  In the polyhydroxyalkanoate having a unit represented by the chemical formula (5) of the present invention, the polyhydroxyalkanoate having a unit represented by the chemical formula (37) is a polyhydroxyalkanoate having a unit represented by the chemical formula (38) as a starting material. It can be produced by esterification using an alkanoate and an esterifying agent.

(In the formula, R ₃₇ is a linear or branched alkyl group having 1 to 12 carbon atoms, an aralkyl group, or a substituent having a saccharide. When n is 0, m is selected from 2 to 8. When n is an integer selected from 2 to 4, m is an integer selected from 0 to 8. When a plurality of units are present, R ₃₇ , m and n are The above meaning is expressed independently for each unit.)

(In the formula, R ₃₈ is hydrogen or a group that forms a salt. When n is 0, m is an integer selected from 2 to 8. Also, n is selected from 2 to 4. When it is an integer, m is an integer selected from 0 to 8. When there are a plurality of units, R ₃₈ , m, and n independently represent the above meaning for each unit.)
As the esterifying agent used, diazomethane and DMF dimethylacetals can be used. For example, polyhydroxyalkanoate having a unit represented by the chemical formula (38) is trimethylsilyldiazomethane, DMF dimethyl acetal, DMF diethyl acetal, DMF dipropyl acetal, DMF diisopropyl acetal, DMF-n-butyl acetal, DMF-tert-butyl. Reacts easily with acetal or DMF dineopentyl acetal to give the corresponding ester. Alcohols such as methanol, ethanol, propanol, isopropyl alcohol, butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, pentyl alcohol, neopentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol , Reaction with saccharides for introducing a sugar structure such as lauryl alcohol, such as D-glucose, D-fructose, and other saccharides, by a method using an acid catalyst or a condensing agent such as DCC To obtain an esterified polyhydroxyalkanoate.

  A polyhydroxyalkanoate having a unit represented by the chemical formula (170) is prepared by reacting with a base using a polyhydroxyalkanoate having a unit represented by the chemical formula (168) as a starting material, and the compound obtained in the above step. It can be produced through a step of reacting with a compound represented by the chemical formula (169).

(In the formula, m is an integer selected from 0 to 8. R ₁₇₀ is a linear or branched alkyl group having 1 to 12 carbon atoms or an aralkyl group. When there are a plurality of units. , R ₁₇₀ and m represent the above meanings independently for each unit.)

(In the formula, m is an integer selected from 0 to 8. X is a halogen atom. R ₁₆₉ is a linear or branched alkyl group having 1 to 12 carbon atoms or an aralkyl group. .)
Compounds represented by the chemical formula (169) include methyl chloroformate, ethyl chloroformate, propyl chloroformate, isopropyl chloroformate, butyl chloroformate, cyclohexyl chloroformate, benzyl chloroformate, methyl bromate, ethyl bromate, and propyl bromate. , Bromobromoformate, butyl bromoformate, cyclohexyl bromate, benzyl bromoformate, methyl chloroacetate, ethyl chloroacetate, propyl chloroacetate, isopropyl chloroacetate, butyl chloroacetate, cyclohexyl chloroacetate, benzyl chloroacetate, methyl bromoacetate Ethyl acetate, propyl bromoacetate, isopropyl bromoacetate, butyl bromoacetate, cyclohexyl bromoacetate, benzyl bromoacetate, methyl 3-chloropropionate, ethyl 3-chloropropionate Propyl 3-chloropropionate, isopropyl 3-chloropropionate, butyl 3-chloropropionate, cyclohexyl 3-chloropropionate, benzyl 3-chloropropionate, methyl 3-bromopropionate, ethyl 3-bromopropionate, Propyl 3-bromopropionate, isopropyl 3-bromopropionate, butyl 3-bromopropionate, cyclohexyl 3-bromopropionate, benzyl 3-bromopropionate, methyl 4-chlorobutyrate, ethyl 4-chlorobutyrate, 4-chloro Propyl butyrate, isopropyl 4-chlorobutyrate, 4-butyl chlorobutyrate, cyclohexyl 4-chlorobutyrate, benzyl 4-chlorobutyrate, methyl 4-bromobutyrate, ethyl 4-bromobutyrate, propyl 4-bromobutyrate, isopropyl 4-bromobutyrate 4-Butyl butyrate 4-bromobutyrate Cyclohexyl acid, benzyl 4-bromobutyrate, methyl 5-chlorovalerate, ethyl 5-chlorovalerate, propyl 5-chlorovalerate, isopropyl 5-chlorovalerate, butyl 5-chlorovalerate, cyclohexyl 5-chlorovalerate Benzyl 5-chlorovalerate, methyl 5-bromovalerate, ethyl 5-bromovalerate, propyl 5-bromovalerate, isopropyl 5-bromovalerate, butyl 5-bromovalerate, cyclohexyl 5-bromovalerate, Benzyl 5-bromovalerate, methyl 6-chlorohexanoate, ethyl 6-chlorohexanoate, propyl 6-chlorohexanoate, isopropyl 6-chlorohexanoate, butyl 6-chlorohexanoate, cyclohexyl 6-chlorohexanoate, 6 -Benzylchlorohexanoate, methyl 6-bromohexanoate, ethyl 6-bromohexanoate, 6-bromohexa Propylate, isopropyl 6-bromohexanoate, butyl 6-bromohexanoate, cyclohexyl 6-bromohexanoate, benzyl 6-bromohexanoate, methyl 7-chloroheptanoate, ethyl 7-chloroheptanoate, 7-chloroheptane Propyl acid, isopropyl 7-chloroheptanoate, butyl 7-chloroheptanoate, cyclohexyl 7-chloroheptanoate, benzyl 7-chloroheptanoate, methyl 7-bromoheptanoate, ethyl 7-bromoheptanoate, 7-bromoheptanoic acid Propyl, isopropyl 7-bromoheptanoate, butyl 7-bromoheptanoate, cyclohexyl 7-bromoheptanoate, benzyl 7-bromooctanoate, methyl 8-chlorooctanoate, ethyl 8-chlorooctanoate, propyl 8-chlorooctanoate , 8-chlorooctanoic acid isopropyl, 8-chloro Butyl octanoate, cyclohexyl 8-chlorooctanoate, benzyl 8-chlorooctanoate, methyl 8-bromooctanoate, ethyl 8-bromooctanoate, propyl 8-bromooctanoate, isopropyl 8-bromooctanoate, 8-bromooctane Acid butyl, cyclohexyl 8-bromooctanoate, benzyl 8-bromooctanoate, methyl 9-chlorononanoate, ethyl 9-chlorononanoate, propyl 9-chlorononanoate, isopropyl 9-chlorononanoate, butyl 9-chlorononanoate, 9-chlorononane Cyclohexyl acid, benzyl 9-chlorononanoate, methyl 9-bromononanoate, ethyl 9-bromononanoate, propyl 9-bromononanoate, isopropyl 9-bromononanoate, butyl 9-bromononanoate, cyclohexyl 9-bromononanoate, benzyl 9-bromononanoate And the like.

  The reaction between the polyhydroxyalkanoate containing a unit represented by the chemical formula (168) and the compound represented by the chemical formula (169) in the present invention will be described in detail.

  The present invention is achieved by subjecting an α-methylene group adjacent to a carbonyl group in the polymer main chain to an addition reaction with a compound represented by the chemical formula (169). Specifically, under the conditions of the addition reaction, a polyhydroxyalkanoate containing a unit represented by the chemical formula (168) and a polyhydroxyalkanoate containing a unit represented by the chemical formula (168) are adjacent to the carbonyl group in the polymer main chain. This is achieved by reacting a base capable of forming an anion with an α-methylene group in the formula, followed by reacting with a compound represented by the chemical formula (169). In the present invention, the amount of the compound represented by the chemical formula (169) to be used is 0.001 to 100-fold molar amount, preferably 0.01 to 10-fold molar amount relative to the unit represented by the chemical formula (168).

  The solvent used in the reaction of the present invention is not particularly limited as long as it is an inert solvent for the reaction and can dissolve the starting material to some extent. For example, hexane, cyclohexane, heptane, ligroin or petroleum ether is used. Aliphatic hydrocarbons; aromatic hydrocarbons such as benzene, toluene or xylene; ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane or diethylene glycol dimethyl ether; or formamide, N, N- Amides such as dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylpyrrolidinone or hexamethylphosphorotriamide are preferred, and tetrahydrofuran is preferred.

  The reaction is carried out in the presence of a base. Bases used include alkyllithiums such as methyllithium and butyllithium; alkali metal disilazides such as lithium hexamethyldisilazide, sodium hexamethyldisilazide and potassium hexamethyldisilazide; lithium diisopropylamide Lithium amides such as lithium dicyclohexylamide, preferably lithium diisopropylamide. Moreover, the usage-amount of the base in this invention is 0.001-100 times mole amount with respect to the unit shown in Chemical formula (168), Preferably, it is 0.01-10 times mole amount.

  In the method of the present invention, the reaction temperature is usually −78 ° C. to 40 ° C., preferably −78 ° C. to 30 ° C.

  In the method of the present invention, the reaction time is usually in the range of 10 minutes to 24 hours. In particular, 10 minutes to 4 hours are preferable.

  In the method of the present invention, among the chemical formula (172), the compound of the chemical formula (176) included in the chemical formula (5) includes the novel compound of the present invention and a method for producing the novel compound. Chemical formula (177) is the novel production method of the present invention.

(In the formula, m is an integer selected from 2 to 8. R ₁₇₆ is a linear or branched alkyl group having 1 to 12 carbon atoms or an aralkyl group. When there are a plurality of units. , R ₁₇₆ and m represent the above meanings independently for each unit.)

(In the formula, m is an integer selected from 0 to 1. R ₁₇₇ is a linear or branched alkyl group having 1 to 12 carbon atoms or an aralkyl group. When there are a plurality of units. , R ₁₇₇ and m have the above meanings independently for each unit.)

(About the manufacturing method of the polyhydroxyalkanoate which has a unit shown by Chemical formula (6))
(A) Production method for obtaining a polyhydroxyalkanoate having a unit represented by the chemical formula (6) from a molecular cyclic diester In the polyhydroxyalkanoate having a unit represented by the chemical formula (6) of the present invention, The polyhydroxyalkanoate having the unit shown can be produced by polymerizing the compound represented by the chemical formula (8) or the compound represented by the chemical formula (10) in the presence of a catalyst.

(In the formula, m is an integer selected from 2 to 8, and n is 0. When a plurality of units are present, m and n represent the above meanings independently for each unit. )

(R ₈ is a linear or branched alkylene group having 1 to 11 carbon atoms, an alkyleneoxyalkylene group (each alkylene group is independently an alkylene group having 1 to 2 carbon atoms), 11 is a linear or branched alkenyl group, or an alkylidene group having 1 to 5 carbon atoms which may be substituted with aryl, and m is an integer selected from 2 to 8.)

(m is an integer selected from 2 to 8.)
The compound represented by the chemical formula (8) is a novel compound in the present invention. A method for synthesizing compound (10), which is one of the compounds included in novel compound (8) of the present invention, will be described.

(A) About the manufacturing method of a novel molecular cyclic diester The compound shown by Chemical formula (40) of m = 2 which is one of the novel compounds (10),

It can be obtained by dehydration condensation of 2-hydroxy-5-hexenoic acid represented by the chemical formula (41).

  For example, using a reactor equipped with Dean-Starktrap, azeotropic dehydration of compound (41) and a catalyst that undergoes dehydration condensation such as p-toluenesulfonic acid is carried out for 24 hours or more in a nitrogen atmosphere in toluene. The compound represented by the chemical formula (40) can be obtained by appropriately removing water accumulated in Dean-Starktrap.

  By using the compound represented by the chemical formula (42) by the same synthesis method as described above, it is possible to synthesize the compound of m = 3 to 8 represented by the chemical formula (10) corresponding thereto.

  The molecular cyclic diester represented by the novel compound (8) produced as described above can be used to proceed to a process for producing a polyester containing a unit represented by the chemical formula (39).

(A) Polyester Production Method Using Molecular Cyclic Diester In the production of a polyester containing a unit represented by the chemical formula (39) using the molecular cyclic diester represented by the novel compound (8) of the present invention, There is no particular limitation, and for example, a solution polymerization method, a slurry polymerization method, a bulk polymerization method and the like can be adopted. Moreover, when using a polymerization solvent, the solvent is not specifically limited, For example, inert solvents, such as C5-C18 aliphatic hydrocarbon, cyclic hydrocarbon, C6-C20 aromatic hydrocarbon, Tetrahydrofuran, chloroform, orthodichlorobenzene, dioxane and the like can be used.

  In the present invention, a known ring-opening polymerization catalyst can be used as the catalyst used for the polymerization. Examples include tin dichloride, tin tetrachloride, stannous fluoride, stannous acetate, stannous stearate, stannous octoate, stannous oxide, stannic oxide, and other tin salts. . Also, triethoxyaluminum, tri-n-propoxy-aluminum, tri-iso-propoxyaluminum, tri-n-butoxyaluminum, tri-iso-butoxyaluminum, aluminum chloride, di-iso-propylzinc, dimethylzinc, diethyl Zinc, zinc chloride, tetra-n-propoxy titanium, tetra-n-butoxy titanium, tetra-n-butoxy titanium, tetra-t-butoxy titanium, antimony trifluoride, lead oxide, lead stearate, titanium tetrachloride, three Examples thereof include boron fluoride, boron trifluoride ether complex, triethylamine, and tributylamine. The amount of these catalysts used is in the range of 0.0001 to 10% by weight, more preferably in the range of 0.001 to 5% by weight, based on the total amount of the monomer compounds.

  In the present invention, a known polymerization initiator can be used as a polymerization initiator in the ring-opening polymerization. Specifically, the aliphatic alcohol may be mono-, di- or polyhydric alcohol, and may be saturated or unsaturated. Specifically, methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, nonanol, decanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, monoalcohols such as p-tert-butylbenzyl alcohol, ethylene glycol, Dialcohols such as butanediol, hexanediol, nonanediol, and tetramethylene glycol, polyhydric alcohols such as glycerol, sorbitol, xylitol, ribitol, and erythritol, and methyl lactate and ethyl lactate can be used. These aliphatic alcohols are usually used in a proportion of 0.01 to 10% by weight based on the total amount of monomers, although there are some differences depending on the conditions such as the type of alcohol used.

  In the present invention, the ring-opening polymerization reaction temperature is 100 to 200 ° C., preferably 120 to 180 ° C. in consideration of the production rate of the polymer and the thermal decomposition temperature of the produced polymer.

  In the present invention, the ring-opening polymerization reaction may be carried out under an inert atmosphere such as nitrogen or argon, or under reduced pressure or under pressure. In this case, a catalyst and alcohol may be added successively.

(B) Production method for obtaining a polyhydroxyalkanoate having a unit represented by the chemical formula (6) from an intramolecular cyclized compound of ω-hydroxycarboxylic acid: a polyhydroxyalkanoate having a unit represented by the chemical formula (6) of the present invention The polyhydroxyalkanoate having a unit represented by the chemical formula (43) can be produced by polymerizing an intramolecular cyclized compound of an ω-hydroxycarboxylic acid represented by the chemical formula (12) in the presence of a catalyst.

(n is an integer selected from 2 to 4, and when n is an integer selected from 2 to 3, m is an integer selected from 0 to 8. When n is 4, m is 0, (It is an integer selected from 2 to 8. When there are a plurality of units, m and n represent the above meanings independently for each unit.)

(n is an integer selected from 2 to 4, and when n is an integer selected from 2 to 3, m is an integer selected from 0 to 8. When n is 4, m is 0, (It is an integer selected from 2 to 8.)
In the production of the polyester containing the unit represented by the chemical formula (39) using the chemical formula (12) which is the intramolecular cyclized compound of the ω-hydroxycarboxylic acid of the present invention, the polymerization method is not particularly limited. A polymerization method, a slurry polymerization method, a bulk polymerization method, or the like can be adopted. Moreover, when using a polymerization solvent, the solvent is not specifically limited, For example, inert solvents, such as C5-C18 aliphatic hydrocarbon, cyclic hydrocarbon, C6-C20 aromatic hydrocarbon, Tetrahydrofuran, chloroform, orthodichlorobenzene, dioxane and the like can be used.

  In the present invention, a known ring-opening polymerization catalyst can be used as the catalyst used for the polymerization. Examples include tin dichloride, tin tetrachloride, stannous fluoride, stannous acetate, stannous stearate, stannous octoate, stannous oxide, stannic oxide, and other tin salts. . Also, triethoxyaluminum, tri-n-propoxy-aluminum, tri-iso-propoxyaluminum, tri-n-butoxyaluminum, tri-iso-butoxyaluminum, aluminum chloride, di-iso-propylzinc, dimethylzinc, diethyl Zinc, zinc chloride, tetra-n-propoxy titanium, tetra-n-butoxy titanium, tetra-n-butoxy titanium, tetra-t-butoxy titanium, antimony trifluoride, lead oxide, lead stearate, titanium tetrachloride, three Examples thereof include boron fluoride, boron trifluoride ether complex, triethylamine, and tributylamine. Preferably, di-iso-propyl zinc, dimethyl zinc, diethyl zinc, boron trifluoride, boron trifluoride ether complex is used.

  The amount of these catalysts used is in the range of 0.0001 to 10% by weight, more preferably in the range of 0.001 to 5% by weight, based on the total amount of the monomer compounds.

  In the present invention, a known polymerization initiator can be used as a polymerization initiator in the ring-opening polymerization. Specifically, the aliphatic alcohol may be mono-, di- or polyhydric alcohol, and may be saturated or unsaturated. Specifically, methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, nonanol, decanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, monoalcohols such as p-tert-butylbenzyl alcohol, ethylene glycol, Dialcohols such as butanediol, hexanediol, nonanediol, and tetramethylene glycol, polyhydric alcohols such as glycerol, sorbitol, xylitol, ribitol, and erythritol, and methyl lactate and ethyl lactate can be used. These aliphatic alcohols are usually used in a proportion of 0.01 to 10% by weight based on the total amount of monomers, although there are some differences depending on the conditions such as the type of alcohol used.

  In the present invention, the ring-opening polymerization reaction temperature is in the range of 25 to 200 ° C, preferably 50 to 200 ° C, more preferably 100 to 180 ° C.

  In the present invention, the ring-opening polymerization reaction may be carried out under an inert atmosphere such as nitrogen or argon, or under reduced pressure or under pressure. In this case, a catalyst and alcohol may be added successively.

  On the other hand, in the polyhydroxyalkanoate having the unit represented by the chemical formula (5) of the present invention, the polyhydroxyalkanoate containing the unit represented by the chemical formula (44) is a cyclic compound which is a novel compound represented by the chemical formula (14) as a starting material. It can be produced by ring-opening polymerization using a diester compound.

(In the formula, R ₄₄ is a linear or branched alkyl group having 1 to 12 carbon atoms or an aralkyl group. N is an integer selected from 0, 2, 3, 4 and n is 0. In some cases, m is an integer selected from 2 to 8, and when n is an integer selected from 2 to 4, m is an integer selected from 2 to 8. When a plurality of units are present, R ₄₄ , m and n represent the above meanings independently for each unit.)

(Wherein R _14a is a linear or branched alkylene group having 1 to 11 carbon atoms, an alkyleneoxyalkylene group (each alkylene group is independently an alkylene group having 1 to 2 carbon atoms), carbon A linear or branched alkenyl group having 1 to 11 carbon atoms, or an alkylidene group having 1 to 5 carbon atoms which may be substituted with aryl, and R _14b is a linear or branched chain having 1 to 12 carbon atoms And n is an integer selected from 0, 2, 3, and 4, n is 0, m is an integer selected from 2 to 8, and n is 2 In the case of .about.4, m is an integer selected from 0 to 8.)
In this case, the polyhydroxyalkanoate unit to be synthesized has a structure consisting of a repeating unit represented by the chemical formula (15).

(15)
(Wherein R _15a is a linear or branched alkylene group having 1 to 11 carbon atoms, an alkyleneoxyalkylene group (each alkylene group is independently an alkylene group having 1 to 2 carbon atoms), carbon A linear or branched alkenyl group having 1 to 11 carbon atoms, or an alkylidene group having 1 to 5 carbon atoms which may be substituted with aryl, and R _15b is a linear or branched chain having 1 to 12 carbon atoms And n is an integer selected from 0, 2, 3, and 4, n is 0, m is an integer selected from 2 to 8, and n is 2 In the case of ˜4, m is an integer selected from 0 to 8. When there are a plurality of units, R _15b , m and n represent the above meanings independently for each unit.
The compound represented by the chemical formula (14) is a novel compound in the present invention. A method for synthesizing the compound (45) represented by the chemical formula (45), which is one of the compounds included in the novel compound (14) of the present invention, will be described.

(m is an integer selected from 2 to 8.)
(A) Method for producing novel molecular cyclic diester A method for synthesizing the compound represented by the chemical formula (45), which is one of the compounds included in the novel compound (14) of the present invention, will be described. For example, L-3- (2-benzyloxycarbonyl) ethyl-1,4-dioxane-2,5-dione represented by the chemical formula (46) where m = 2 is synthesized from L-glutamic acid as a starting material. be able to. Specifically, the carboxyl group at the γ-position of L-glutamic acid is esterified using benzyl alcohol as in the compound represented by chemical formula (47). Next, diazo hydrolysis is performed to convert an amino group into a hydroxyl group as in the compound represented by chemical formula (48). Next, a coupling reaction with bromoacetyl chloride is performed in the presence of a base such as triethylamine under ethers or aromatic hydrocarbons, preferably diethyl ether as a solvent, to obtain a compound represented by the chemical formula (49). . Furthermore, as a solvent, intramolecular cyclization with sodium hydrogen carbonate in an aprotic polar solvent such as dimethylformamide or N-methylpyrrolidone is performed, and L-3- (2-benzyloxycarbonyl represented by the chemical formula (46) is obtained. ) Ethyl-1,4-dioxane-2,5-dione is obtained.

  By using the compound represented by the chemical formula (50) by the same synthesis method as described above, it is possible to synthesize the compound of m = 3 to 8 represented by the chemical formula (45) corresponding thereto.

  The molecular cyclic diester represented by the novel compound (14) produced as described above can be used to proceed to a process for producing a polyester containing a unit represented by the chemical formula (44).

(A) Polyester Production Method Using Molecular Cyclic Diester In the production of a polyester containing a unit represented by the chemical formula (44) using the molecular cyclic diester represented by the novel compound (14) of the present invention, the polymerization method is as follows. There is no particular limitation, and for example, a solution polymerization method, a slurry polymerization method, a bulk polymerization method and the like can be adopted. Moreover, when using a polymerization solvent, the solvent is not specifically limited, For example, inert solvents, such as C5-C18 aliphatic hydrocarbon, cyclic hydrocarbon, C6-C20 aromatic hydrocarbon, Tetrahydrofuran, chloroform, orthodichlorobenzene, dioxane and the like can be used.

  In the present invention, a known ring-opening polymerization catalyst can be used as the catalyst used for the polymerization. Examples include tin dichloride, tin tetrachloride, stannous fluoride, stannous acetate, stannous stearate, stannous octoate, stannous oxide, stannic oxide, and other tin salts. . Also, triethoxyaluminum, tri-n-propoxy-aluminum, tri-iso-propoxyaluminum, tri-n-butoxyaluminum, tri-iso-butoxyaluminum, aluminum chloride, di-iso-propylzinc, dimethylzinc, diethyl Zinc, zinc chloride, tetra-n-propoxy titanium, tetra-n-butoxy titanium, tetra-n-butoxy titanium, tetra-t-butoxy titanium, antimony trifluoride, lead oxide, lead stearate, titanium tetrachloride, three Examples thereof include boron fluoride, boron trifluoride ether complex, triethylamine, and tributylamine. The amount of these catalysts used is in the range of 0.0001 to 10% by weight, more preferably in the range of 0.001 to 5% by weight, based on the total amount of the monomer compounds.

  In the present invention, a known polymerization initiator can be used as a polymerization initiator in the ring-opening polymerization. Specifically, the aliphatic alcohol may be mono-, di- or polyhydric alcohol, and may be saturated or unsaturated. Specifically, methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, nonanol, decanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, monoalcohols such as p-tert-butylbenzyl alcohol, ethylene glycol, Dialcohols such as butanediol, hexanediol, nonanediol, and tetramethylene glycol, polyhydric alcohols such as glycerol, sorbitol, xylitol, ribitol, and erythritol, and methyl lactate and ethyl lactate can be used. These aliphatic alcohols are usually used in a proportion of 0.01 to 10% by weight based on the total amount of monomers, although there are some differences depending on the conditions such as the type of alcohol used.

  In the present invention, the ring-opening polymerization reaction temperature is 100 to 200 ° C., preferably 120 to 180 ° C. in consideration of the production rate of the polymer and the thermal decomposition temperature of the produced polymer.

  In the present invention, the ring-opening polymerization reaction may be carried out under an inert atmosphere such as nitrogen or argon, or under reduced pressure or under pressure. In this case, a catalyst and alcohol may be added successively.

  The polyhydroxyalkanoate according to the present invention is mainly composed of the unit represented by the chemical formula (1), (5) or (6) described above, but it is used for changing various physical properties such as mechanical properties and decomposition properties. Further, a copolymer obtained by copolymerizing the second component or the like may be used. For example, a unit represented by the chemical formula (7) can be further contained in the molecule.

(R ₇ is a linear or branched alkylene group having 1 to 11 carbon atoms, an alkyleneoxyalkylene group (each alkylene group is independently an alkylene group having 1 to 2 carbon atoms) or aryl. (Alkylidene group having 1 to 5 carbon atoms which may be used. When there are a plurality of units, R ₇ represents the above meaning independently for each unit.)
As specific examples of the second component, α-hydroxycarboxylic acid cyclic diesters and lactones which are intramolecular ring-closing compounds of ω-hydroxycarboxylic acid can be copolymerized. Furthermore, specific examples of cyclic diesters of α-hydroxycarboxylic acid include glycolic acid, lactic acid, α-hydroxybutyric acid, α-hydroxyisobutyric acid, α-hydroxyvaleric acid, α-hydroxyisovaleric acid, α-hydroxy- Examples include intermolecular cyclic diesters such as α-methylbutyric acid, α-hydroxycaproic acid, α-hydroxyisocaproic acid, α-hydroxy-β-methylvaleric acid, α-hydroxyheptanoic acid, mandelic acid, β-phenyllactic acid, etc. . Moreover, what has asymmetric carbon may be any of L-form, D-form, racemic form, and meso form. In addition, the cyclic diester may be formed by different α-oxyacid molecules. Specifically, it is a cyclic diester between glycolic acid and lactic acid, such as 3-methyl-2,5-diketo-1,4-dioxane. Further, lactones which are intramolecular ring-closing compounds of ω-hydroxycarboxylic acid include β-propiolactone, β-butyrolactone, β-isovalerolactone, β-caprolactone, β-isocaprolactone, β-methyl-β- Intramolecular ring-closing compounds such as valerolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, ε-caprolactone, 11-oxydecanoic acid lactone, p-dioxanone and 1,5-dioxepan-2-one It is not limited to these.

  The number average molecular weight of the polyhydroxyalkanoate obtained by polymerization can be obtained with various molecular weights by changing conditions such as the type and amount of the polymerization catalyst, the polymerization temperature, and the polymerization time, but preferably 1000 to 100,000.

  The molecular weight of the polyhydroxyalkanoate of the present invention can be measured as a relative molecular weight or an absolute molecular weight. It can be easily measured by, for example, GPC (gel permeation chromatography). As a specific GPC measurement method, the polyhydroxyalkanoate is dissolved in a soluble solvent in advance, and measurement is performed with the same mobile phase. As the detector, a differential refraction detector (RI) or an ultraviolet detector (UV) can be used according to the polyhydroxyalkanoate to be measured. The molecular weight is determined as a relative comparison with a sample (polystyrene, polymethyl methacrylate, etc.). The solvent may be selected from those in which the polymer is soluble, such as dimethylformamide (DMF), dimethyl sulfoxide (DMSO), chloroform, tetrahydrofuran (THF), toluene, hexafluoroisopropanol (HFIP). In the case of a polar solvent, it can also be measured by adding a salt.

  In the present invention, the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured as described above is in the range of 1 to 10. Is preferably used.

  The reaction solvent, reaction temperature, reaction time, purification method, etc. in the chemical reaction of the present invention are not limited to the above methods.

  The present invention will be described in more detail with reference to the following examples. However, the method of the present invention is not limited to these examples.

(m is an integer selected from 2 to 8.)
(Example 1)
[Synthesis of 3,6-di (3-butenyl) -1,4-dioxane-2,5-dione represented by chemical formula (10) with m = 2 from 2-hydroxy-5-hexenoic acid]
In a 1 L flask equipped with a reflux condenser and a Dean-Stark trap, 3.0 g of 2-hydroxy-5-hexenoic acid, 400 ml of toluene and 30 mg of p-toluenesulfonic acid were added and refluxed in a nitrogen atmosphere. Water collected in the trap was removed from time to time. The mixture was refluxed for 72 hours and then cooled. After washing twice with 10 ml saturated aqueous sodium hydrogen carbonate solution, the obtained crude product was distilled under reduced pressure in the presence of zinc oxide to give the desired 3,6-di (3-butenyl) -1,4-dioxane-2. , 5-dione 1.06 g (41% yield) was obtained.

In order to specify the structure of the obtained compound, NMR analysis was performed under the following conditions.

<Measurement equipment> FT-NMR: Bruker DPX400
Resonance frequency: ¹ H = 400 MHz
<Measurement conditions> Measurement nuclide: ¹ H
Solvent used: DMSO-d ₆
Measurement temperature: room temperature

As a result, the obtained compound was confirmed to be the desired 3,6-di (3-butenyl) -1,4-dioxane-2,5-dione.

(Example 2)
Synthesis of 3,6-di (4-pentenyl) -1,4-dioxane-2,5-dione represented by chemical formula (10) and m = 3 from 2-hydroxy-6-heptenoic acid Performed in the same manner except that 2-hydroxy-6-heptenoic acid was used instead of hydroxy-5-hexenoic acid, 3,6-di (4-pentenyl) -1,4-dioxane-2,5-dione 1.10 g (42% yield) was obtained.

  In order to specify the structure of the obtained compound, NMR analysis was carried out under the same conditions as in Example 1. As a result, the desired 3,6-di (4-pentenyl) -1,4-dioxane-2,5- Confirmed to be dione.

Example 3
Synthesis of 3,6-di (5-hexenyl) -1,4-dioxane-2,5-dione represented by chemical formula (10) with m = 4 from 2-hydroxy-7-octenoic acid Performed in the same manner except that 2-hydroxy-7-octenoic acid was used instead of hydroxy-5-hexenoic acid, 3,6-di (5-hexenyl) -1,4-dioxane-2,5-dione 1.05 g (yield 40%) was obtained. In order to specify the structure of the obtained compound, NMR analysis was carried out under the same conditions as in Example 1. As a result, the intended 3,6-di (5-hexenyl) -1,4-dioxane-2,5- Confirmed to be dione.

Example 4
Synthesis of 3,6-di (6-heptenyl) -1,4-dioxane-2,5-dione represented by chemical formula (10) with m = 5 from 2-hydroxy-8-nonenoic acid The same procedure was followed except that 2-hydroxy-8-nonenoic acid was used instead of hydroxy-5-hexenoic acid, and 3,6-di (6-heptenyl) -1,4-dioxane-2,5- 1.07 g (yield 40%) of dione was obtained. In order to specify the structure of the obtained compound, NMR analysis was performed under the same conditions as in Example 1. As a result, the desired 3,6-di (6-heptenyl) -1,4-dioxane-2,5 was obtained. -I confirmed it was a dione.

(Example 5)
Synthesis of 3,6-di (2-propenyl) -1,4-dioxane-2,5-dione represented by chemical formula (10) and m = 1 from 2-hydroxy-4-pentenoic acid Performed in the same manner except that 2-hydroxy-4-pentenoic acid was used instead of hydroxy-5-hexenoic acid, 3,6-di (2-propenyl) -1,4-dioxane-2,5-dione 1.09 g (43% yield) was obtained. In order to specify the structure of the obtained compound, NMR analysis was carried out under the same conditions as in Example 1. As a result, the desired 3,6-di (2-propenyl) -1,4-dioxane-2,5- Confirmed to be dione.

Example 6
[Polyester synthesis using 3,6-di (3-butenyl) -1,4-dioxane-2,5-dione]
3,6-di (3-butenyl) -1,4-dioxane-2,5-dione 1.12 g (5.0 mmol), 2 mol of 0.01 mol / L tin octylate (tin 2-ethylhexanoate) in toluene, 0.01 mol / L p-tert-butylbenzyl alcohol in toluene 2 ml was charged into a polymerization ampule, dried under reduced pressure for 1 hour, purged with nitrogen, sealed under reduced pressure, heated to 150 ° C, Ring-opening polymerization was performed. The reaction was terminated after 1 hour and cooled. The obtained polymer was dissolved in chloroform and reprecipitated in 10 times the amount of methanol required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 0.95 g of polymer. In order to specify the structure of the obtained polymer, NMR analysis was performed under the following conditions.

<Measurement equipment> FT-NMR: Bruker DPX400
Resonance frequency: ¹ H = 400 MHz
<Measurement conditions> Measurement nuclide: ¹ H
Solvent: TMS / CDCl ₃
Measurement temperature: room temperature

As a result, it was confirmed to be a polyhydroxyalkanoate composed of a unit represented by the following chemical formula (51).

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 16500 and the weight average molecular weight Mw = 20000.

(Example 7)
[Polyester synthesis using 3,6-di (3-butenyl) -1,4-dioxane-2,5-dione and L-lactide]
3,6-di (3-butenyl) -1,4-dioxane-2,5-dione 0.11 g (0.5 mmol), L-lactide 0.65 g (4.5 mmol), 0.01 mol / L tin octylate (2- 2 ml of toluene solution of tin ethylhexanoate) and 2 ml of 0.01 mol / L toluene solution of p-tert-butylbenzyl alcohol were charged into the polymerization ampule, dried under reduced pressure for 1 hour and purged with nitrogen, and then under reduced pressure. Sealed and heated to 150 ° C. to perform ring-opening polymerization. The reaction was terminated after 1 hour and cooled. The obtained polymer was dissolved in chloroform and reprecipitated in 10 times the amount of methanol required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 0.63 g of polymer. As a result of conducting NMR analysis under the same conditions as in Example 6 in order to specify the structure of the obtained polymer, it was a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (52) as a monomer unit. It was confirmed. Moreover, it was confirmed that the ratio of the monomer unit was 9 mol% A unit and 91 mol% B unit.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 18200 and the weight average molecular weight Mw = 24000.

(Example 8)
[Polyester synthesis using 3,6-di (4-pentenyl) -1,4-dioxane-2,5-dione and L-lactide]
3,6-di (4-pentenyl) -1,4-dioxane-2,5-dione 0.13 g (0.5 mmol), L-lactide 0.65 g (4.5 mmol), 0.01 mol / L tin octylate (2- 2 ml of toluene solution of tin ethylhexanoate) and 2 ml of 0.01 mol / L toluene solution of p-tert-butylbenzyl alcohol were charged into the polymerization ampule, dried under reduced pressure for 1 hour and purged with nitrogen, and then under reduced pressure. Sealed and heated to 150 ° C. to perform ring-opening polymerization. The reaction was terminated after 1 hour and cooled. The obtained polymer was dissolved in chloroform and reprecipitated in 10 times the amount of methanol required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 0.66 g of polymer.

  As a result of conducting NMR analysis under the same conditions as in Example 6 to specify the structure of the obtained polymer, it is a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (53) as a monomer unit. It was confirmed. Moreover, it was confirmed that the ratio of the monomer unit was 9 mol% A unit and 91 mol% B unit.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 17800 and the weight average molecular weight Mw = 24200.

Example 9
[Polyester synthesis using 3,6-di (5-hexenyl) -1,4-dioxane-2,5-dione and L-lactide]
3,6-di (5-hexenyl) -1,4-dioxane-2,5-dione 0.14 g (0.5 mmol), L-lactide 0.65 g (4.5 mmol), 0.01 mol / L tin octylate (2- 2 ml of toluene solution of tin ethylhexanoate) and 2 ml of 0.01 mol / L toluene solution of p-tert-butylbenzyl alcohol were charged into the polymerization ampule, dried under reduced pressure for 1 hour and purged with nitrogen, and then under reduced pressure. Sealed and heated to 150 ° C. to perform ring-opening polymerization. The reaction was terminated after 1 hour and cooled. The obtained polymer was dissolved in chloroform and reprecipitated in 10 times the amount of methanol required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 0.62 g of polymer. As a result of performing NMR analysis under the same conditions as in Example 6 in order to specify the structure of the obtained polymer, it is a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (54) as a monomer unit. It was confirmed. Moreover, it was confirmed that the ratio of the monomer unit was 8 mol% of A unit and 92 mol% of B unit.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 16500 and the weight average molecular weight Mw = 21900.

(Example 10)
[Polyester synthesis using 3,6-di (6-heptenyl) -1,4-dioxane-2,5-dione and L-lactide]
3,6-di (6-heptenyl) -1,4-dioxane-2,5-dione 0.15 g (0.5 mmol), L-lactide 0.65 g (4.5 mmol), 0.01 mol / L tin octylate (2- 2 ml of toluene solution of tin ethylhexanoate) and 2 ml of 0.01 mol / L toluene solution of p-tert-butylbenzyl alcohol were charged into the polymerization ampule, dried under reduced pressure for 1 hour and purged with nitrogen, and then under reduced pressure. Sealed and heated to 150 ° C. to perform ring-opening polymerization. The reaction was terminated after 1 hour and cooled. The obtained polymer was dissolved in chloroform and reprecipitated in 10 times the amount of methanol required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 0.64 g of polymer. As a result of performing NMR analysis under the same conditions as in Example 6 in order to specify the structure of the obtained polymer, it is a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (55) as a monomer unit. It was confirmed. Moreover, it was confirmed that the ratio of the monomer unit was A unit 7 mol% and B unit 93 mol%.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 15700 and the weight average molecular weight Mw = 21800.

(Example 11)
[Polyester synthesis using 3,6-di (2-propenyl) -1,4-dioxane-2,5-dione and L-lactide]
3,6-di (2-propenyl) -1,4-dioxane-2,5-dione 0.10 g (0.5 mmol), L-lactide 0.65 g (4.5 mmol), 0.01 mol / L tin octylate (2- 2 ml of toluene solution of tin ethylhexanoate) and 2 ml of 0.01 mol / L toluene solution of p-tert-butylbenzyl alcohol were charged into the polymerization ampule, dried under reduced pressure for 1 hour and purged with nitrogen, and then under reduced pressure. Sealed and heated to 150 ° C. to perform ring-opening polymerization. The reaction was terminated after 1 hour and cooled. The obtained polymer was dissolved in chloroform and reprecipitated in 10 times the amount of methanol required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 0.65 g of polymer. As a result of performing NMR analysis under the same conditions as in Example 6 in order to specify the structure of the obtained polymer, it is a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (56) as a monomer unit. It was confirmed. Moreover, it was confirmed that the ratio of the monomer unit was 9 mol% A unit and 91 mol% B unit.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn was 17200, and the weight average molecular weight Mw was 22500.

(Example 12)
[Polyester synthesis using 3,6-di (2-propenyl) -1,4-dioxane-2,5-dione and L-lactide]
3,6-di (2-propenyl) -1,4-dioxane-2,5-dione 0.98 g (5.0 mmol), L-lactide 6.49 g (45.0 mmol), 0.01 mol / L tin octylate (2- 20 ml of toluene solution of tin ethylhexanoate) and 20 ml of 0.01 mol / L p-tert-butylbenzyl alcohol toluene solution were placed in a polymerization ampule, dried under reduced pressure for 2 hours, and purged with nitrogen, then under reduced pressure. Sealed and heated to 150 ° C. to perform ring-opening polymerization. The reaction was terminated after 1 hour and cooled. The obtained polymer was dissolved in chloroform and reprecipitated in 10 times the amount of methanol required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 6.55 g of polymer. As a result of conducting NMR analysis under the same conditions as in Example 6 to specify the structure of the obtained polymer, it is a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (57) as a monomer unit. It was confirmed. Moreover, it was confirmed that the ratio of the monomer unit was 9 mol% A unit and 91 mol% B unit.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 17400 and the weight average molecular weight Mw = 23300.

(Example 13)
[Polyester synthesis using 3,6-di (2-propenyl) -1,4-dioxane-2,5-dione and L-lactide]
3,6-di (2-propenyl) -1,4-dioxane-2,5-dione 0.049 g (0.25 mmol), L-lactide 0.68 g (4.75 mmol), 0.01 mol / L tin octylate (2- 2 ml of toluene solution of tin ethylhexanoate) and 2 ml of 0.01 mol / L toluene solution of p-tert-butylbenzyl alcohol were charged into the polymerization ampule, dried under reduced pressure for 1 hour and purged with nitrogen, and then under reduced pressure. Sealed and heated to 150 ° C. to perform ring-opening polymerization. The reaction was terminated after 1 hour and cooled. The obtained polymer was dissolved in chloroform and reprecipitated in 10 times the amount of methanol required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 0.64 g of polymer. As a result of conducting NMR analysis under the same conditions as in Example 6 in order to specify the structure of the obtained polymer, it is a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (58) as a monomer unit. It was confirmed. Moreover, it was confirmed that the ratio of the monomer unit was 4 mol% of A unit and 96 mol% of B unit.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 18000 and the weight average molecular weight Mw = 2500.

(Example 14)
[Polyester synthesis using 3,6-di (2-propenyl) -1,4-dioxane-2,5-dione and L-lactide]
3,6-di (2-propenyl) -1,4-dioxane-2,5-dione 0.15 g (0.75 mmol), L-lactide 0.61 g (4.25 mmol), 0.01 mol / L tin octylate (2- 2 ml of toluene solution of tin ethylhexanoate) and 2 ml of 0.01 mol / L toluene solution of p-tert-butylbenzyl alcohol were charged into the polymerization ampule, dried under reduced pressure for 1 hour and purged with nitrogen, and then under reduced pressure. Sealed and heated to 150 ° C. to perform ring-opening polymerization. The reaction was terminated after 1 hour and cooled. The obtained polymer was dissolved in chloroform and reprecipitated in 10 times the amount of methanol required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 0.64 g of polymer. As a result of conducting NMR analysis under the same conditions as in Example 6 in order to specify the structure of the obtained polymer, it is a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (59) as a monomer unit. It was confirmed. Moreover, it was confirmed that the ratio of the monomer unit was 14 mol% of A unit and 86 mol% of B unit.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn was 15800, and the weight average molecular weight Mw was 19900.

(Example 15)
[Polyester synthesis using 3,6-di (2-propenyl) -1,4-dioxane-2,5-dione and L-lactide]
3,6-di (2-propenyl) -1,4-dioxane-2,5-dione 0.20 g (1.0 mmol), L-lactide 0.58 g (4.0 mmol), 0.01 mol / L tin octylate (2- 2 ml of toluene solution of tin ethylhexanoate) and 2 ml of 0.01 mol / L toluene solution of p-tert-butylbenzyl alcohol were charged into the polymerization ampule, dried under reduced pressure for 1 hour and purged with nitrogen, and then under reduced pressure. Sealed and heated to 150 ° C. to perform ring-opening polymerization. The reaction was terminated after 1 hour and cooled. The obtained polymer was dissolved in chloroform and reprecipitated in 10 times the amount of methanol required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 0.62 g of polymer. As a result of conducting NMR analysis under the same conditions as in Example 6 in order to specify the structure of the obtained polymer, the polymer unit is a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (60). It was confirmed. Further, it was confirmed that the proportion of the monomer units was 18 mol% for A unit and 82 mol% for B unit.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 14700 and the weight average molecular weight Mw = 18600.

(Example 16)
[Polyester synthesis using 3,6-di (2-propenyl) -1,4-dioxane-2,5-dione and glycolide (1,4-dioxane-2,5-dione)]
3,6-di (2-propenyl) -1,4-dioxane-2,5-dione 0.10 g (0.5 mmol), glycolide 0.52 g (4.5 mmol), 0.01 mol / L tin octylate (2-ethylhexane) 2 ml of toluene solution of tin oxide), 2 ml of 0.01 mol / L toluene solution of p-tert-butylbenzyl alcohol were charged into a polymerization ampule, dried under reduced pressure for 1 hour, and purged with nitrogen, and then sealed under reduced pressure. And heated to 150 ° C. to perform ring-opening polymerization. The reaction was terminated after 1 hour and cooled. The obtained polymer was dissolved in chloroform and reprecipitated in 10 times the amount of methanol required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 0.53 g of polymer. As a result of conducting NMR analysis under the same conditions as in Example 6 to specify the structure of the obtained polymer, it is a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (61) as a monomer unit. It was confirmed. Moreover, it was confirmed that the ratio of the monomer unit was 10 mol% of A unit and 90 mol% of B unit.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 18500 and the weight average molecular weight Mw = 24200.

(Example 17)
[Polyester synthesis using 3,6-di (2-propenyl) -1,4-dioxane-2,5-dione and mandelide (3,6-diphenyl-1,4-dioxane-2,5-dione)]
3,6-di (2-propenyl) -1,4-dioxane-2,5-dione 0.10 g (0.5 mmol), mandelide 1.21 g (4.5 mmol), 0.01 mol / L tin octylate (2-ethylhexane) 2 ml of toluene solution of tin oxide), 2 ml of 0.01 mol / L toluene solution of p-tert-butylbenzyl alcohol were charged into a polymerization ampule, dried under reduced pressure for 1 hour, and purged with nitrogen, and then sealed under reduced pressure. And heated to 150 ° C. to perform ring-opening polymerization. The reaction was terminated after 1 hour and cooled. The obtained polymer was dissolved in chloroform and reprecipitated in 10 times the amount of methanol required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 1.05 g of polymer. As a result of performing NMR analysis under the same conditions as in Example 6 in order to specify the structure of the obtained polymer, it is a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (62) as a monomer unit. It was confirmed. Moreover, it was confirmed that the ratio of the monomer unit was 8 mol% of A unit and 92 mol% of B unit.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 17000 and the weight average molecular weight Mw = 31500.

(Example 18)
Oxidation reaction of polyhydroxyalkanoate composed of unit represented by chemical formula (51) synthesized in Example 6

  0.50 g of polyhydroxyalkanoate composed of the unit represented by the chemical formula (51) obtained in Example 6 was added to an eggplant flask, and dissolved by adding 30 ml of acetone. This was placed in an ice bath, and 5 ml of acetic acid and 3.54 g of 18-crown-6-ether were added and stirred. Next, 2.82 g of potassium permanganate was slowly added in an ice bath, stirred in the ice bath for 2 hours, and further stirred at room temperature for 18 hours. After completion of the reaction, 60 ml of ethyl acetate was added, and 45 ml of water was further added. Sodium bisulfite was then added until the peracid was removed. Thereafter, the liquidity was adjusted to pH = 1 with 1.0 mol / L (= 1.0 N) hydrochloric acid. The organic layer was extracted and washed 3 times with 1.0 mol / L hydrochloric acid. After recovering the organic layer, the solvent was distilled off to recover the crude polymer. Next, it was washed with 50 ml of water and 50 ml of methanol, and further washed with 50 ml of water three times, and then the polymer was recovered. Next, it was dissolved in THF and reprecipitated in 50 times the amount of THF required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 0.48 g of polymer. As a result of conducting NMR analysis under the same conditions as in Example 6 to identify the structure of the obtained polymer, it was confirmed that the monomer unit was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (63) It was done.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn was 12400, and the weight average molecular weight Mw was 16200.

(Example 19)
Oxidation reaction of polyhydroxyalkanoate composed of unit represented by chemical formula (52) synthesized in Example 7

  0.50 g of a polyhydroxyalkanoate copolymer (A: 9 mol%, B: 91 mol%) composed of the unit represented by the chemical formula (52) obtained in Example 7 was added to an eggplant flask, and dissolved by adding 30 ml of acetone. did. This was placed in an ice bath, and 5 ml of acetic acid and 0.47 g of 18-crown-6-ether were added and stirred. Next, 0.38 g of potassium permanganate was slowly added in an ice bath, stirred for 2 hours in an ice bath, and further stirred for 18 hours at room temperature. After completion of the reaction, 60 ml of ethyl acetate was added, and 45 ml of water was further added. Sodium bisulfite was then added until the peracid was removed. Thereafter, the liquidity was adjusted to pH = 1 with 1.0 mol / L (= 1.0 N) hydrochloric acid. The organic layer was extracted and washed 3 times with 1.0 mol / L hydrochloric acid. After recovering the organic layer, the solvent was distilled off to recover the crude polymer. Next, it was washed with 50 ml of water and 50 ml of methanol, and further washed with 50 ml of water three times, and then the polymer was recovered. Next, it was dissolved in 3 ml of THF and reprecipitated in 50 times the amount of THF required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 0.44 g of polymer. As a result of conducting NMR analysis under the same conditions as in Example 6 to identify the structure of the obtained polymer, it was confirmed that the monomer unit was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (64) It was done.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 13200 and the weight average molecular weight Mw = 18200.

  Furthermore, in order to calculate the unit of the obtained polyhydroxyalkanoate, it calculated by methyl-esterifying the carboxyl group in the side chain terminal of polyhydroxyalkanoate using trimethylsilyldiazomethane. 30 mg of the target polyhydroxyalkanoate was added to a 100 ml eggplant flask, and dissolved by adding 2.1 ml of chloroform and 0.7 ml of methanol. To this was added 0.5 ml of a 2 mol / L trimethylsilyldiazomethane-hexane solution, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the solvent was distilled off and the polymer was recovered. The polymer was recovered after washing with 50 ml of methanol. 31 mg of polyhydroxyalkanoate was obtained by drying under reduced pressure.

  NMR analysis was performed using the same method as in Example 6. As a result, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (64) was a copolymer of 8 mol% for the C unit and 92 mol% for the D unit.

(Example 20)
Oxidation reaction of polyhydroxyalkanoate composed of unit represented by chemical formula (53) synthesized in Example 8

  0.50 g of a polyhydroxyalkanoate copolymer (A: 9 mol%, B: 91 mol%) composed of the unit represented by the chemical formula (53) obtained in Example 8 was added to an eggplant flask and dissolved by adding 30 ml of acetone. did. This was placed in an ice bath, and 5 ml of acetic acid and 0.46 g of 18-crown-6-ether were added and stirred. Next, 0.37 g of potassium permanganate was slowly added in an ice bath, stirred for 2 hours in an ice bath, and further stirred for 18 hours at room temperature. After completion of the reaction, 60 ml of ethyl acetate was added, and 45 ml of water was further added. Sodium bisulfite was then added until the peracid was removed. Thereafter, the liquidity was adjusted to pH = 1 with 1.0 mol / L (= 1.0 N) hydrochloric acid. The organic layer was extracted and washed 3 times with 1.0 mol / L hydrochloric acid. After recovering the organic layer, the solvent was distilled off to recover the crude polymer. Next, it was washed with 50 ml of water and 50 ml of methanol, and further washed with 50 ml of water three times, and then the polymer was recovered. Next, it was dissolved in THF and reprecipitated in 50 times the amount of THF required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 0.42 g of polymer. As a result of conducting NMR analysis under the same conditions as in Example 6 to identify the structure of the obtained polymer, it was confirmed that the monomer unit was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (65) It was done.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 13000 and the weight average molecular weight Mw = 18100.

  Furthermore, in order to calculate the unit of the obtained polyhydroxyalkanoate, it calculated by methyl-esterifying the carboxyl group in the side chain terminal of polyhydroxyalkanoate using trimethylsilyldiazomethane. 30 mg of the target polyhydroxyalkanoate was added to a 100 ml eggplant flask, and dissolved by adding 2.1 ml of chloroform and 0.7 ml of methanol. To this was added 0.5 ml of a 2 mol / L trimethylsilyldiazomethane-hexane solution, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the solvent was distilled off and the polymer was recovered. The polymer was recovered after washing with 50 ml of methanol. 29 mg of polyhydroxyalkanoate was obtained by drying under reduced pressure.

  NMR analysis was performed using the same method as in Example 6. As a result, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (65) was a copolymer of 8 mol% for the C unit and 92 mol% for the D unit.

(Example 21)
Oxidation reaction of polyhydroxyalkanoate composed of unit represented by chemical formula (54) synthesized in Example 9

  0.50 g of a polyhydroxyalkanoate copolymer (A: 8 mol%, B: 92 mol%) composed of the unit represented by the chemical formula (54) obtained in Example 9 was added to an eggplant flask and dissolved by adding 30 ml of acetone. did. This was placed in an ice bath, and 5 ml of acetic acid and 0.40 g of 18-crown-6-ether were added and stirred. Next, 0.32 g of potassium permanganate was slowly added in an ice bath, stirred for 2 hours in an ice bath, and further stirred for 18 hours at room temperature. After completion of the reaction, 60 ml of ethyl acetate was added, and 45 ml of water was further added. Sodium bisulfite was then added until the peracid was removed. Thereafter, the liquidity was adjusted to pH = 1 with 1.0 mol / L (1.0 N) hydrochloric acid. The organic layer was extracted and washed 3 times with 1.0 mol / L hydrochloric acid. After recovering the organic layer, the solvent was distilled off to recover the crude polymer. Next, it was washed with 50 ml of water and 50 ml of methanol, and further washed with 50 ml of water three times, and then the polymer was recovered. Next, it was dissolved in THF and reprecipitated in 50 times the amount of THF required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 0.44 g of polymer. As a result of conducting NMR analysis under the same conditions as in Example 6 to identify the structure of the obtained polymer, it was confirmed that the monomer unit was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (66) It was done.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 11700 and the weight average molecular weight Mw = 16400.

  Furthermore, in order to calculate the unit of the obtained polyhydroxyalkanoate, it calculated by methyl-esterifying the carboxyl group in the side chain terminal of polyhydroxyalkanoate using trimethylsilyldiazomethane. 30 mg of the target polyhydroxyalkanoate was added to a 100 ml eggplant flask, and dissolved by adding 2.1 ml of chloroform and 0.7 ml of methanol. To this was added 0.5 ml of a 2 mol / L trimethylsilyldiazomethane-hexane solution, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the solvent was distilled off and the polymer was recovered. The polymer was recovered after washing with 50 ml of methanol. By drying under reduced pressure, 28 mg of polyhydroxyalkanoate was obtained.

  NMR analysis was performed using the same method as in Example 6. As a result, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (66) was a copolymer of 8 mol% for the C unit and 92 mol% for the D unit.

(Example 22)
Oxidation reaction of polyhydroxyalkanoate composed of unit represented by chemical formula (55) synthesized in Example 10

  0.50 g of a polyhydroxyalkanoate copolymer (A: 7 mol%, B: 93 mol%) composed of the unit represented by the chemical formula (55) obtained in Example 8 was added to an eggplant flask, and dissolved by adding 30 ml of acetone. did. This was placed in an ice bath, 5 ml of acetic acid and 0.35 g of 18-crown-6-ether were added and stirred. Next, 0.28 g of potassium permanganate was slowly added in an ice bath, stirred for 2 hours in an ice bath, and further stirred for 18 hours at room temperature. After completion of the reaction, 60 ml of ethyl acetate was added, and 45 ml of water was further added. Sodium bisulfite was then added until the peracid was removed. Thereafter, the liquidity was adjusted to pH = 1 with 1.0 mol / L (1.0 N) hydrochloric acid. The organic layer was extracted and washed 3 times with 1.0 mol / L hydrochloric acid. After recovering the organic layer, the solvent was distilled off to recover the crude polymer. Next, it was washed with 50 ml of water and 50 ml of methanol, and further washed with 50 ml of water three times, and then the polymer was recovered. Next, it was dissolved in THF and reprecipitated in 50 times the amount of THF required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 0.42 g of polymer. As a result of conducting NMR analysis under the same conditions as in Example 6 to identify the structure of the obtained polymer, it was confirmed that the monomer unit was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (67) It was done.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 11400 and the weight average molecular weight Mw = 16300.

  Furthermore, in order to calculate the unit of the obtained polyhydroxyalkanoate, it calculated by methyl-esterifying the carboxyl group in the side chain terminal of polyhydroxyalkanoate using trimethylsilyldiazomethane.

  30 mg of the target polyhydroxyalkanoate was added to a 100 ml eggplant flask, and dissolved by adding 2.1 ml of chloroform and 0.7 ml of methanol. To this was added 0.5 ml of a 2 mol / L trimethylsilyldiazomethane-hexane solution, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the solvent was distilled off and the polymer was recovered. The polymer was recovered after washing with 50 ml of methanol. By drying under reduced pressure, 30 mg of polyhydroxyalkanoate was obtained.

  NMR analysis was performed using the same method as in Example 6. As a result, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (67) was a copolymer of 7 mol% for the C unit and 93 mol% for the D unit.

(Example 23)
Oxidation reaction of polyhydroxyalkanoate composed of unit represented by chemical formula (56) synthesized in Example 11

  0.50 g of a polyhydroxyalkanoate copolymer (A: 9 mol%, B: 91 mol%) composed of the unit represented by the chemical formula (56) obtained in Example 11 was added to an eggplant flask, and dissolved by adding 30 ml of acetone. did. This was placed in an ice bath, and 5 ml of acetic acid and 0.48 g of 18-crown-6-ether were added and stirred. Next, 0.38 g of potassium permanganate was slowly added in an ice bath, stirred for 2 hours in an ice bath, and further stirred for 18 hours at room temperature. After completion of the reaction, 60 ml of ethyl acetate was added, and 45 ml of water was further added. Sodium bisulfite was then added until the peracid was removed. Thereafter, the liquidity was adjusted to pH = 1 with 1.0 mol / L (1.0 N) hydrochloric acid. The organic layer was extracted and washed 3 times with 1.0 mol / L hydrochloric acid. After recovering the organic layer, the solvent was distilled off to recover the crude polymer. Next, it was washed with 50 ml of water and 50 ml of methanol, and further washed with 50 ml of water three times, and then the polymer was recovered. Next, it was dissolved in THF and reprecipitated in 50 times the amount of THF required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 0.45 g of polymer. As a result of conducting NMR analysis under the same conditions as in Example 6 to identify the structure of the obtained polymer, it was confirmed that the monomer unit was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (68) It was done.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 12,800 and the weight average molecular weight Mw = 17700.

  Furthermore, in order to calculate the unit of the obtained polyhydroxyalkanoate, it calculated by methyl-esterifying the carboxyl group in the side chain terminal of polyhydroxyalkanoate using trimethylsilyldiazomethane. 30 mg of the target polyhydroxyalkanoate was added to a 100 ml eggplant flask, and dissolved by adding 2.1 ml of chloroform and 0.7 ml of methanol. To this was added 0.5 ml of a 2 mol / L trimethylsilyldiazomethane-hexane solution, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the solvent was distilled off and the polymer was recovered. The polymer was recovered after washing with 50 ml of methanol. 29 mg of polyhydroxyalkanoate was obtained by drying under reduced pressure.

  NMR analysis was performed using the same method as in Example 6. As a result, it was confirmed that the unit of polyhydroxyalkanoate represented by the chemical formula (68) was a copolymer of 8 mol% for the C unit and 92 mol% for the D unit.

(Example 24)
Oxidation reaction of polyhydroxyalkanoate composed of unit represented by chemical formula (57) synthesized in Example 12

  6.00 g of a polyhydroxyalkanoate copolymer (A: 9 mol%, B: 91 mol%) comprising the unit represented by the chemical formula (57) obtained in Example 12 was added to an eggplant flask and dissolved by adding 360 ml of acetone. did. This was placed in an ice bath, and 60 ml of acetic acid and 5.75 g of 18-crown-6-ether were added and stirred. Next, 4.59 g of potassium permanganate was slowly added in an ice bath, and the mixture was stirred in the ice bath for 2 hours and further stirred at room temperature for 18 hours. After completion of the reaction, 720 ml of ethyl acetate was added, and 540 ml of water was further added. Sodium bisulfite was then added until the peracid was removed. Thereafter, the liquidity was adjusted to pH = 1 with 1.0 mol / L (1.0 N) hydrochloric acid. The organic layer was extracted and washed 3 times with 1.0 mol / L hydrochloric acid. After recovering the organic layer, the solvent was distilled off to recover the crude polymer. Next, after washing with 600 ml of water and 600 ml of methanol, and further washing with 600 ml of water three times, the polymer was recovered. Next, it was dissolved in THF and reprecipitated in 50 times the amount of THF required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 5.30 g of polymer. As a result of conducting NMR analysis under the same conditions as in Example 6 to identify the structure of the obtained polymer, it was confirmed that the monomer unit was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (69) It was done.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 13200 and the weight average molecular weight Mw = 18300.

  Furthermore, in order to calculate the unit of the obtained polyhydroxyalkanoate, it calculated by methyl-esterifying the carboxyl group in the side chain terminal of polyhydroxyalkanoate using trimethylsilyldiazomethane. 30 mg of the target polyhydroxyalkanoate was added to a 100 ml eggplant flask, and dissolved by adding 2.1 ml of chloroform and 0.7 ml of methanol. To this was added 0.5 ml of a 2 mol / L trimethylsilyldiazomethane-hexane solution, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the solvent was distilled off and the polymer was recovered. The polymer was recovered after washing with 50 ml of methanol. By drying under reduced pressure, 28 mg of polyhydroxyalkanoate was obtained.

  NMR analysis was performed using the same method as in Example 6. As a result, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (69) was a copolymer of 8 mol% for the C unit and 92 mol% for the D unit.

(Example 25)
Oxidation reaction of polyhydroxyalkanoate composed of unit represented by chemical formula (58) synthesized in Example 13

  0.50 g of a polyhydroxyalkanoate copolymer (A: 4 mol%, B: 96 mol%) composed of the unit represented by the chemical formula (58) obtained in Example 13 was added to an eggplant flask and dissolved by adding 30 ml of acetone. did. This was placed in an ice bath, and 5 ml of acetic acid and 0.22 g of 18-crown-6-ether were added and stirred. Next, 0.17 g of potassium permanganate was slowly added in an ice bath, stirred for 2 hours in an ice bath, and further stirred for 18 hours at room temperature. After completion of the reaction, 60 ml of ethyl acetate was added, and 45 ml of water was further added. Sodium bisulfite was then added until the peracid was removed. Thereafter, the liquidity was adjusted to pH = 1 with 1.0 mol / L (1.0 N) hydrochloric acid. The organic layer was extracted and washed 3 times with 1.0 mol / L hydrochloric acid. After recovering the organic layer, the solvent was distilled off to recover the crude polymer. Next, it was washed with 50 ml of water and 50 ml of methanol, and further washed with 50 ml of water three times, and then the polymer was recovered. Next, it was dissolved in THF and reprecipitated in 50 times the amount of THF required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 0.45 g of polymer. As a result of conducting NMR analysis under the same conditions as in Example 6 to identify the structure of the obtained polymer, it was confirmed that the monomer unit was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (70) It was done.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn was 12800, and the weight average molecular weight Mw was 16500.

  Furthermore, in order to calculate the unit of the obtained polyhydroxyalkanoate, it calculated by methyl-esterifying the carboxyl group in the side chain terminal of polyhydroxyalkanoate using trimethylsilyldiazomethane. 30 mg of the target polyhydroxyalkanoate was added to a 100 ml eggplant flask, and dissolved by adding 2.1 ml of chloroform and 0.7 ml of methanol. To this was added 0.5 ml of a 2 mol / L trimethylsilyldiazomethane-hexane solution, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the solvent was distilled off and the polymer was recovered. The polymer was recovered after washing with 50 ml of methanol. 29 mg of polyhydroxyalkanoate was obtained by drying under reduced pressure.

  NMR analysis was performed using the same method as in Example 6. As a result, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (70) was a copolymer of 4 mol% for the C unit and 96 mol% for the D unit.

(Example 26)
Oxidation reaction of polyhydroxyalkanoate composed of unit represented by chemical formula (59) synthesized in Example 14

  0.50 g of a polyhydroxyalkanoate copolymer (A: 14 mol%, B: 86 mol%) composed of the unit represented by the chemical formula (59) obtained in Example 14 was added to an eggplant flask and dissolved by adding 30 ml of acetone. did. This was placed in an ice bath, and 5 ml of acetic acid and 0.73 g of 18-crown-6-ether were added and stirred. Next, 0.58 g of potassium permanganate was slowly added in an ice bath, stirred for 2 hours in an ice bath, and further stirred for 18 hours at room temperature. After completion of the reaction, 60 ml of ethyl acetate was added, and 45 ml of water was further added. Sodium bisulfite was then added until the peracid was removed. Thereafter, the liquidity was adjusted to pH = 1 with 1.0 mol / L (1.0 N) hydrochloric acid. The organic layer was extracted and washed 3 times with 1.0 mol / L hydrochloric acid. After recovering the organic layer, the solvent was distilled off to recover the crude polymer. Next, it was washed with 50 ml of water and 50 ml of methanol, and further washed with 50 ml of water three times, and then the polymer was recovered. Next, it was dissolved in THF and reprecipitated in 50 times the amount of THF required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 0.44 g of polymer. As a result of conducting NMR analysis under the same conditions as in Example 6 to identify the structure of the obtained polymer, it was confirmed that the monomer unit was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (71) It was done.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 10600 and the weight average molecular weight Mw = 13800.

  Furthermore, in order to calculate the unit of the obtained polyhydroxyalkanoate, it calculated by methyl-esterifying the carboxyl group in the side chain terminal of polyhydroxyalkanoate using trimethylsilyldiazomethane. 30 mg of the target polyhydroxyalkanoate was added to a 100 ml eggplant flask, and dissolved by adding 2.1 ml of chloroform and 0.7 ml of methanol. To this was added 0.5 ml of a 2 mol / L trimethylsilyldiazomethane-hexane solution, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the solvent was distilled off and the polymer was recovered. The polymer was recovered after washing with 50 ml of methanol. By drying under reduced pressure, 27 mg of polyhydroxyalkanoate was obtained.

  NMR analysis was performed using the same method as in Example 6. As a result, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (71) was a copolymer of 13 mol% for the C unit and 87 mol% for the D unit.

(Example 27)
Oxidation reaction of polyhydroxyalkanoate composed of unit represented by chemical formula (60) synthesized in Example 15

  0.50 g of a polyhydroxyalkanoate copolymer (A: 18 mol%, B: 82 mol%) consisting of the unit represented by the chemical formula (60) obtained in Example 15 was added to an eggplant flask, and dissolved by adding 30 ml of acetone. did. This was placed in an ice bath, and 5 ml of acetic acid and 0.93 g of 18-crown-6-ether were added and stirred. Next, 0.74 g of potassium permanganate was slowly added in an ice bath, stirred for 2 hours in an ice bath, and further stirred for 18 hours at room temperature. After completion of the reaction, 60 ml of ethyl acetate was added, and 45 ml of water was further added. Sodium bisulfite was then added until the peracid was removed. Thereafter, the liquidity was adjusted to pH = 1 with 1.0 mol / L (1.0 N) hydrochloric acid. The organic layer was extracted and washed 3 times with 1.0 mol / L hydrochloric acid. After recovering the organic layer, the solvent was distilled off to recover the crude polymer. Next, it was washed with 50 ml of water and 50 ml of methanol, and further washed with 50 ml of water three times, and then the polymer was recovered. Next, it was dissolved in THF and reprecipitated in 50 times the amount of THF required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 0.43 g of polymer. As a result of conducting NMR analysis under the same conditions as in Example 6 to identify the structure of the obtained polymer, it was confirmed that the monomer unit was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (72). It was done.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 10100 and the weight average molecular weight Mw = 13200.

  Furthermore, in order to calculate the unit of the obtained polyhydroxyalkanoate, it calculated by methyl-esterifying the carboxyl group in the side chain terminal of polyhydroxyalkanoate using trimethylsilyldiazomethane. 30 mg of the target polyhydroxyalkanoate was added to a 100 ml eggplant flask, and dissolved by adding 2.1 ml of chloroform and 0.7 ml of methanol. To this was added 0.5 ml of a 2 mol / L trimethylsilyldiazomethane-hexane solution, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the solvent was distilled off and the polymer was recovered. The polymer was recovered after washing with 50 ml of methanol. By drying under reduced pressure, 28 mg of polyhydroxyalkanoate was obtained.

  NMR analysis was performed using the same method as in Example 6. As a result, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (72) was a copolymer of 16 mol% for the C unit and 84 mol% for the D unit.

(Example 28)
Oxidation reaction of polyhydroxyalkanoate composed of unit represented by chemical formula (61) synthesized in Example 16

  0.50 g of a polyhydroxyalkanoate copolymer (A: 10 mol%, B: 90 mol%) composed of the unit represented by the chemical formula (61) obtained in Example 16 was added to an eggplant flask and dissolved by adding 30 ml of acetone. did. This was placed in an ice bath, and 5 ml of acetic acid and 0.64 g of 18-crown-6-ether were added and stirred. Next, 0.51 g of potassium permanganate was slowly added in an ice bath, stirred for 2 hours in an ice bath, and further stirred for 18 hours at room temperature. After completion of the reaction, 60 ml of ethyl acetate was added, and 45 ml of water was further added. Sodium bisulfite was then added until the peracid was removed. Thereafter, the liquidity was adjusted to pH = 1 with 1.0 mol / L (1.0 N) hydrochloric acid. The organic layer was extracted and washed 3 times with 1.0 mol / L hydrochloric acid. After recovering the organic layer, the solvent was distilled off to recover the crude polymer. Next, it was washed with 50 ml of water and 50 ml of methanol, and further washed with 50 ml of water three times, and then the polymer was recovered. Next, it was dissolved in THF and reprecipitated in 50 times the amount of THF required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 0.44 g of polymer. As a result of conducting NMR analysis under the same conditions as in Example 6 to identify the structure of the obtained polymer, it was confirmed that the monomer unit was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (73) It was done.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 13200 and the weight average molecular weight Mw = 17700.

  Furthermore, in order to calculate the unit of the obtained polyhydroxyalkanoate, it calculated by methyl-esterifying the carboxyl group in the side chain terminal of polyhydroxyalkanoate using trimethylsilyldiazomethane. 30 mg of the target polyhydroxyalkanoate was added to a 100 ml eggplant flask, and dissolved by adding 2.1 ml of chloroform and 0.7 ml of methanol. To this was added 0.5 ml of a 2 mol / L trimethylsilyldiazomethane-hexane solution, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the solvent was distilled off and the polymer was recovered. The polymer was recovered after washing with 50 ml of methanol. By drying under reduced pressure, 30 mg of polyhydroxyalkanoate was obtained.

  NMR analysis was performed using the same method as in Example 6. As a result, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (73) was a copolymer of 9 mol% for the C unit and 91 mol% for the D unit.

(Example 29)
Oxidation reaction of polyhydroxyalkanoate composed of unit represented by chemical formula (62) synthesized in Example 17

  0.50 g of a polyhydroxyalkanoate copolymer (A: 8 mol%, B: 92 mol%) comprising the unit represented by the chemical formula (62) obtained in Example 17 was added to an eggplant flask, and dissolved by adding 30 ml of acetone. did. This was placed in an ice bath, and 5 ml of acetic acid and 0.24 g of 18-crown-6-ether were added and stirred. Next, 0.19 g of potassium permanganate was slowly added in an ice bath, stirred for 2 hours in an ice bath, and further stirred for 18 hours at room temperature. After completion of the reaction, 60 ml of ethyl acetate was added, and 45 ml of water was further added. Sodium bisulfite was then added until the peracid was removed. Thereafter, the liquidity was adjusted to pH = 1 with 1.0 mol / L (1.0 N) hydrochloric acid. The organic layer was extracted and washed 3 times with 1.0 mol / L hydrochloric acid. After recovering the organic layer, the solvent was distilled off to recover the crude polymer. Next, it was washed with 50 ml of water and 50 ml of methanol, and further washed with 50 ml of water three times, and then the polymer was recovered. Next, it was dissolved in THF and reprecipitated in 50 times the amount of THF required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 0.44 g of polymer. As a result of conducting NMR analysis under the same conditions as in Example 6 in order to specify the structure of the obtained polymer, it was confirmed that the monomer unit was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (74). It was done.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 12,500 and the weight average molecular weight Mw = 24300.

  Furthermore, in order to calculate the unit of the obtained polyhydroxyalkanoate, it calculated by methyl-esterifying the carboxyl group in the side chain terminal of polyhydroxyalkanoate using trimethylsilyldiazomethane. 30 mg of the target polyhydroxyalkanoate was added to a 100 ml eggplant flask, and dissolved by adding 2.1 ml of chloroform and 0.7 ml of methanol. To this was added 0.5 ml of a 2 mol / L trimethylsilyldiazomethane-hexane solution, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the solvent was distilled off and the polymer was recovered. The polymer was recovered after washing with 50 ml of methanol. 29 mg of polyhydroxyalkanoate was obtained by drying under reduced pressure.

  NMR analysis was performed using the same method as in Example 6. As a result, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (74) was a copolymer of 7 mol% for the C unit and 93 mol% for the D unit.

(Example 30)
Condensation reaction between 2-hydroxybenzenesulfonic acid and a polyhydroxyalkanoate composed of the unit represented by the chemical formula (64) synthesized in Example 19

Under a nitrogen atmosphere, 0.40 g of a polymer synthesized with a polyhydroxyalkanoate copolymer (C: 8 mol%, D: 92 mol%) comprising the unit represented by the chemical formula (64) obtained in Example 19 was obtained. 0.36 g of benzenesulfonic acid was placed in a 100 ml three-necked flask, 15.0 ml of pyridine was added and stirred, and then 1.09 ml of triphenyl phosphite was added and heated at 120 ° C. for 6 hours. After completion of the reaction, it was recovered by reprecipitation in 150 ml of ethanol. The obtained polymer was washed with 1.0 mol / L (= 1.0 N) hydrochloric acid for 1 day, then washed by stirring in water for 1 day, and dried under reduced pressure to obtain 0.32 g of polymer. The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: heavy DMSO; measurement temperature: room temperature), Fourier transform-infrared absorption Analysis was performed by (FT-IR) spectrum (Nicolet AVATAR360FT-IR). As a result of IR measurement, the peak of 1695 cm ⁻¹ derived from carboxylic acid decreased, and a new peak derived from the amide group was observed at 1658 cm ⁻¹ .

^From the result of ¹ H-NMR, since the peak derived from the aromatic ring having a 2-aminobenzenesulfonic acid structure is shifted, the obtained polymer has a unit represented by the following chemical formula (75) as a monomer unit. It was confirmed to be a polyhydroxyalkanoate containing.

Further, it was confirmed that the unit of polyhydroxyalkanoate represented by the chemical formula (75) was a copolymer of 8 mol% for E unit and 92 mol% for F unit. The average molecular weight of the obtained polymer is gel permeation chromatography (GPC; Tosoh HLC-8120, column; Polymer Laboratories PLgel 5μ MIXED-C, solvent; DMF / LiBr 0.1% (w / v), polystyrene conversion) It was evaluated by. As a result, the number average molecular weight M _n = 11300 and the weight average molecular weight M _w = 16000.

(Example 31)
Condensation reaction of 2-hydroxybenzenesulfonic acid with a polyhydroxyalkanoate composed of the unit represented by the chemical formula (65) synthesized in Example 20

Under a nitrogen atmosphere, 0.40 g of a polymer synthesized with a polyhydroxyalkanoate copolymer (C: 8 mol%, D: 92 mol%) consisting of the unit represented by the chemical formula (65) obtained in Example 20 was obtained. 0.36 g of benzenesulfonic acid was placed in a 100 ml three-necked flask, 15.0 ml of pyridine was added and stirred, 1.07 ml of triphenyl phosphite was added, and the mixture was heated at 120 ° C. for 6 hours. After completion of the reaction, it was recovered by reprecipitation in 150 ml of ethanol. The obtained polymer was washed with 1.0 mol / L (= 1.0 N) hydrochloric acid for 1 day, then washed by stirring in water for 1 day, and dried under reduced pressure to obtain 0.33 g of polymer. The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: heavy DMSO; measurement temperature: room temperature), Fourier transform-infrared absorption Analysis was performed by (FT-IR) spectrum (Nicolet AVATAR360FT-IR). As a result of IR measurement, the peak of 1695 cm ⁻¹ derived from carboxylic acid decreased, and a new peak derived from the amide group was observed at 1658 cm ⁻¹ .

^From the result of ¹ H-NMR, since the peak derived from the aromatic ring having a 2-aminobenzenesulfonic acid structure is shifted, the obtained polymer has a unit represented by the following chemical formula (76) as a monomer unit. It was confirmed to be a polyhydroxyalkanoate containing.

Further, it was confirmed that the unit of polyhydroxyalkanoate represented by the chemical formula (76) was a copolymer of 8 mol% for E unit and 92 mol% for F unit. The average molecular weight of the obtained polymer is gel permeation chromatography (GPC; Tosoh HLC-8120, column; Polymer Laboratories PLgel 5μ MIXED-C, solvent; DMF / LiBr 0.1% (w / v), polystyrene conversion) It was evaluated by. As a result, the number average molecular weight M _n = 11500 and the weight average molecular weight M _w = 17300.

(Example 32)
Condensation reaction between a polyhydroxyalkanoate composed of the unit represented by the chemical formula (66) synthesized in Example 21 and 2-aminobenzenesulfonic acid

Under a nitrogen atmosphere, 0.40 g of a polymer synthesized with a polyhydroxyalkanoate copolymer (C: 8 mol%, D: 92 mol%) comprising the unit represented by the chemical formula (66) obtained in Example 21 was obtained. After adding 0.35 g of benzenesulfonic acid to a 100 ml three-necked flask and adding 15.0 ml of pyridine and stirring, 1.06 ml of triphenyl phosphite was added and heated at 120 ° C. for 6 hours. After completion of the reaction, it was recovered by reprecipitation in 150 ml of ethanol. The obtained polymer was washed with 1.0 mol / L (= 1.0 N) hydrochloric acid for 1 day, then washed by stirring in water for 1 day, and dried under reduced pressure to obtain 0.34 g of polymer. The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: heavy DMSO; measurement temperature: room temperature), Fourier transform-infrared absorption Analysis was performed by (FT-IR) spectrum (Nicolet AVATAR360FT-IR). As a result of IR measurement, the peak of 1695 cm ⁻¹ derived from carboxylic acid decreased, and a new peak derived from the amide group was observed at 1658 cm ⁻¹ .

^From the result of ¹ H-NMR, since the peak derived from the aromatic ring having a 2-aminobenzenesulfonic acid structure is shifted, the obtained polymer has a unit represented by the following chemical formula (77) as a monomer unit. It was confirmed to be a polyhydroxyalkanoate containing.

Further, it was confirmed that the unit of polyhydroxyalkanoate represented by the chemical formula (77) was a copolymer of 8 mol% for E unit and 92 mol% for F unit. The average molecular weight of the obtained polymer is gel permeation chromatography (GPC; Tosoh HLC-8120, column; Polymer Laboratories PLgel 5μ MIXED-C, solvent; DMF / LiBr 0.1% (w / v), polystyrene conversion) It was evaluated by. As a result, the number average molecular weight M _n = 10100 and the weight average molecular weight M _w = 14300.

(Example 33)
Condensation reaction between a polyhydroxyalkanoate composed of the unit represented by the chemical formula (67) synthesized in Example 22 and 2-aminobenzenesulfonic acid

In a nitrogen atmosphere, 0.40 g of a polymer synthesized with a polyhydroxyalkanoate copolymer (C: 7 mol%, D: 93 mol%) comprising the unit represented by the chemical formula (67) obtained in Example 22 was obtained. After putting 0.31 g of benzenesulfonic acid in a 100 ml three-necked flask and adding 15.0 ml of pyridine and stirring, 0.92 ml of triphenyl phosphite was added and heated at 120 ° C. for 6 hours. After completion of the reaction, it was recovered by reprecipitation in 150 ml of ethanol. The obtained polymer was washed with 1.0 mol / L (= 1.0 N) hydrochloric acid for 1 day, then washed by stirring in water for 1 day, and dried under reduced pressure to obtain 0.33 g of polymer. The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: heavy DMSO; measurement temperature: room temperature), Fourier transform-infrared absorption Analysis was performed by (FT-IR) spectrum (Nicolet AVATAR360FT-IR). As a result of IR measurement, the peak of 1695 cm ⁻¹ derived from carboxylic acid decreased, and a new peak derived from the amide group was observed at 1658 cm ⁻¹ .

^From the result of ¹ H-NMR, since the peak derived from the aromatic ring of 2-aminobenzenesulfonic acid structure is shifted, the obtained polymer has a unit represented by the following chemical formula (78) as a monomer unit. It was confirmed to be a polyhydroxyalkanoate containing.

Further, it was confirmed that the unit of polyhydroxyalkanoate represented by the chemical formula (78) was a copolymer of 7 mol% for the E unit and 93 mol% for the F unit. The average molecular weight of the obtained polymer is gel permeation chromatography (GPC; Tosoh HLC-8120, column; Polymer Laboratories PLgel 5μ MIXED-C, solvent; DMF / LiBr 0.1% (w / v), polystyrene conversion) It was evaluated by. As a result, the number average molecular weight M _n = 9900 and the weight average molecular weight M _w = 14400.

Example 34
Condensation reaction of 2-hydroxybenzenesulfonic acid with a polyhydroxyalkanoate composed of the unit represented by chemical formula (68) synthesized in Example 23

Under a nitrogen atmosphere, 0.40 g of a polymer synthesized with a polyhydroxyalkanoate copolymer (C: 8 mol%, D: 92 mol%) composed of the unit represented by the chemical formula (68) obtained in Example 23 was obtained. 0.37 g of benzenesulfonic acid was placed in a 100 ml three-necked flask, 15.0 ml of pyridine was added and stirred, and then 1.10 ml of triphenyl phosphite was added and heated at 120 ° C. for 6 hours. After completion of the reaction, it was recovered by reprecipitation in 150 ml of ethanol. The obtained polymer was washed with 1.0 mol / L (= 1.0 N) hydrochloric acid for 1 day, then washed by stirring in water for 1 day, and dried under reduced pressure to obtain 0.32 g of polymer. The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: heavy DMSO; measurement temperature: room temperature), Fourier transform-infrared absorption Analysis was performed by (FT-IR) spectrum (Nicolet AVATAR360FT-IR). As a result of IR measurement, the peak of 1695 cm ⁻¹ derived from carboxylic acid decreased, and a new peak derived from the amide group was observed at 1658 cm ⁻¹ .

^From the result of ¹ H-NMR, since the peak derived from the aromatic ring of 2-aminobenzenesulfonic acid structure is shifted, the obtained polymer has a unit represented by the following chemical formula (79) as a monomer unit. It was confirmed to be a polyhydroxyalkanoate containing.

Further, it was confirmed that the unit of polyhydroxyalkanoate represented by the chemical formula (79) was a copolymer of 8 mol% for the E unit and 92 mol% for the F unit. The average molecular weight of the obtained polymer is gel permeation chromatography (GPC; Tosoh HLC-8120, column; Polymer Laboratories PLgel 5μ MIXED-C, solvent; DMF / LiBr 0.1% (w / v), polystyrene conversion) It was evaluated by. As a result, the number average molecular weight M _n = 11800 and the weight average molecular weight M _w = 16600.

(Example 35)
Condensation reaction of polyhydroxyalkanoate composed of the unit represented by the chemical formula (69) synthesized in Example 24 and p-toluidine-2-sulfonic acid

0.40 g of p-toluidine polymer synthesized with a polyhydroxyalkanoate copolymer (C: 8 mol%, D: 92 mol%) comprising the unit represented by the chemical formula (69) obtained in Example 24 under a nitrogen atmosphere After putting 0.39 g of -2-sulfonic acid in a 100 ml three-necked flask and adding 15.0 ml of pyridine and stirring, 1.10 ml of triphenyl phosphite was added and heated at 120 ° C. for 6 hours. After completion of the reaction, it was recovered by reprecipitation in 150 ml of ethanol. The obtained polymer was washed with 1.0 mol / L (= 1.0 N) hydrochloric acid for 1 day, then washed by stirring in water for 1 day, and dried under reduced pressure to obtain 0.33 g of polymer. The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: heavy DMSO; measurement temperature: room temperature), Fourier transform-infrared absorption Analysis was performed by (FT-IR) spectrum (Nicolet AVATAR360FT-IR). As a result of IR measurement, the peak of 1695 cm ⁻¹ derived from carboxylic acid decreased, and a new peak derived from the amide group was observed at 1658 cm ⁻¹ .

^From the result of ¹ H-NMR, since the peak derived from the aromatic ring of p-toluidine-2-sulfonic acid structure is shifted, the obtained polymer is represented by the following chemical formula (80) as a monomer unit. It was confirmed to be a polyhydroxyalkanoate containing unit.

Further, it was confirmed that the unit of polyhydroxyalkanoate represented by the chemical formula (80) was a copolymer of 8 mol% for E unit and 92 mol% for F unit. The average molecular weight of the obtained polymer is gel permeation chromatography (GPC; Tosoh HLC-8120, column; Polymer Laboratories PLgel 5μ MIXED-C, solvent; DMF / LiBr 0.1% (w / v), polystyrene conversion) It was evaluated by. As a result, the number average molecular weight M _n = 11,000 and the weight average molecular weight M _w = 15700.

Example 36
Condensation reaction between a polyhydroxyalkanoate composed of the unit represented by the chemical formula (69) synthesized in Example 24 and 4-aminobenzenesulfonic acid

In a nitrogen atmosphere, 0.40 g of a polymer synthesized with a polyhydroxyalkanoate copolymer (C: 8 mol%, D: 92 mol%) composed of the unit represented by the chemical formula (69) obtained in Example 24 was obtained. 0.37 g of benzenesulfonic acid was placed in a 100 ml three-necked flask, 15.0 ml of pyridine was added and stirred, and then 1.10 ml of triphenyl phosphite was added and heated at 120 ° C. for 6 hours. After completion of the reaction, it was recovered by reprecipitation in 150 ml of ethanol. The obtained polymer was washed with 1.0 mol / L (= 1.0 N) hydrochloric acid for 1 day, then washed by stirring in water for 1 day, and dried under reduced pressure to obtain 0.31 g of polymer. The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: heavy DMSO; measurement temperature: room temperature), Fourier transform-infrared absorption Analysis was performed by (FT-IR) spectrum (Nicolet AVATAR360FT-IR). As a result of IR measurement, the peak of 1695 cm ⁻¹ derived from carboxylic acid decreased, and a new peak derived from the amide group was observed at 1658 cm ⁻¹ .

^From the result of ¹ H-NMR, since the peak derived from the aromatic ring having a 4-aminobenzenesulfonic acid structure is shifted, the obtained polymer has a unit represented by the following chemical formula (81) as a monomer unit. It was confirmed to be a polyhydroxyalkanoate containing.

Further, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (81) was a copolymer of 8 mol% for the E unit and 92 mol% for the F unit. The average molecular weight of the obtained polymer is gel permeation chromatography (GPC; Tosoh HLC-8120, column; Polymer Laboratories PLgel 5μ MIXED-C, solvent; DMF / LiBr 0.1% (w / v), polystyrene conversion) It was evaluated by. As a result, the number average molecular weight M _n = 10700 and the weight average molecular weight M _w = 15700.

(Example 37)
Condensation reaction of polyhydroxyalkanoate composed of the unit represented by chemical formula (69) synthesized in Example 24 and 3-aminobenzenesulfonic acid

Under a nitrogen atmosphere, 0.40 g of a polymer synthesized with a polyhydroxyalkanoate copolymer (C: 8 mol%, D: 92 mol%) consisting of the unit represented by the chemical formula (69) obtained in Example 24 was obtained. 0.37 g of benzenesulfonic acid was placed in a 100 ml three-necked flask, 15.0 ml of pyridine was added and stirred, and then 1.10 ml of triphenyl phosphite was added and heated at 120 ° C. for 6 hours. After completion of the reaction, it was recovered by reprecipitation in 150 ml of ethanol. The obtained polymer was washed with 1.0 mol / L (= 1.0 N) hydrochloric acid for 1 day, then washed by stirring in water for 1 day, and dried under reduced pressure to obtain 0.32 g of polymer. The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: heavy DMSO; measurement temperature: room temperature), Fourier transform-infrared absorption Analysis was performed by (FT-IR) spectrum (Nicolet AVATAR360FT-IR). As a result of IR measurement, the peak of 1695 cm ⁻¹ derived from carboxylic acid decreased, and a new peak derived from the amide group was observed at 1658 cm ⁻¹ .

^From the result of ¹ H-NMR, since the peak derived from the aromatic ring having a 3-aminobenzenesulfonic acid structure is shifted, the obtained polymer has a unit represented by the following chemical formula (82) as a monomer unit. It was confirmed to be a polyhydroxyalkanoate containing.

Further, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (82) was a copolymer of 8 mol% for the E unit and 92 mol% for the F unit. The average molecular weight of the obtained polymer is gel permeation chromatography (GPC; Tosoh HLC-8120, column; Polymer Laboratories PLgel 5μ MIXED-C, solvent; DMF / LiBr 0.1% (w / v), polystyrene conversion) It was evaluated by. As a result, the number average molecular weight M _n = 11300 and the weight average molecular weight M _w = 16200.

(Example 38)
Condensation reaction of polyhydroxyalkanoate composed of the unit represented by chemical formula (69) synthesized in Example 24 and 4-methoxyaniline-2-sulfonic acid

Under a nitrogen atmosphere, 0.40 g of a polymer synthesized with a polyhydroxyalkanoate copolymer (C: 8 mol%, D: 92 mol%) composed of the unit represented by the chemical formula (69) obtained in Example 24 was obtained. After placing 0.43 g of aniline-2-sulfonic acid in a 100 ml three-necked flask and adding 15.0 ml of pyridine and stirring, 1.10 ml of triphenyl phosphite was added and heated at 120 ° C. for 6 hours. After completion of the reaction, it was recovered by reprecipitation in 150 ml of ethanol. The obtained polymer was washed with 1.0 mol / L (= 1.0 N) hydrochloric acid for 1 day, then washed by stirring in water for 1 day, and dried under reduced pressure to obtain 0.34 g of polymer. The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: heavy DMSO; measurement temperature: room temperature), Fourier transform-infrared absorption Analysis was performed by (FT-IR) spectrum (Nicolet AVATAR360FT-IR). As a result of IR measurement, the peak of 1695 cm ⁻¹ derived from carboxylic acid decreased, and a new peak derived from the amide group was observed at 1658 cm ⁻¹ .

^From the result of ¹ H-NMR, since the peak derived from the aromatic ring of 4-methoxyaniline-2-sulfonic acid structure is shifted, the obtained polymer is represented by the following chemical formula (83) as a monomer unit. It was confirmed that this was a polyhydroxyalkanoate containing unit.

Further, it was confirmed that the unit of polyhydroxyalkanoate represented by the chemical formula (83) was a copolymer of 8 mol% for the E unit and 92 mol% for the F unit. The average molecular weight of the obtained polymer is gel permeation chromatography (GPC; Tosoh HLC-8120, column; Polymer Laboratories PLgel 5μ MIXED-C, solvent; DMF / LiBr 0.1% (w / v), polystyrene conversion) It was evaluated by. As a result, the number average molecular weight M _n = 11000 and the weight average molecular weight M _w = 16100.

(Example 39)
Condensation reaction of polyhydroxyalkanoate composed of the unit represented by chemical formula (69) synthesized in Example 24 and 4-aminobenzenesulfonic acid phenyl ester

In a nitrogen atmosphere, 0.40 g of a polymer synthesized with a polyhydroxyalkanoate copolymer (C: 8 mol%, D: 92 mol%) composed of the unit represented by the chemical formula (69) obtained in Example 24 was obtained. Benzenesulfonic acid phenyl ester 0.53 g was placed in a 100 ml three-necked flask, 15.0 ml of pyridine was added and stirred, 1.10 ml of triphenyl phosphite was added, and the mixture was heated at 120 ° C. for 6 hours. After completion of the reaction, it was recovered by reprecipitation in 150 ml of ethanol. The obtained polymer was washed with 1.0 mol / L (= 1.0 N) hydrochloric acid for 1 day, then washed by stirring in water for 1 day, and dried under reduced pressure to obtain 0.35 g of polymer. The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: heavy DMSO; measurement temperature: room temperature), Fourier transform-infrared absorption Analysis was performed by (FT-IR) spectrum (Nicolet AVATAR360FT-IR). As a result of IR measurement, the peak of 1695 cm ⁻¹ derived from carboxylic acid decreased, and a new peak derived from the amide group was observed at 1658 cm ⁻¹ .

^From the result of ¹ H-NMR, since the peak derived from the aromatic ring of the 4-aminobenzenesulfonic acid phenyl ester structure is shifted, the obtained polymer is represented by the following chemical formula (84) as a monomer unit. It was confirmed to be a polyhydroxyalkanoate containing unit.

Further, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (84) was a copolymer of 8 mol% for the E unit and 92 mol% for the F unit. The average molecular weight of the obtained polymer is gel permeation chromatography (GPC; Tosoh HLC-8120, column; Polymer Laboratories PLgel 5μ MIXED-C, solvent; DMF / LiBr 0.1% (w / v), polystyrene conversion) It was evaluated by. As a result, the number average molecular weight M _n = 11500 and the weight average molecular weight M _w = 17100.

(Example 40)
Condensation reaction of polyhydroxyalkanoate composed of the unit represented by the chemical formula (69) synthesized in Example 24 and 2-aminobenzenesulfonic acid phenyl ester

Under a nitrogen atmosphere, 0.40 g of a polymer synthesized with a polyhydroxyalkanoate copolymer (C: 8 mol%, D: 92 mol%) comprising the unit represented by the chemical formula (69) obtained in Example 24 was obtained. Benzenesulfonic acid phenyl ester 0.53 g was placed in a 100 ml three-necked flask, 15.0 ml of pyridine was added and stirred, 1.10 ml of triphenyl phosphite was added, and the mixture was heated at 120 ° C. for 6 hours. After completion of the reaction, it was recovered by reprecipitation in 150 ml of ethanol. The obtained polymer was washed with 1.0 mol / L (= 1.0 N) hydrochloric acid for 1 day, then washed by stirring in water for 1 day, and dried under reduced pressure to obtain 0.34 g of polymer. The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: heavy DMSO; measurement temperature: room temperature), Fourier transform-infrared absorption Analysis was performed by (FT-IR) spectrum (Nicolet AVATAR360FT-IR). As a result of IR measurement, the peak of 1695 cm ⁻¹ derived from carboxylic acid decreased, and a new peak derived from the amide group was observed at 1658 cm ⁻¹ .

^From the result of ¹ H-NMR, since the peak derived from the aromatic ring of 2-aminobenzenesulfonic acid phenyl ester structure is shifted, the obtained polymer is represented by the following chemical formula (85) as a monomer unit. It was confirmed to be a polyhydroxyalkanoate containing unit.

Further, it was confirmed that the unit of polyhydroxyalkanoate represented by the chemical formula (85) was a copolymer of 8 mol% for the E unit and 92 mol% for the F unit. The average molecular weight of the obtained polymer is gel permeation chromatography (GPC; Tosoh HLC-8120, column; Polymer Laboratories PLgel 5μ MIXED-C, solvent; DMF / LiBr 0.1% (w / v), polystyrene conversion) It was evaluated by. As a result, the number average molecular weight M _n = 11300 and the weight average molecular weight M _w = 16800.

(Example 41)
Condensation reaction between a polyhydroxyalkanoate composed of the unit represented by the chemical formula (69) synthesized in Example 24 and 2-amino-1-naphthalenesulfonic acid

Under a nitrogen atmosphere, 0.40 g of a polymer synthesized with a polyhydroxyalkanoate copolymer (C: 8 mol%, D: 92 mol%) comprising the unit represented by the chemical formula (69) obtained in Example 24 was obtained. A solution of 0.47 g of -1-naphthalenesulfonic acid was placed in a 100 ml three-necked flask, and 15.0 ml of pyridine was added and stirred. After completion of the reaction, it was recovered by reprecipitation in 150 ml of ethanol. The obtained polymer was washed with 1.0 mol / L (= 1.0 N) hydrochloric acid for 1 day, then washed by stirring in water for 1 day, and dried under reduced pressure to obtain 0.37 g of polymer. The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: heavy DMSO; measurement temperature: room temperature), Fourier transform-infrared absorption Analysis was performed by (FT-IR) spectrum (Nicolet AVATAR360FT-IR). As a result of IR measurement, the peak of 1695 cm ⁻¹ derived from carboxylic acid decreased, and a new peak derived from the amide group was observed at 1658 cm ⁻¹ .

^From the result of ¹ H-NMR, since the peak derived from the aromatic ring of 2-amino-1-naphthalenesulfonic acid structure is shifted, the obtained polymer is represented by the following chemical formula (86) as a monomer unit. It was confirmed that this was a polyhydroxyalkanoate containing unit.

Further, it was confirmed that the unit of polyhydroxyalkanoate represented by the chemical formula (86) was a copolymer of 8 mol% for E unit and 92 mol% for F unit. The average molecular weight of the obtained polymer is gel permeation chromatography (GPC; Tosoh HLC-8120, column; Polymer Laboratories PLgel 5μ MIXED-C, solvent; DMF / LiBr 0.1% (w / v), polystyrene conversion) It was evaluated by. As a result, the number average molecular weight M _n = 11000 and the weight average molecular weight M _w = 16600.

(Example 42)
Condensation reaction of polyhydroxyalkanoate composed of the unit represented by the chemical formula (69) synthesized in Example 24 and 1-naphthylamine-8-sulfonic acid

In a nitrogen atmosphere, 0.40 g of a polymer synthesized with a polyhydroxyalkanoate copolymer (C: 8 mol%, D: 92 mol%) consisting of the unit represented by the chemical formula (69) obtained in Example 24 was obtained. After placing 0.47 g of -8-sulfonic acid in a 100 ml three-necked flask and adding 15.0 ml of pyridine and stirring, 1.10 ml of triphenyl phosphite was added and heated at 120 ° C. for 6 hours. After completion of the reaction, it was recovered by reprecipitation in 150 ml of ethanol. The obtained polymer was washed with 1.0 mol / L (= 1.0 N) hydrochloric acid for 1 day, then washed by stirring in water for 1 day, and dried under reduced pressure to obtain 0.36 g of polymer. The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: heavy DMSO; measurement temperature: room temperature), Fourier transform-infrared absorption Analysis was performed by (FT-IR) spectrum (Nicolet AVATAR360FT-IR). As a result of IR measurement, the peak of 1695 cm ⁻¹ derived from carboxylic acid decreased, and a new peak derived from the amide group was observed at 1658 cm ⁻¹ .

^From the result of ¹ H-NMR, since the peak derived from the aromatic ring having a 1-naphthylamine-8-sulfonic acid structure is shifted, the obtained polymer is represented by the following chemical formula (87) as a monomer unit. It was confirmed to be a polyhydroxyalkanoate containing unit.

Further, it was confirmed that the unit of polyhydroxyalkanoate represented by the chemical formula (87) was a copolymer of 8 mol% for the E unit and 92 mol% for the F unit. The average molecular weight of the obtained polymer is gel permeation chromatography (GPC; Tosoh HLC-8120, column; Polymer Laboratories PLgel 5μ MIXED-C, solvent; DMF / LiBr 0.1% (w / v), polystyrene conversion) It was evaluated by. As a result, the number average molecular weight M _n = 10900 and the weight average molecular weight M _w = 17100.

(Example 43)
Condensation reaction of polyhydroxyalkanoate composed of the unit represented by chemical formula (69) synthesized in Example 24 and 2-amino-2-methylpropanesulfonic acid

Under a nitrogen atmosphere, 0.40 g of a polymer synthesized with a polyhydroxyalkanoate copolymer (C: 8 mol%, D: 92 mol%) comprising the unit represented by the chemical formula (69) obtained in Example 24 was obtained. After putting 0.32 g of -2-methylpropanesulfonic acid in a 100 ml three-necked flask and adding 15.0 ml of pyridine and stirring, 1.10 ml of triphenyl phosphite was added and heated at 120 ° C. for 6 hours. After completion of the reaction, it was recovered by reprecipitation in 150 ml of ethanol. The obtained polymer was washed with 1.0 mol / L (= 1.0 N) hydrochloric acid for 1 day, then washed by stirring in water for 1 day, and dried under reduced pressure to obtain 0.33 g of polymer. The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: heavy DMSO; measurement temperature: room temperature), Fourier transform-infrared absorption Analysis was performed by (FT-IR) spectrum (Nicolet AVATAR360FT-IR). As a result of IR measurement, the peak at 1695 cm ⁻¹ derived from carboxylic acid decreased, and a new peak derived from the amide group was observed at 1668 cm ⁻¹ .

^From the result of ¹ H-NMR, since the peak derived from methylene having a 2-amino-2-methylpropanesulfonic acid structure is shifted, the obtained polymer is represented by the following chemical formula (88) as a monomer unit. It was confirmed that this was a polyhydroxyalkanoate containing unit.

Further, it was confirmed that the unit of polyhydroxyalkanoate represented by the chemical formula (88) was a copolymer of 8 mol% for E unit and 92 mol% for F unit. The average molecular weight of the obtained polymer is gel permeation chromatography (GPC; Tosoh HLC-8120, column; Polymer Laboratories PLgel 5μ MIXED-C, solvent; DMF / LiBr 0.1% (w / v), polystyrene conversion) It was evaluated by. As a result, the number average molecular weight M _n = 10300 and the weight average molecular weight M _w = 14700.

(Example 44)
Condensation reaction between polyhydroxyalkanoate composed of the unit represented by the chemical formula (69) synthesized in Example 24 and taurine

Under a nitrogen atmosphere, 0.40 g of a polymer synthesized with a polyhydroxyalkanoate copolymer (C: 8 mol%, D: 92 mol%) consisting of the unit represented by the chemical formula (69) obtained in Example 24, and 0.26 g of taurine Was added to 1 ml of pyridine and stirred, and then 1.10 ml of triphenyl phosphite was added and heated at 120 ° C. for 6 hours. After completion of the reaction, it was recovered by reprecipitation in 150 ml of ethanol. The obtained polymer was washed with 1.0 mol / L (= 1.0 N) hydrochloric acid for 1 day, then washed by stirring in water for 1 day, and dried under reduced pressure to obtain 0.33 g of polymer. The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: heavy DMSO; measurement temperature: room temperature), Fourier transform-infrared absorption Analysis was performed by (FT-IR) spectrum (Nicolet AVATAR360FT-IR). As a result of IR measurement, the peak at 1695 cm ⁻¹ derived from carboxylic acid decreased, and a new peak derived from the amide group was observed at 1668 cm ⁻¹ .

^From the result of ¹ H-NMR, since the peak derived from methylene having a taurine structure is shifted, the obtained polymer is a polyhydroxyalkanoate containing a unit represented by the following chemical formula (89) as a monomer unit. It was confirmed that there was.

Further, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (89) was a copolymer of 8 mol% for the E unit and 92 mol% for the F unit. The average molecular weight of the obtained polymer is gel permeation chromatography (GPC; Tosoh HLC-8120, column; Polymer Laboratories PLgel 5μ MIXED-C, solvent; DMF / LiBr 0.1% (w / v), polystyrene conversion) It was evaluated by. As a result, the number average molecular weight M _n = 9900 and the weight average molecular weight M _w = 14100.

(Example 45)
Condensation reaction of 2-hydroxybenzenesulfonic acid with a polyhydroxyalkanoate composed of the unit represented by the chemical formula (70) synthesized in Example 25

Under a nitrogen atmosphere, 0.40 g of a polymer synthesized with a polyhydroxyalkanoate copolymer (C: 4 mol%, D: 96 mol%) consisting of the unit represented by the chemical formula (70) obtained in Example 25 was obtained. 0.18 g of benzenesulfonic acid was placed in a 100 ml three-necked flask, 15.0 ml of pyridine was added and stirred, 0.57 ml of triphenyl phosphite was added, and the mixture was heated at 120 ° C. for 6 hours. After completion of the reaction, it was recovered by reprecipitation in 150 ml of ethanol. The obtained polymer was washed with 1.0 mol / L (= 1.0 N) hydrochloric acid for 1 day, then washed by stirring in water for 1 day, and dried under reduced pressure to obtain 0.32 g of polymer. The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: heavy DMSO; measurement temperature: room temperature), Fourier transform-infrared absorption Analysis was performed by (FT-IR) spectrum (Nicolet AVATAR360FT-IR). As a result of IR measurement, the peak of 1695 cm ⁻¹ derived from carboxylic acid decreased, and a new peak derived from the amide group was observed at 1658 cm ⁻¹ .

^From the result of ¹ H-NMR, since the peak derived from the aromatic ring having a 2-aminobenzenesulfonic acid structure is shifted, the obtained polymer has a unit represented by the following chemical formula (90) as a monomer unit. It was confirmed to be a polyhydroxyalkanoate containing.

Further, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (90) was a copolymer of 4 mol% for the E unit and 96 mol% for the F unit. The average molecular weight of the obtained polymer is gel permeation chromatography (GPC; Tosoh HLC-8120, column; Polymer Laboratories PLgel 5μ MIXED-C, solvent; DMF / LiBr 0.1% (w / v), polystyrene conversion) It was evaluated by. As a result, the number average molecular weight M _n = 12000 and the weight average molecular weight M _w = 15800.

Example 46
Condensation reaction between a polyhydroxyalkanoate composed of the unit represented by the chemical formula (71) synthesized in Example 26 and 2-aminobenzenesulfonic acid

In a nitrogen atmosphere, 0.40 g of a polymer synthesized with a polyhydroxyalkanoate copolymer (C: 13 mol%, D: 87 mol%) composed of the unit represented by the chemical formula (71) obtained in Example-26 was obtained. After putting 0.58 g of aminobenzenesulfonic acid into a 100 ml three-necked flask and adding 15.0 ml of pyridine and stirring, 1.74 ml of triphenyl phosphite was added and heated at 120 ° C. for 6 hours. After completion of the reaction, it was recovered by reprecipitation in 150 ml of ethanol. The obtained polymer was washed with 1.0 mol / L (= 1.0 N) hydrochloric acid for 1 day, then washed by stirring in water for 1 day, and dried under reduced pressure to obtain 0.32 g of polymer. The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: heavy DMSO; measurement temperature: room temperature), Fourier transform-infrared absorption Analysis was performed by (FT-IR) spectrum (Nicolet AVATAR360FT-IR). As a result of IR measurement, the peak of 1695 cm ⁻¹ derived from carboxylic acid decreased, and a new peak derived from the amide group was observed at 1658 cm ⁻¹ .

^From the result of ¹ H-NMR, since the peak derived from the aromatic ring having a 2-aminobenzenesulfonic acid structure is shifted, the obtained polymer has a unit represented by the following chemical formula (91) as a monomer unit. It was confirmed to be a polyhydroxyalkanoate containing.

Further, it was confirmed that the unit of polyhydroxyalkanoate represented by the chemical formula (91) was a copolymer of 13 mol% for E unit and 87 mol% for F unit. The average molecular weight of the obtained polymer is gel permeation chromatography (GPC; Tosoh HLC-8120, column; Polymer Laboratories PLgel 5μ MIXED-C, solvent; DMF / LiBr 0.1% (w / v), polystyrene conversion) It was evaluated by. As a result, the number average molecular weight M _n = 9500 and the weight average molecular weight M _w = 12600.

(Example 47)
Condensation reaction of 2-hydroxybenzenesulfonic acid with a polyhydroxyalkanoate composed of the unit represented by the chemical formula (72) synthesized in Example 27

  In a nitrogen atmosphere, 0.40 g of a polymer synthesized with a polyhydroxyalkanoate copolymer (C: 16 mol%, D: 84 mol%) comprising the unit represented by the chemical formula (72) obtained in Example 27 was obtained. After adding 0.70 g of benzenesulfonic acid to a 100 ml three-necked flask and adding 15.0 ml of pyridine and stirring, 2.11 ml of triphenyl phosphite was added and heated at 120 ° C. for 6 hours. After completion of the reaction, it was recovered by reprecipitation in 150 ml of ethanol. The obtained polymer was washed with 1.0 mol / L (= 1.0 N) hydrochloric acid for 1 day, then washed by stirring in water for 1 day, and dried under reduced pressure to obtain 0.32 g of polymer.

The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: heavy DMSO; measurement temperature: room temperature), Fourier transform-infrared absorption Analysis was performed by (FT-IR) spectrum (Nicolet AVATAR360FT-IR). As a result of IR measurement, the peak of 1695 cm ⁻¹ derived from carboxylic acid decreased, and a new peak derived from the amide group was observed at 1658 cm ⁻¹ .

^From the result of ¹ H-NMR, since the peak derived from the aromatic ring having a 2-aminobenzenesulfonic acid structure is shifted, the obtained polymer has a unit represented by the following chemical formula (92) as a monomer unit. It was confirmed to be a polyhydroxyalkanoate containing.

Further, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (92) was a copolymer of 16 mol% for the E unit and 84 mol% for the F unit. The average molecular weight of the obtained polymer is gel permeation chromatography (GPC; Tosoh HLC-8120, column; Polymer Laboratories PLgel 5μ MIXED-C, solvent; DMF / LiBr 0.1% (w / v), polystyrene conversion) It was evaluated by. As a result, the number average molecular weight M _n = 9100 and the weight average molecular weight M _w = 12200.

Example 48
Condensation reaction between a polyhydroxyalkanoate composed of the unit represented by the chemical formula (73) synthesized in Example 28 and 2-aminobenzenesulfonic acid

Under a nitrogen atmosphere, 0.40 g of a polymer synthesized with a polyhydroxyalkanoate copolymer (C: 9 mol%, D: 91 mol%) composed of the unit represented by the chemical formula (73) obtained in Example 28 was obtained. 0.49 g of benzenesulfonic acid was placed in a 100 ml three-necked flask, 15.0 ml of pyridine was added and stirred, 1.48 ml of triphenyl phosphite was added, and the mixture was heated at 120 ° C. for 6 hours. After completion of the reaction, it was recovered by reprecipitation in 150 ml of ethanol. The obtained polymer was washed with 1.0 mol / L (= 1.0 N) hydrochloric acid for 1 day, then washed by stirring in water for 1 day, and dried under reduced pressure to obtain 0.35 g of polymer. The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: heavy DMSO; measurement temperature: room temperature), Fourier transform-infrared absorption Analysis was performed by (FT-IR) spectrum (Nicolet AVATAR360FT-IR). As a result of IR measurement, the peak of 1695 cm ⁻¹ derived from carboxylic acid decreased, and a new peak derived from the amide group was observed at 1658 cm ⁻¹ .

^From the result of ¹ H-NMR, since the peak derived from the aromatic ring having a 2-aminobenzenesulfonic acid structure is shifted, the obtained polymer has a unit represented by the following chemical formula (93) as a monomer unit. It was confirmed to be a polyhydroxyalkanoate containing.

Further, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (93) was a copolymer of 9 mol% for the E unit and 91 mol% for the F unit. The average molecular weight of the obtained polymer is gel permeation chromatography (GPC; Tosoh HLC-8120, column; Polymer Laboratories PLgel 5μ MIXED-C, solvent; DMF / LiBr 0.1% (w / v), polystyrene conversion) It was evaluated by. As a result, the number average molecular weight M _n = 11900 and the weight average molecular weight M _w = 16200.

(Example 49)
Condensation reaction of polyhydroxyalkanoate composed of the unit represented by the chemical formula (74) synthesized in Example 29 and 2-aminobenzenesulfonic acid

In a nitrogen atmosphere, 0.40 g of a polymer synthesized with a polyhydroxyalkanoate copolymer (C: 7 mol%, D: 93 mol%) comprising the unit represented by the chemical formula (74) obtained in Example 29 was obtained. 0.18 g of benzenesulfonic acid was placed in a 100 ml three-necked flask, 15.0 ml of pyridine was added and stirred, 0.55 ml of triphenyl phosphite was added, and the mixture was heated at 120 ° C. for 6 hours. After completion of the reaction, it was recovered by reprecipitation in 150 ml of ethanol. The obtained polymer was washed with 1.0 mol / L (= 1.0 N) hydrochloric acid for 1 day, then washed by stirring in water for 1 day, and dried under reduced pressure to obtain 0.34 g of polymer. The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: heavy DMSO; measurement temperature: room temperature), Fourier transform-infrared absorption Analysis was performed by (FT-IR) spectrum (Nicolet AVATAR360FT-IR). As a result of IR measurement, the peak of 1695 cm ⁻¹ derived from carboxylic acid decreased, and a new peak derived from the amide group was observed at 1658 cm ⁻¹ .

^From the result of ¹ H-NMR, since the peak derived from the aromatic ring of 2-aminobenzenesulfonic acid structure is shifted, the obtained polymer has a unit represented by the following chemical formula (94) as a monomer unit. It was confirmed to be a polyhydroxyalkanoate containing.

Further, it was confirmed that the unit of polyhydroxyalkanoate represented by the chemical formula (94) was a copolymer of 7 mol% for the E unit and 93 mol% for the F unit. The average molecular weight of the obtained polymer is gel permeation chromatography (GPC; Tosoh HLC-8120, column; Polymer Laboratories PLgel 5μ MIXED-C, solvent; DMF / LiBr 0.1% (w / v), polystyrene conversion) It was evaluated by. As a result, the number average molecular weight M _n = 11400 and the weight average molecular weight M _w = 23100.

(Example 50)
Esterification reaction of polyhydroxyalkanoate composed of unit represented by chemical formula (75) synthesized in Example 30

  0.30 g of a polyhydroxyalkanoate copolymer (E: 8 mol%, F: 92 mol%) composed of the unit represented by the chemical formula (75) obtained in Example 30 was added to an eggplant flask, and 21.0 ml of chloroform and 7.0% of methanol were added. Add ml to dissolve and cool to 0 ° C. To this was added 1.35 ml of a 2 mol / L trimethylsilyldiazomethane-hexane solution (manufactured by Aldrich), and the mixture was stirred for 4 hours. After completion of the reaction, the solvent was removed by an evaporator, and then the polymer was recovered.

Further, 21.0 ml of chloroform and 7.0 ml of methanol were added to redissolve the polymer, and the solvent was distilled off with an evaporator. This operation was repeated three times. The polymer collected here was dried under reduced pressure to obtain 0.30 g of a polymer. The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: heavy DMSO; measurement temperature: room temperature). ^From the result of ¹ H-NMR, since a peak derived from methyl sulfonate is seen at 3 to 4 ppm, the obtained polymer is a polyhydroxyalkanoate containing a unit represented by the following chemical formula (95) as a monomer unit. It was confirmed that.

Further, it was confirmed that the unit of polyhydroxyalkanoate represented by the chemical formula (95) was a copolymer of 8 mol% for G unit and 92 mol% for H unit. In addition, the acid value titration using the potentiometric titrator AT510 (manufactured by Kyoto Electronics Co., Ltd.) revealed that the sulfonic acid was methyl sulfonate because no peak derived from sulfonic acid was observed. . The average molecular weight of the obtained polymer is gel permeation chromatography (GPC; Tosoh HLC-8120, column; Polymer Laboratories PLgel 5μ MIXED-C, solvent; DMF / LiBr 0.1% (w / v), polystyrene conversion) It was evaluated by. As a result, the number average molecular weight M _n = 10900 and the weight average molecular weight M _w = 15600.

(Example 51)
Esterification reaction of polyhydroxyalkanoate composed of unit represented by chemical formula (78) synthesized in Example 33

  0.30 g of a polyhydroxyalkanoate copolymer (E: 7 mol%, F: 93 mol%) comprising the unit represented by the chemical formula (78) obtained in Example 33 was added to an eggplant flask, and 21.0 ml of chloroform and 7.0% of methanol were added. Add ml to dissolve and cool to 0 ° C. To this was added 1.17 ml of a 2 mol / L trimethylsilyldiazomethane-hexane solution (manufactured by Aldrich), and the mixture was stirred for 4 hours. After completion of the reaction, the solvent was removed by an evaporator, and then the polymer was recovered.

Further, 21.0 ml of chloroform and 7.0 ml of methanol were added to redissolve the polymer, and the solvent was distilled off with an evaporator. This operation was repeated three times. The polymer collected here was dried under reduced pressure to obtain 0.30 g of a polymer. The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: heavy DMSO; measurement temperature: room temperature). ^From the result of ¹ H-NMR, since a peak derived from methyl sulfonate is seen at 3 to 4 ppm, the obtained polymer is a polyhydroxyalkanoate containing a unit represented by the following chemical formula (96) as a monomer unit. It was confirmed that.

  Further, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (96) was a copolymer of 7 mol% for G unit and 93 mol% for H unit.

In addition, the acid value titration using the potentiometric titrator AT510 (manufactured by Kyoto Electronics Co., Ltd.) revealed that the sulfonic acid was methyl sulfonate because no peak derived from sulfonic acid was observed. . The average molecular weight of the obtained polymer is gel permeation chromatography (GPC; Tosoh HLC-8120, column; Polymer Laboratories PLgel 5μ MIXED-C, solvent; DMF / LiBr 0.1% (w / v), polystyrene conversion) It was evaluated by. As a result, the number average molecular weight M _n = 9700 and the weight average molecular weight M _w = 13800.

(Example 52)
Esterification reaction of polyhydroxyalkanoate composed of unit represented by chemical formula (79) synthesized in Example 34

  0.30 g of a polyhydroxyalkanoate copolymer (E: 8 mol%, F: 92 mol%) composed of the unit represented by the chemical formula (79) obtained in Example 34 was added to an eggplant flask, and 21.0 ml of chloroform and 7.0% of methanol were added. Add ml to dissolve and cool to 0 ° C. To this, 1.36 ml of a 2 mol / L trimethylsilyldiazomethane-hexane solution (manufactured by Aldrich) was added and stirred for 4 hours. After completion of the reaction, the solvent was removed by an evaporator, and then the polymer was recovered.

Further, 21.0 ml of chloroform and 7.0 ml of methanol were added to redissolve the polymer, and the solvent was distilled off with an evaporator. This operation was repeated three times. The polymer collected here was dried under reduced pressure to obtain 0.31 g of polymer. The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: heavy DMSO; measurement temperature: room temperature). ^From the result of ¹ H-NMR, since a peak derived from methyl sulfonate is seen at 3 to 4 ppm, the obtained polymer is a polyhydroxyalkanoate containing a unit represented by the following chemical formula (97) as a monomer unit. It was confirmed that.

Further, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (97) was a copolymer of 8 mol% for G unit and 92 mol% for H unit. In addition, the acid value titration using the potentiometric titrator AT510 (manufactured by Kyoto Electronics Co., Ltd.) revealed that the sulfonic acid was methyl sulfonate because no peak derived from sulfonic acid was observed. . The average molecular weight of the obtained polymer is gel permeation chromatography (GPC; Tosoh HLC-8120, column; Polymer Laboratories PLgel 5μ MIXED-C, solvent; DMF / LiBr 0.1% (w / v), polystyrene conversion) It was evaluated by. As a result, the number average molecular weight M _n = 11600 and the weight average molecular weight M _w = 16900.

(Example 53)
Esterification reaction of polyhydroxyalkanoate composed of unit represented by chemical formula (80) synthesized in Example 35

0.30 g of a polyhydroxyalkanoate copolymer (E: 8 mol%, F: 92 mol%) composed of the unit represented by the chemical formula (80) obtained in Example 35 was added to an eggplant flask, 21.0 ml of chloroform, 7.0% of methanol. Add ml to dissolve and cool to 0 ° C. To this was added 1.35 ml of a 2 mol / L trimethylsilyldiazomethane-hexane solution (manufactured by Aldrich), and the mixture was stirred for 4 hours. After completion of the reaction, the solvent was removed by an evaporator, and then the polymer was recovered. Further, 21.0 ml of chloroform and 7.0 ml of methanol were added to redissolve the polymer, and the solvent was distilled off with an evaporator. This operation was repeated three times. The polymer collected here was dried under reduced pressure to obtain 0.30 g of a polymer. The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: heavy DMSO; measurement temperature: room temperature). ^From the result of ¹ H-NMR, since a peak derived from methyl sulfonate is seen at 3 to 4 ppm, the obtained polymer is a polyhydroxyalkanoate containing a unit represented by the following chemical formula (98) as a monomer unit. It was confirmed that.

Further, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (98) was a copolymer of 8 mol% for G unit and 92 mol% for H unit. In addition, the acid value titration using the potentiometric titrator AT510 (manufactured by Kyoto Electronics Co., Ltd.) revealed that the sulfonic acid was methyl sulfonate because no peak derived from sulfonic acid was observed. . The average molecular weight of the obtained polymer is gel permeation chromatography (GPC; Tosoh HLC-8120, column; Polymer Laboratories PLgel 5μ MIXED-C, solvent; DMF / LiBr 0.1% (w / v), polystyrene conversion) It was evaluated by. As a result, the number average molecular weight M _n = 10500 and the weight average molecular weight M _w = 15500.

Example 54
Esterification reaction of polyhydroxyalkanoate composed of unit represented by chemical formula (83) synthesized in Example 38

0.30 g of a polyhydroxyalkanoate copolymer (E: 8 mol%, F: 92 mol%) composed of the unit represented by the chemical formula (83) obtained in Example 38 was added to an eggplant flask, and 21.0 ml of chloroform and 7.0% of methanol were added. Add ml to dissolve and cool to 0 ° C. To this was added 1.33 ml of a 2 mol / L trimethylsilyldiazomethane-hexane solution (manufactured by Aldrich), and the mixture was stirred for 4 hours. After completion of the reaction, the solvent was removed by an evaporator, and then the polymer was recovered. Further, 21.0 ml of chloroform and 7.0 ml of methanol were added to redissolve the polymer, and the solvent was distilled off with an evaporator. This operation was repeated three times. The polymer collected here was dried under reduced pressure to obtain 0.30 g of a polymer. The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: heavy DMSO; measurement temperature: room temperature). ^From the result of ¹ H-NMR, since a peak derived from methyl sulfonate is seen at 3 to 4 ppm, the obtained polymer is a polyhydroxyalkanoate containing a unit represented by the following chemical formula (99) as a monomer unit. It was confirmed that.

Further, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (99) was a copolymer of 8 mol% for G unit and 92 mol% for H unit. In addition, the acid value titration using the potentiometric titrator AT510 (manufactured by Kyoto Electronics Co., Ltd.) revealed that the sulfonic acid was methyl sulfonate because no peak derived from sulfonic acid was observed. . The average molecular weight of the obtained polymer is gel permeation chromatography (GPC; Tosoh HLC-8120, column; Polymer Laboratories PLgel 5μ MIXED-C, solvent; DMF / LiBr 0.1% (w / v), polystyrene conversion) It was evaluated by. As a result, the number average molecular weight M _n = 10700 and the weight average molecular weight M _w = 15900.

Example 55
Esterification reaction of polyhydroxyalkanoate composed of unit represented by chemical formula (86) synthesized in Example 41

0.30 g of a polyhydroxyalkanoate copolymer (E: 8 mol%, F: 92 mol%) composed of the unit represented by the chemical formula (86) obtained in Example 43 was added to an eggplant flask, and 21.0 ml of chloroform and 7.0% of methanol were added. Add ml to dissolve and cool to 0 ° C. To this, 1.30 ml of a 2 mol / L trimethylsilyldiazomethane-hexane solution (manufactured by Aldrich) was added and stirred for 4 hours. After completion of the reaction, the solvent was removed by an evaporator, and then the polymer was recovered. Further, 21.0 ml of chloroform and 7.0 ml of methanol were added to redissolve the polymer, and the solvent was distilled off with an evaporator. This operation was repeated three times. The polymer collected here was dried under reduced pressure to obtain 0.30 g of a polymer. The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: heavy DMSO; measurement temperature: room temperature). ^From the result of ¹ H-NMR, since a peak derived from methyl sulfonate is observed at 3 to 4 ppm, the obtained polymer is a polyhydroxyalkanoate containing a unit represented by the following chemical formula (100) as a monomer unit. It was confirmed that.

  Further, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (100) was a copolymer of 8 mol% for G unit and 92 mol% for H unit.

In addition, the acid value titration using the potentiometric titrator AT510 (manufactured by Kyoto Electronics Co., Ltd.) revealed that the sulfonic acid was methyl sulfonate because no peak derived from sulfonic acid was observed. . The average molecular weight of the obtained polymer is gel permeation chromatography (GPC; Tosoh HLC-8120, column; Polymer Laboratories PLgel 5μ MIXED-C, solvent; DMF / LiBr 0.1% (w / v), polystyrene conversion) It was evaluated by. As a result, the number average molecular weight M _n = 10900 and the weight average molecular weight M _w = 17200.

Example 56
Esterification reaction of polyhydroxyalkanoate composed of unit represented by chemical formula (88) synthesized in Example 43

  0.30 g of a polyhydroxyalkanoate copolymer (E: 8 mol%, F: 92 mol%) composed of the unit represented by the chemical formula (88) obtained in Example 43 was added to an eggplant flask, and 21.0 ml of chloroform and 7.0% of methanol were added. Add ml to dissolve and cool to 0 ° C. To this, 1.39 ml of a 2 mol / L trimethylsilyldiazomethane-hexane solution (manufactured by Aldrich) was added and stirred for 4 hours. After completion of the reaction, the solvent was removed by an evaporator, and then the polymer was recovered.

Further, 21.0 ml of chloroform and 7.0 ml of methanol were added to redissolve the polymer, and the solvent was distilled off with an evaporator. This operation was repeated three times. The polymer collected here was dried under reduced pressure to obtain 0.31 g of polymer. The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: heavy DMSO; measurement temperature: room temperature). ^From the result of ¹ H-NMR, since a peak derived from methyl sulfonate is seen at 3 to 4 ppm, the obtained polymer is a polyhydroxyalkanoate containing a unit represented by the following chemical formula (101) as a monomer unit. It was confirmed that.

Further, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (101) was a copolymer of 8 mol% for G unit and 92 mol% for H unit. In addition, the acid value titration using the potentiometric titrator AT510 (manufactured by Kyoto Electronics Co., Ltd.) revealed that the sulfonic acid was methyl sulfonate because no peak derived from sulfonic acid was observed. . The average molecular weight of the obtained polymer is gel permeation chromatography (GPC; Tosoh HLC-8120, column; Polymer Laboratories PLgel 5μ MIXED-C, solvent; DMF / LiBr 0.1% (w / v), polystyrene conversion) It was evaluated by. As a result, the number average molecular weight M _n = 9900 and the weight average molecular weight M _w = 14500.

(Example 57)
Esterification reaction of polyhydroxyalkanoate composed of unit represented by chemical formula (94) synthesized in Example 49

0.30 g of a polyhydroxyalkanoate copolymer (E: 7 mol%, F: 93 mol%) consisting of the unit represented by the chemical formula (94) obtained in Example 49 was added to an eggplant flask, and 21.0 ml of chloroform and 7.0% of methanol were added. Add ml to dissolve and cool to 0 ° C. To this was added 0.73 ml of a 2 mol / L trimethylsilyldiazomethane-hexane solution (manufactured by Aldrich), and the mixture was stirred for 4 hours. After completion of the reaction, the solvent was removed by an evaporator, and then the polymer was recovered. Further, 21.0 ml of chloroform and 7.0 ml of methanol were added to redissolve the polymer, and the solvent was distilled off with an evaporator. This operation was repeated three times. The polymer collected here was dried under reduced pressure to obtain 0.30 g of a polymer. The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: heavy DMSO; measurement temperature: room temperature). ^From the result of ¹ H-NMR, since a peak derived from methyl sulfonate is seen at 3 to 4 ppm, the obtained polymer is a polyhydroxyalkanoate containing a unit represented by the following chemical formula (102) as a monomer unit. It was confirmed that.

Further, it was confirmed that the unit of polyhydroxyalkanoate represented by the chemical formula (102) was a copolymer of 7 mol% for G unit and 93 mol% for H unit. In addition, the acid value titration using the potentiometric titrator AT510 (manufactured by Kyoto Electronics Co., Ltd.) revealed that the sulfonic acid was methyl sulfonate because no peak derived from sulfonic acid was observed. . The average molecular weight of the obtained polymer is gel permeation chromatography (GPC; Tosoh HLC-8120, column; Polymer Laboratories PLgel 5μ MIXED-C, solvent; DMF / LiBr 0.1% (w / v), polystyrene conversion) It was evaluated by. As a result, the number average molecular weight M _n = 11200 and the weight average molecular weight M _w = 23000.

  (Example 58)

[Polyester Synthesis Using Tetrahydro-6- (2-propenyl) -2H-pyran-2-one represented by Chemical Formula (103)]
Tetrahydro-6- (2-propenyl) -2H-pyran-2-one 1.40 g (10.0 mmol), 2 mol / L di-iso-propylzinc in toluene solution 20 μl, 0.01 mol / L p-tert-butylbenzyl 8 ml of a toluene solution of alcohol was placed in a polymerization ampule, dried under reduced pressure for 1 hour and purged with nitrogen, then sealed under reduced pressure and heated to 150 ° C. to perform ring-opening polymerization. The reaction was terminated after 10 hours and cooled. The obtained polymer was dissolved in chloroform and reprecipitated in 10 times the amount of methanol required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 0.46 g of polymer. As a result of conducting NMR analysis under the same conditions as in Example 6 in order to specify the structure of the obtained polymer, it was confirmed that the monomer unit was a polyhydroxyalkanoate composed of a unit represented by the following chemical formula (104) It was done.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight was Mn = 10100, and the weight average molecular weight was Mw = 1100.

(Example 59)
[Polyester synthesis using tetrahydro-6- (2-propenyl) -2H-pyran-2-one and L-lactide]
Tetrahydro-6- (2-propenyl) -2H-pyran-2-one 0.42 g (3.0 mmol), L-lactide 1.01 g (7.0 mmol), 2 mol / L di-iso-propylzinc in toluene solution 20 μl, 0.01 8 ml of toluene solution of mol / L of p-tert-butylbenzyl alcohol was charged into a polymerization ampule, dried under reduced pressure for 1 hour, purged with nitrogen, sealed under reduced pressure, heated to 150 ° C. and opened. Ring polymerization was performed. The reaction was terminated after 10 hours and cooled. The obtained polymer was dissolved in chloroform and reprecipitated in 10 times the amount of methanol required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 0.84 g of polymer. As a result of conducting NMR analysis under the same conditions as in Example 6 to specify the structure of the obtained polymer, it is a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (105) as a monomer unit. It was confirmed. Further, it was confirmed that the ratio of the monomer unit was 17 mol% for the A unit and 83 mol% for the B unit.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 68100 and the weight average molecular weight Mw = 104200.

(Example 60)
[Polyester synthesis using tetrahydro-6- (2-propenyl) -2H-pyran-2-one and L-lactide]
Tetrahydro-6- (2-propenyl) -2H-pyran-2-one 0.28 g (2.0 mmol), L-lactide 1.15 g (8.0 mmol), 2 mol / L di-iso-propylzinc in toluene solution 20 μl, 0.01 8 ml of toluene solution of mol / L of p-tert-butylbenzyl alcohol was placed in a polymerization ampule, dried under reduced pressure for 1 hour, purged with nitrogen, sealed under reduced pressure, heated to 150 ° C., and opened. Ring polymerization was performed. The reaction was terminated after 10 hours and cooled. The obtained polymer was dissolved in chloroform and reprecipitated in 10 times the amount of methanol required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 1.06 g of polymer. As a result of performing NMR analysis under the same conditions as in Example 6 in order to specify the structure of the obtained polymer, it is a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (106) as a monomer unit. It was confirmed. Moreover, it was confirmed that the ratio of the monomer unit was 11 mol% of A unit and 89 mol% of B unit.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 142500 and the weight average molecular weight Mw = 233700.

(Example 61)
[Polyester synthesis using tetrahydro-6- (2-propenyl) -2H-pyran-2-one and mandelide]
Tetrahydro-6- (2-propenyl) -2H-pyran-2-one 0.28 g (2.0 mmol), mandelide 2.15 g (8.0 mmol), 2 mol / L di-iso-propylzinc in toluene solution 20 μl, 0.01 mol / 8 ml of toluene solution of p-tert-butylbenzyl alcohol in L was charged into a polymerization ampule, dried under reduced pressure for 1 hour, purged with nitrogen, sealed under reduced pressure, heated to 150 ° C., and ring-opening polymerization. Went. The reaction was terminated after 10 hours and cooled. The obtained polymer was dissolved in chloroform and reprecipitated in 10 times the amount of methanol required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 1.59 g of polymer. As a result of performing NMR analysis under the same conditions as in Example 6 in order to specify the structure of the obtained polymer, it is a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (107) as a monomer unit. It was confirmed. Further, it was confirmed that the proportion of the monomer units was 12 mol% for the A unit and 88 mol% for the B unit.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 12000 and the weight average molecular weight Mw = 24200.

  (Example 62)

[Polyester Synthesis Using Tetrahydro-6- (4-pentenyl) -2H-pyran-2-one represented by Chemical Formula (108) and L-lactide]
Tetrahydro-6- (4-pentenyl) -2H-pyran-2-one 0.34 g (2.0 mmol), L-lactide 1.15 g (8.0 mmol), 2 mol / L di-iso-propylzinc in toluene solution 20 μl, 0.01 8 ml of toluene solution of mol / L of p-tert-butylbenzyl alcohol was charged into a polymerization ampule, dried under reduced pressure for 1 hour, purged with nitrogen, sealed under reduced pressure, heated to 150 ° C. and opened. Ring polymerization was performed. The reaction was terminated after 10 hours and cooled. The obtained polymer was dissolved in chloroform and reprecipitated in 10 times the amount of methanol required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 0.89 g of polymer. As a result of conducting NMR analysis under the same conditions as in Example 6 in order to specify the structure of the obtained polymer, it is a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (109) as a monomer unit. It was confirmed. Moreover, it was confirmed that the ratio of the monomer unit was 8 mol% of A unit and 92 mol% of B unit.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 49000 and the weight average molecular weight Mw = 88200.

(Example 63)
[Polyester synthesis using tetrahydro-6- (4-pentenyl) -2H-pyran-2-one and δ-valerolactone]
Tetrahydro-6- (4-pentenyl) -2H-pyran-2-one 0.34 g (2.0 mmol), δ-valerolactone 0.80 g (8.0 mmol), 2 mol / L di-iso-propylzinc in toluene solution 20 μl, A toluene solution of 0.01 mol / L p-tert-butylbenzyl alcohol in toluene was charged into a polymerization ampule, dried under reduced pressure for 1 hour, purged with nitrogen, sealed under reduced pressure, and heated to 150 ° C. Ring-opening polymerization was performed. The reaction was terminated after 10 hours and cooled. The obtained polymer was dissolved in chloroform and reprecipitated in 10 times the amount of methanol required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 0.89 g of polymer. As a result of conducting NMR analysis under the same conditions as in Example 6 in order to specify the structure of the obtained polymer, it is a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (110) as a monomer unit. It was confirmed. Moreover, it was confirmed that the ratio of the monomer unit was 8 mol% of A unit and 92 mol% of B unit.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 8900 and the weight average molecular weight Mw = 11900.

  (Example 64)

[Polyester synthesis using dihydro-5- (2-propenyl) -2 (3H) -furanone represented by chemical formula (111) and L-lactide]
Dihydro-5- (2-propenyl) -2 (3H) -furanone 0.63 g (5.0 mmol), L-lactide 0.72 g (5.0 mmol), 2 mol / L diethylzinc in toluene 20 μl, 0.01 mol / L p 8 ml of toluene solution of tert-butylbenzyl alcohol was charged into a polymerization ampule, dried under reduced pressure for 1 hour and purged with nitrogen, then sealed under reduced pressure and heated to 150 ° C. to perform ring-opening polymerization. . The reaction was terminated after 10 hours and cooled. The obtained polymer was dissolved in chloroform and reprecipitated in 10 times the amount of methanol required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 0.58 g of polymer. As a result of conducting NMR analysis under the same conditions as in Example 6 in order to specify the structure of the obtained polymer, it is a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (112) as a monomer unit. It was confirmed. Moreover, it was confirmed that the ratio of the monomer unit was A unit 7 mol% and B unit 93 mol%.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 7200 and the weight average molecular weight Mw = 9300.

  Example 65

[Polyester Synthesis Using Dihydro-5- (4-pentenyl) -2 (3H) -furanone represented by Chemical Formula (113) and δ-valerolactone]
Dihydro-5- (4-pentenyl) -2 (3H) -furanone 0.77 g (5.0 mmol), δ-valerolactone 0.40 g (5.0 mmol), 2 mol / L diethylzinc in toluene 20 μl, 0.01 mol / L A toluene solution of p-tert-butylbenzyl alcohol in an amount of 8 ml was charged into a polymerization ampule, dried under reduced pressure for 1 hour, purged with nitrogen, sealed under reduced pressure, heated to 150 ° C., and subjected to ring-opening polymerization. It was. The reaction was terminated after 10 hours and cooled. The obtained polymer was dissolved in chloroform and reprecipitated in 10 times the amount of methanol required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 0.39 g of polymer. As a result of performing NMR analysis under the same conditions as in Example 6 in order to specify the structure of the obtained polymer, it is a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (114) as a monomer unit. It was confirmed. Moreover, it was confirmed that the ratio of the monomer unit was 6 mol% of A unit and 94 mol% of B unit.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 6400 and the weight average molecular weight Mw = 8600.

  Example 66

[Polyester Synthesis Using Dihydro-5- (5-hexenyl) -2 (3H) -furanone represented by Chemical Formula (115) and Glycolide]
Dihydro-5- (5-hexenyl) -2 (3H) -furanone 0.84 g (5.0 mmol), glycolide 0.58 g (5.0 mmol), 2 mol / L diethylzinc in toluene 20 μl, 0.01 mol / L p-tert -8 ml of a toluene solution of butylbenzyl alcohol was charged into a polymerization ampule, dried under reduced pressure for 1 hour and purged with nitrogen, then sealed under reduced pressure and heated to 150 ° C to perform ring-opening polymerization. The reaction was terminated after 10 hours and cooled. The obtained polymer was dissolved in chloroform and reprecipitated in 10 times the amount of methanol required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 0.53 g of polymer. As a result of conducting NMR analysis under the same conditions as in Example 6 in order to specify the structure of the obtained polymer, it was a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (116) as a monomer unit. It was confirmed. Moreover, it was confirmed that the ratio of the monomer unit was A unit 7 mol% and B unit 93 mol%.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 6800 and the weight average molecular weight Mw = 8800.

Example 67
Oxidation reaction of polyhydroxyalkanoate composed of unit represented by chemical formula (106) synthesized in Example 60

  0.50 g of a polyhydroxyalkanoate copolymer (A: 11 mol%, B: 89 mol%) composed of the unit represented by the chemical formula (106) obtained in Example 60 was added to an eggplant flask and dissolved by adding 30 ml of acetone. did. This was placed in an ice bath, 5 ml of acetic acid and 0.55 g of 18-crown-6-ether were added and stirred. Next, 0.44 g of potassium permanganate was slowly added in an ice bath, stirred for 2 hours in an ice bath, and further stirred for 18 hours at room temperature. After completion of the reaction, 60 ml of ethyl acetate was added, and 45 ml of water was further added. Sodium bisulfite was then added until the peracid was removed. Thereafter, the liquidity was adjusted to pH = 1 with 1.0 mol / L (1.0 N) hydrochloric acid. The organic layer was extracted and washed 3 times with 1.0 mol / L hydrochloric acid. After recovering the organic layer, the solvent was distilled off to recover the crude polymer. Next, it was washed with 50 ml of water and 50 ml of methanol, and further washed with 50 ml of water three times, and then the polymer was recovered. Next, it was dissolved in THF and reprecipitated in 50 times the amount of THF required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 0.43 g of polymer. As a result of conducting NMR analysis under the same conditions as in Example 6 to identify the structure of the obtained polymer, it was confirmed that the monomer unit was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (117) It was done.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 98500 and the weight average molecular weight Mw = 166400.

  Furthermore, in order to calculate the unit of the obtained polyhydroxyalkanoate, it calculated by methyl-esterifying the carboxyl group in the side chain terminal of polyhydroxyalkanoate using trimethylsilyldiazomethane. 30 mg of the target polyhydroxyalkanoate was added to a 100 ml eggplant flask, and dissolved by adding 2.1 ml of chloroform and 0.7 ml of methanol. To this was added 0.5 ml of a 2 mol / L trimethylsilyldiazomethane-hexane solution, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the solvent was distilled off and the polymer was recovered. The polymer was recovered after washing with 50 ml of methanol. 29 mg of polyhydroxyalkanoate was obtained by drying under reduced pressure. NMR analysis was performed using the same method as in Example 6. As a result, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (117) was a copolymer of 10 mol% for the C unit and 90 mol% for the D unit.

Example 68
Oxidation reaction of polyhydroxyalkanoate composed of unit represented by chemical formula (107) synthesized in Example 61

  0.50 g of a polyhydroxyalkanoate copolymer (A: 12 mol%, B: 88 mol%) composed of the unit represented by the chemical formula (107) obtained in Example 61 was added to an eggplant flask and dissolved by adding 30 ml of acetone. did. This was placed in an ice bath, 5 ml of acetic acid and 0.35 g of 18-crown-6-ether were added and stirred. Next, 0.28 g of potassium permanganate was slowly added in an ice bath, stirred for 2 hours in an ice bath, and further stirred for 18 hours at room temperature. After completion of the reaction, 60 ml of ethyl acetate was added, and 45 ml of water was further added. Sodium bisulfite was then added until the peracid was removed. Thereafter, the liquidity was adjusted to pH = 1 with 1.0 mol / L (1.0 N) hydrochloric acid. The organic layer was extracted and washed 3 times with 1.0 mol / L hydrochloric acid. After recovering the organic layer, the solvent was distilled off to recover the crude polymer. Next, it was washed with 50 ml of water and 50 ml of methanol, and further washed with 50 ml of water three times, and then the polymer was recovered. Next, it was dissolved in THF and reprecipitated in 50 times the amount of THF required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 0.44 g of polymer. As a result of conducting NMR analysis under the same conditions as in Example 6 to identify the structure of the obtained polymer, it was confirmed that the monomer unit was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (118) It was done.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 8400 and the weight average molecular weight Mw = 16300.

  Furthermore, in order to calculate the unit of the obtained polyhydroxyalkanoate, it calculated by methyl-esterifying the carboxyl group in the side chain terminal of polyhydroxyalkanoate using trimethylsilyldiazomethane. 30 mg of the target polyhydroxyalkanoate was added to a 100 ml eggplant flask, and dissolved by adding 2.1 ml of chloroform and 0.7 ml of methanol. To this was added 0.5 ml of a 2 mol / L trimethylsilyldiazomethane-hexane solution, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the solvent was distilled off and the polymer was recovered. The polymer was recovered after washing with 50 ml of methanol. By drying under reduced pressure, 30 mg of polyhydroxyalkanoate was obtained.

  NMR analysis was performed using the same method as in Example 6. As a result, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (118) was a copolymer of 11 mol% for the C unit and 89 mol% for the D unit.

(Example 69)
Oxidation reaction of polyhydroxyalkanoate composed of unit represented by chemical formula (109) synthesized in Example 62

  0.50 g of a polyhydroxyalkanoate copolymer (A: 8 mol%, B: 92 mol%) consisting of the unit represented by the chemical formula (109) obtained in Example 62 was added to an eggplant flask and dissolved by adding 30 ml of acetone. did. This was placed in an ice bath, and 5 ml of acetic acid and 0.40 g of 18-crown-6-ether were added and stirred. Next, 0.32 g of potassium permanganate was slowly added in an ice bath, stirred for 2 hours in an ice bath, and further stirred for 18 hours at room temperature. After completion of the reaction, 60 ml of ethyl acetate was added, and 45 ml of water was further added. Sodium bisulfite was then added until the peracid was removed. Thereafter, the liquidity was adjusted to pH = 1 with 1.0 mol / L (1.0 N) hydrochloric acid. The organic layer was extracted and washed 3 times with 1.0 mol / L hydrochloric acid. After recovering the organic layer, the solvent was distilled off to recover the crude polymer. Next, it was washed with 50 ml of water and 50 ml of methanol, and further washed with 50 ml of water three times, and then the polymer was recovered. Next, it was dissolved in THF and reprecipitated in 50 times the amount of THF required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 0.43 g of polymer. As a result of conducting NMR analysis under the same conditions as in Example 6 to identify the structure of the obtained polymer, it was confirmed that the monomer unit was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (119) It was done.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 32500 and the weight average molecular weight Mw = 59500.

  Furthermore, in order to calculate the unit of the obtained polyhydroxyalkanoate, it calculated by methyl-esterifying the carboxyl group in the side chain terminal of polyhydroxyalkanoate using trimethylsilyldiazomethane. 30 mg of the target polyhydroxyalkanoate was added to a 100 ml eggplant flask, and dissolved by adding 2.1 ml of chloroform and 0.7 ml of methanol. To this was added 0.5 ml of a 2 mol / L trimethylsilyldiazomethane-hexane solution, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the solvent was distilled off and the polymer was recovered. The polymer was recovered after washing with 50 ml of methanol. By drying under reduced pressure, 28 mg of polyhydroxyalkanoate was obtained.

  NMR analysis was performed using the same method as in Example 6. As a result, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (119) was a copolymer of 7 mol% for the C unit and 93 mol% for the D unit.

Example 70
Oxidation reaction of polyhydroxyalkanoate composed of unit represented by chemical formula (110) synthesized in Example 63

  0.50 g of a polyhydroxyalkanoate copolymer (A: 8 mol%, B: 92 mol%) comprising the unit represented by the chemical formula (110) obtained in Example 63 was added to an eggplant flask, and dissolved by adding 30 ml of acetone. did. This was placed in an ice bath, and 5 ml of acetic acid and 0.30 g of 18-crown-6-ether were added and stirred. Next, 0.24 g of potassium permanganate was slowly added in an ice bath, stirred in the ice bath for 2 hours, and further stirred at room temperature for 18 hours. After completion of the reaction, 60 ml of ethyl acetate was added, and 45 ml of water was further added. Sodium bisulfite was then added until the peracid was removed. Thereafter, the liquidity was adjusted to pH = 1 with 1.0 mol / L (1.0 N) hydrochloric acid. The organic layer was extracted and washed 3 times with 1.0 mol / L hydrochloric acid. After recovering the organic layer, the solvent was distilled off to recover the crude polymer. Next, it was washed with 50 ml of water and 50 ml of methanol, and further washed with 50 ml of water three times, and then the polymer was recovered. Next, it was dissolved in THF and reprecipitated in 50 times the amount of THF required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 0.42 g of polymer. As a result of conducting NMR analysis under the same conditions as in Example 6 to identify the structure of the obtained polymer, it was confirmed that the monomer unit was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (120) It was done.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 7300 and the weight average molecular weight Mw = 9900.

  Furthermore, in order to calculate the unit of the obtained polyhydroxyalkanoate, it calculated by methyl-esterifying the carboxyl group in the side chain terminal of polyhydroxyalkanoate using trimethylsilyldiazomethane. 30 mg of the target polyhydroxyalkanoate was added to a 100 ml eggplant flask, and dissolved by adding 2.1 ml of chloroform and 0.7 ml of methanol. To this was added 0.5 ml of a 2 mol / L trimethylsilyldiazomethane-hexane solution, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the solvent was distilled off and the polymer was recovered. The polymer was recovered after washing with 50 ml of methanol. By drying under reduced pressure, 27 mg of polyhydroxyalkanoate was obtained.

  NMR analysis was performed using the same method as in Example 6. As a result, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (120) was a copolymer of 7 mol% for the C unit and 93 mol% for the D unit.

Example 71
Oxidation reaction of polyhydroxyalkanoate composed of unit represented by chemical formula (112) synthesized in Example 64

  0.50 g of a polyhydroxyalkanoate copolymer (A: 7 mol%, B: 93 mol%) composed of the unit represented by the chemical formula (112) obtained in Example 64 was added to an eggplant flask, and dissolved by adding 30 ml of acetone. did. This was placed in an ice bath, and 5 ml of acetic acid and 0.37 g of 18-crown-6-ether were added and stirred. Next, 0.29 g of potassium permanganate was slowly added in an ice bath, stirred for 2 hours in an ice bath, and further stirred for 18 hours at room temperature. After completion of the reaction, 60 ml of ethyl acetate was added, and 45 ml of water was further added. Sodium bisulfite was then added until the peracid was removed. Thereafter, the liquidity was adjusted to pH = 1 with 1.0 mol / L (1.0 N) hydrochloric acid. The organic layer was extracted and washed 3 times with 1.0 mol / L hydrochloric acid. After recovering the organic layer, the solvent was distilled off to recover the crude polymer. Next, it was washed with 50 ml of water and 50 ml of methanol, and further washed with 50 ml of water three times, and then the polymer was recovered. Next, it was dissolved in THF and reprecipitated in 50 times the amount of THF required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 0.43 g of polymer. As a result of conducting NMR analysis under the same conditions as in Example 6 to identify the structure of the obtained polymer, it was confirmed that the monomer unit was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (121) It was done.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 6400 and the weight average molecular weight Mw = 8400.

  Furthermore, in order to calculate the unit of the obtained polyhydroxyalkanoate, it calculated by methyl-esterifying the carboxyl group in the side chain terminal of polyhydroxyalkanoate using trimethylsilyldiazomethane. 30 mg of the target polyhydroxyalkanoate was added to a 100 ml eggplant flask, and dissolved by adding 2.1 ml of chloroform and 0.7 ml of methanol. To this was added 0.5 ml of a 2 mol / L trimethylsilyldiazomethane-hexane solution, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the solvent was distilled off and the polymer was recovered. The polymer was recovered after washing with 50 ml of methanol. By drying under reduced pressure, 27 mg of polyhydroxyalkanoate was obtained.

  NMR analysis was performed using the same method as in Example 6. As a result, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (121) was a copolymer of 7 mol% for the C unit and 93 mol% for the D unit.

(Example 72)
Oxidation reaction of polyhydroxyalkanoate composed of unit represented by chemical formula (116) synthesized in Example 66

  0.50 g of a polyhydroxyalkanoate copolymer (A: 7 mol%, B: 93 mol%) consisting of the unit represented by the chemical formula (116) obtained in Example 66 was added to an eggplant flask and dissolved by adding 30 ml of acetone. did. This was placed in an ice bath, and 5 ml of acetic acid and 0.42 g of 18-crown-6-ether were added and stirred. Next, 0.34 g of potassium permanganate was slowly added in an ice bath, stirred for 2 hours in an ice bath, and further stirred for 18 hours at room temperature. After completion of the reaction, 60 ml of ethyl acetate was added, and 45 ml of water was further added. Sodium bisulfite was then added until the peracid was removed. Thereafter, the liquidity was adjusted to pH = 1 with 1.0 mol / L (1.0 N) hydrochloric acid. The organic layer was extracted and washed 3 times with 1.0 mol / L hydrochloric acid. After recovering the organic layer, the solvent was distilled off to recover the crude polymer. Next, it was washed with 50 ml of water and 50 ml of methanol, and further washed with 50 ml of water three times, and then the polymer was recovered. Next, it was dissolved in THF and reprecipitated in 50 times the amount of THF required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 0.45 g of polymer. As a result of conducting NMR analysis under the same conditions as in Example 6 to specify the structure of the obtained polymer, it was confirmed that the monomer unit was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (122) It was done.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 6200 and the weight average molecular weight Mw = 8400.

  Furthermore, in order to calculate the unit of the obtained polyhydroxyalkanoate, it calculated by methyl-esterifying the carboxyl group in the side chain terminal of polyhydroxyalkanoate using trimethylsilyldiazomethane. 30 mg of the target polyhydroxyalkanoate was added to a 100 ml eggplant flask, and dissolved by adding 2.1 ml of chloroform and 0.7 ml of methanol. To this was added 0.5 ml of a 2 mol / L trimethylsilyldiazomethane-hexane solution, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the solvent was distilled off and the polymer was recovered. The polymer was recovered after washing with 50 ml of methanol. By drying under reduced pressure, 28 mg of polyhydroxyalkanoate was obtained.

  NMR analysis was performed using the same method as in Example 6. As a result, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (122) was a copolymer of 7 mol% for the C unit and 93 mol% for the D unit.

(Example 73)
Condensation reaction between a polyhydroxyalkanoate composed of the unit represented by the chemical formula (117) synthesized in Example 67 and 2-aminobenzenesulfonic acid

Under a nitrogen atmosphere, 0.40 g of a polymer synthesized with a polyhydroxyalkanoate copolymer (C: 10 mol%, D: 90 mol%) comprising the unit represented by the chemical formula (117) obtained in Example 67 was obtained. 0.43 g of benzenesulfonic acid was placed in a 100 ml three-necked flask, 15.0 ml of pyridine was added and stirred, and then 1.29 ml of triphenyl phosphite was added and heated at 120 ° C. for 6 hours. After completion of the reaction, it was recovered by reprecipitation in 150 ml of ethanol. The obtained polymer was washed with 1.0 mol / L (= 1.0 N) hydrochloric acid for 1 day, then washed by stirring in water for 1 day, and dried under reduced pressure to obtain 0.34 g of polymer. The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: heavy DMSO; measurement temperature: room temperature), Fourier transform-infrared absorption Analysis was performed by (FT-IR) spectrum (Nicolet AVATAR360FT-IR). As a result of IR measurement, the peak of 1695 cm ⁻¹ derived from carboxylic acid decreased, and a new peak derived from the amide group was observed at 1658 cm ⁻¹ .

^From the result of ¹ H-NMR, since the peak derived from the aromatic ring of 2-aminobenzenesulfonic acid structure is shifted, the obtained polymer has a unit represented by the following chemical formula (123) as a monomer unit. It was confirmed to be a polyhydroxyalkanoate containing.

Further, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (123) was a copolymer of 10 mol% for the E unit and 90 mol% for the F unit. The average molecular weight of the obtained polymer is gel permeation chromatography (GPC; Tosoh HLC-8120, column; Polymer Laboratories PLgel 5μ MIXED-C, solvent; DMF / LiBr 0.1% (w / v), polystyrene conversion) It was evaluated by. As a result, the number average molecular weight M _n = 83500 and the weight average molecular weight M _w = 146500.

Example 74
Condensation reaction between a polyhydroxyalkanoate composed of the unit represented by the chemical formula (118) synthesized in Example 68 and 4-methoxyaniline-2-sulfonic acid

Under a nitrogen atmosphere, 0.40 g of a polymer synthesized with a polyhydroxyalkanoate copolymer (C: 11 mol%, D: 89 mol%) comprising the unit represented by the chemical formula (118) obtained in Example 68 was obtained. After placing 0.33 g of aniline-2-sulfonic acid in a 100 ml three-necked flask and adding 15.0 ml of pyridine and stirring, 0.84 ml of triphenyl phosphite was added and heated at 120 ° C. for 6 hours. After completion of the reaction, it was recovered by reprecipitation in 150 ml of ethanol. The obtained polymer was washed with 1.0 mol / L (= 1.0 N) hydrochloric acid for 1 day, then washed by stirring in water for 1 day, and dried under reduced pressure to obtain 0.35 g of polymer. The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: heavy DMSO; measurement temperature: room temperature), Fourier transform-infrared absorption Analysis was performed by (FT-IR) spectrum (Nicolet AVATAR360FT-IR). As a result of IR measurement, the peak of 1695 cm ⁻¹ derived from carboxylic acid decreased, and a new peak derived from the amide group was observed at 1658 cm ⁻¹ .

^From the result of ¹ H-NMR, since the peak derived from the aromatic ring having a 4-methoxyaniline-2-sulfonic acid structure is shifted, the obtained polymer is represented by the following chemical formula (124) as a monomer unit. It was confirmed that this was a polyhydroxyalkanoate containing unit.

Further, it was confirmed that the unit of polyhydroxyalkanoate represented by the chemical formula (124) was a copolymer of 11 mol% for the E unit and 89 mol% for the F unit. The average molecular weight of the obtained polymer is gel permeation chromatography (GPC; Tosoh HLC-8120, column; Polymer Laboratories PLgel 5μ MIXED-C, solvent; DMF / LiBr 0.1% (w / v), polystyrene conversion) It was evaluated by. As a result, the number average molecular weight M _n = 8400 and the weight average molecular weight M _w = 16400.

(Example 75)
Condensation reaction between a polyhydroxyalkanoate composed of the unit represented by the chemical formula (119) synthesized in Example 69 and 2-amino-1-naphthalenesulfonic acid

Under a nitrogen atmosphere, 0.40 g of a polymer synthesized with a polyhydroxyalkanoate copolymer (C: 7 mol%, D: 93 mol%) consisting of the unit represented by the chemical formula (119) obtained in Example 69 was obtained. -1-Naphthalenesulfonic acid 0.39 g was placed in a 100 ml three-necked flask, 15.0 ml of pyridine was added and stirred, 0.91 ml of triphenyl phosphite was added, and the mixture was heated at 120 ° C. for 6 hours. After completion of the reaction, it was recovered by reprecipitation in 150 ml of ethanol. The obtained polymer was washed with 1.0 mol / L (= 1.0 N) hydrochloric acid for 1 day, then washed by stirring in water for 1 day, and dried under reduced pressure to obtain 0.34 g of polymer. The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: heavy DMSO; measurement temperature: room temperature), Fourier transform-infrared absorption Analysis was performed by (FT-IR) spectrum (Nicolet AVATAR360FT-IR). As a result of IR measurement, the peak of 1695 cm ⁻¹ derived from carboxylic acid decreased, and a new peak derived from the amide group was observed at 1658 cm ⁻¹ .

^From the result of ¹ H-NMR, since the peak derived from the aromatic ring of 2-amino-1-naphthalenesulfonic acid structure is shifted, the obtained polymer is represented by the following chemical formula (125) as a monomer unit. It was confirmed that this was a polyhydroxyalkanoate containing unit.

Further, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (125) was a copolymer of 7 mol% for the E unit and 93 mol% for the F unit. The average molecular weight of the obtained polymer is gel permeation chromatography (GPC; Tosoh HLC-8120, column; Polymer Laboratories PLgel 5μ MIXED-C, solvent; DMF / LiBr 0.1% (w / v), polystyrene conversion) It was evaluated by. As a result, the number average molecular weight M _n = 30100 and the weight average molecular weight M _w = 54500.

(Example 76)
Condensation reaction of polyhydroxyalkanoate composed of the unit represented by the chemical formula (120) synthesized in Example 70 and 2-amino-2-methylpropanesulfonic acid

Under a nitrogen atmosphere, 0.40 g of a polymer synthesized with a polyhydroxyalkanoate copolymer (C: 7 mol%, D: 93 mol%) consisting of the unit represented by the chemical formula (120) obtained in Example 70 was obtained. After putting 0.20 g of -2-methylpropanesulfonic acid in a 100 ml three-necked flask and adding 15.0 ml of pyridine and stirring, 0.69 ml of triphenyl phosphite was added and heated at 120 ° C. for 6 hours. After completion of the reaction, it was recovered by reprecipitation in 150 ml of ethanol. The obtained polymer was washed with 1.0 mol / L (= 1.0 N) hydrochloric acid for 1 day, then washed by stirring in water for 1 day, and dried under reduced pressure to obtain 0.32 g of polymer. The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: heavy DMSO; measurement temperature: room temperature), Fourier transform-infrared absorption Analysis was performed by (FT-IR) spectrum (Nicolet AVATAR360FT-IR). As a result of IR measurement, the peak at 1695 cm ⁻¹ derived from carboxylic acid decreased, and a new peak derived from the amide group was observed at 1668 cm ⁻¹ .

^From the result of ¹ H-NMR, since the peak derived from methylene having a 2-amino-2-methylpropanesulfonic acid structure is shifted, the obtained polymer is represented by the following chemical formula (126) as a monomer unit. It was confirmed that this was a polyhydroxyalkanoate containing unit.

Further, it was confirmed that the unit of polyhydroxyalkanoate represented by the chemical formula (126) was a copolymer of 7 mol% for E unit and 93 mol% for F unit. The average molecular weight of the obtained polymer is gel permeation chromatography (GPC; Tosoh HLC-8120, column; Polymer Laboratories PLgel 5μ MIXED-C, solvent; DMF / LiBr 0.1% (w / v), polystyrene conversion) It was evaluated by. As a result, the number average molecular weight M _n = 7000 and the weight average molecular weight M _w = 9700.

Example 77
Condensation reaction of polyhydroxyalkanoate composed of the unit represented by the chemical formula (121) synthesized in Example 71 and 2-aminobenzenesulfonic acid phenyl ester

Under a nitrogen atmosphere, 0.40 g of a polymer synthesized with a polyhydroxyalkanoate copolymer (C: 7 mol%, D: 93 mol%) consisting of the unit represented by the chemical formula (121) obtained in Example 71 was obtained. Benzenesulfonic acid phenyl ester 0.45 g was placed in a 100 ml three-necked flask, 15.0 ml of pyridine was added and stirred, 0.95 ml of triphenyl phosphite was added, and the mixture was heated at 120 ° C. for 6 hours. After completion of the reaction, it was recovered by reprecipitation in 150 ml of ethanol. The obtained polymer was washed with 1.0 mol / L (= 1.0 N) hydrochloric acid for 1 day, then washed by stirring in water for 1 day, and dried under reduced pressure to obtain 0.36 g of polymer. The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: heavy DMSO; measurement temperature: room temperature), Fourier transform-infrared absorption Analysis was performed by (FT-IR) spectrum (Nicolet AVATAR360FT-IR). As a result of IR measurement, the peak of 1695 cm ⁻¹ derived from carboxylic acid decreased, and a new peak derived from the amide group was observed at 1658 cm ⁻¹ .

^From the result of ¹ H-NMR, since the peak derived from the aromatic ring of the 2-aminobenzenesulfonic acid phenyl ester structure is shifted, the obtained polymer is represented by the following chemical formula (127) as a monomer unit. It was confirmed to be a polyhydroxyalkanoate containing unit.

Further, it was confirmed that the unit of polyhydroxyalkanoate represented by the chemical formula (127) was a copolymer of 7 mol% for E unit and 93 mol% for F unit. The average molecular weight of the obtained polymer is gel permeation chromatography (GPC; Tosoh HLC-8120, column; Polymer Laboratories PLgel 5μ MIXED-C, solvent; DMF / LiBr 0.1% (w / v), polystyrene conversion) It was evaluated by. As a result, the number average molecular weight M _n = 6200 and the weight average molecular weight M _w = 8200.

(Example 78)
Condensation reaction between polyhydroxyalkanoate composed of the unit represented by the chemical formula (122) synthesized in Example 72 and taurine

Under a nitrogen atmosphere, 0.40 g of a polymer synthesized with a polyhydroxyalkanoate copolymer (C: 7 mol%, D: 93 mol%) consisting of the unit represented by the chemical formula (122) obtained in Example 72, and 0.26 g of taurine Was added to 1 ml of pyridine and stirred, and then 1.09 ml of triphenyl phosphite was added and heated at 120 ° C. for 6 hours. After completion of the reaction, it was recovered by reprecipitation in 150 ml of ethanol. The obtained polymer was washed with 1.0 mol / L (= 1.0 N) hydrochloric acid for 1 day, then washed by stirring in water for 1 day, and dried under reduced pressure to obtain 0.34 g of polymer. The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: heavy DMSO; measurement temperature: room temperature), Fourier transform-infrared absorption Analysis was performed by (FT-IR) spectrum (Nicolet AVATAR360FT-IR). As a result of IR measurement, the peak at 1695 cm ⁻¹ derived from carboxylic acid decreased, and a new peak derived from the amide group was observed at 1668 cm ⁻¹ .

^From the result of ¹ H-NMR, since the peak derived from methylene having a taurine structure is shifted, the obtained polymer is a polyhydroxyalkanoate containing a unit represented by the following chemical formula (128) as a monomer unit. It was confirmed that there was.

Further, it was confirmed that the unit of polyhydroxyalkanoate represented by the chemical formula (128) was a copolymer of 7 mol% for the E unit and 93 mol% for the F unit. The average molecular weight of the obtained polymer is gel permeation chromatography (GPC; Tosoh HLC-8120, column; Polymer Laboratories PLgel 5μ MIXED-C, solvent; DMF / LiBr 0.1% (w / v), polystyrene conversion) It was evaluated by. As a result, the number average molecular weight M _n = 6300 and the weight average molecular weight M _w = 8700.

(Example 79)
Synthesis of L-3- (2-benzyloxycarbonyl) ethyl-1,4-dioxane-2,5-dione represented by the chemical formula (46)

  Dissolve 20 g of L-glutamic acid in 200 ml of 80% sulfuric acid, add and react with 500 g of benzyl alcohol while keeping the temperature at 70 ° C. Obtained. 100 g of this crude product is added to 1400 ml of 0.5 mol / L (= 1.0 N) sulfuric acid, and while stirring at 0-5 ° C., 100 ml of an aqueous solution containing 45.2 g of sodium nitrite is added dropwise over about 3 hours and stirred for 30 minutes. Continued. Further, 30 ml of an aqueous solution containing 9.4 g of sodium nitrite was dropped over about 30 minutes and left at room temperature overnight. The mixture was extracted with ether, the extract was dried over sodium sulfate, concentrated, and the remaining crude crystals were purified by silica gel column chromatography and recrystallization to obtain a compound represented by the chemical formula (48). 20 g of this compound and 17.4 g of bromoacetyl chloride were dissolved in 300 ml of ether, cooled to 5 ° C. or less, and 50 ml of an ether solution containing 9.5 g of 1.1-fold molar amount of triethylamine was added dropwise over 30 minutes. The reaction mixture was further stirred at room temperature for 6 hours, filtered, and 50 ml of water was added to the filtrate and stirred for 30 minutes. Water was added several times for liquid separation, sodium sulfate was added to the ether layer, dried, and concentrated to obtain 28.3 g of the compound represented by the chemical formula (49). Yield 94%.

  A 50 ml DMF solution of 10 g of the compound represented by the chemical formula (49) was added dropwise to a 950 ml DMF (heterogeneous solution) 3.6 g sodium bicarbonate at room temperature over about 8 hours. The mixture was further reacted at the same temperature for 12 hours, filtered, DMF was concentrated, and the residue was washed with 50 ml of isopropanol. After filtration, the obtained white powder was dissolved in 200 ml of acetone, insoluble matter was removed by filtration, and the filtrate was concentrated. The residue was washed with a small amount of isopropanol, filtered and dried thoroughly. This white powder was sublimated and recrystallized from 400 ml of isopropanol to obtain 1.9 g of L-3- (2-benzyloxycarbonyl) ethyl-1,4-dioxane-2,5-dione represented by the chemical formula (46). 24%).

Example 80
Synthesis of L-3- (3-benzyloxycarbonyl) propyl-1,4-dioxane-2,5-dione represented by the chemical formula (129)

  Including 200 g of L-2-aminoadipic acid dissolved in 200 ml of 80% sulfuric acid and reacting by adding 500 g of benzyl alcohol while maintaining the temperature at 70 ° C., containing a compound represented by the chemical formula (130) in which the carboxyl group at the 6-position is protected A crude product was obtained. 100 g of this crude product is added to 1400 ml of 0.5 mol / L (= 1.0 N) sulfuric acid, 100 ml of an aqueous solution containing 41.7 g of sodium nitrite is added dropwise over about 3 hours while stirring at 0 to 5 ° C., and the mixture is stirred for 30 minutes. Continued. Further, 30 ml of an aqueous solution containing 8.9 g of sodium nitrite was dropped over about 30 minutes and left at room temperature overnight. The mixture was extracted with ether, the extract was dried over sodium sulfate, concentrated, and the remaining crude crystals were purified by silica gel column chromatography and recrystallization to obtain the compound represented by the chemical formula (131). 20 g of this compound and 16.4 g of bromoacetyl chloride were dissolved in 300 ml of ether, cooled to 5 ° C. or less, and 50 ml of an ether solution containing 8.8 g of 1.1-fold molar amount of triethylamine was added dropwise over 30 minutes. The reaction mixture was further stirred at room temperature for 6 hours, filtered, and 50 ml of water was added to the filtrate and stirred for 30 minutes. Water was added several times for liquid separation, sodium sulfate was added to the ether layer, dried, and concentrated to obtain 27.0 g of the compound represented by the chemical formula (132). Yield 92%.

  A solution of 10 g of the compound represented by the chemical formula (132) in 50 ml of DMF was added dropwise to a 950 ml of DMF (heterogeneous solution) in 3.4 g of sodium hydrogencarbonate at room temperature over about 8 hours. The mixture was further reacted at the same temperature for 12 hours, filtered, DMF was concentrated, and the residue was washed with 50 ml of isopropanol. After filtration, the obtained white powder was dissolved in 200 ml of acetone, insoluble matter was removed by filtration, and the filtrate was concentrated. The residue was washed with a small amount of isopropanol, filtered and dried thoroughly. The white powder was sublimated and recrystallized from 400 ml of isopropanol to obtain 2.1 g (yield) of L-3- (3-benzyloxycarbonyl) propyl-1,4-dioxane-2,5-dione represented by the chemical formula (129). 26%).

Example 81
Synthesis of 3- (5-benzyloxycarbonyl) pentyl-1,4-dioxane-2,5-dione represented by the chemical formula (133)

  A crude product containing a compound represented by the chemical formula (134) in which 20 g of 2-amino sebacic acid is dissolved in 200 ml of 80% sulfuric acid and reacted with 500 g of benzyl alcohol while maintaining at 70 ° C. Got. 100 g of this crude product is added to 1400 ml of 0.5 mol / L (= 1.0 N) sulfuric acid, and while stirring at 0 to 5 ° C., 100 ml of an aqueous solution containing 37.6 g of sodium nitrite is added dropwise over about 3 hours and stirred for 30 minutes. Continued. Further, 30 ml of an aqueous solution containing 8.0 g of sodium nitrite was dropped over about 30 minutes and left at room temperature overnight. The mixture was extracted with ether, the extract was dried over sodium sulfate and concentrated, and the remaining crude crystals were purified by silica gel column chromatography and recrystallization to obtain the compound represented by the chemical formula (135). 20 g of this compound and 14.7 g of bromoacetyl chloride were dissolved in 300 ml of ether, cooled to 5 ° C. or less, and 50 ml of an ether solution containing 7.9 g of 1.1-fold molar amount of triethylamine was added dropwise over 30 minutes. The reaction mixture was further stirred at room temperature for 6 hours, filtered, and 50 ml of water was added to the filtrate and stirred for 30 minutes. Water was added several times to perform liquid separation, and sodium ether was added to the ether layer for drying, followed by concentration to obtain 25.8 g of a compound represented by the chemical formula (136). Yield 90%.

  A solution of 10 g of the compound represented by the chemical formula (136) in 50 ml of DMF was added dropwise to a 950 ml of DMF (heterogeneous solution) in 3.0 g of sodium bicarbonate at room temperature over about 8 hours. The mixture was further reacted at the same temperature for 12 hours, filtered, DMF was concentrated, and the residue was washed with 50 ml of isopropanol. After filtration, the obtained white powder was dissolved in 200 ml of acetone, insoluble matter was removed by filtration, and the filtrate was concentrated. The residue was washed with a small amount of isopropanol, filtered and dried thoroughly. This white powder was sublimated and recrystallized from 400 ml of isopropanol to give 2.0 g (yield of L-3- (3-benzyloxycarbonyl) pentyl-1,4-dioxane-2,5-dione represented by the chemical formula (133). 25%).

(Example 82)
[Polyester synthesis using L-3- (2-benzyloxycarbonyl) ethyl-1,4-dioxane-2,5-dione and L-lactide]

  L-3- (2-benzyloxycarbonyl) ethyl-1,4-dioxane-2,5-dione synthesized in Example 79 0.29 g (1.0 mmol), L-lactide 1.44 g (10.0 mmol), 0.01 mol / 4 ml of a toluene solution of tin octylate (tin 2-ethylhexanoate) was placed in a polymerization ampule, dried under reduced pressure for 1 hour, purged with nitrogen, sealed under reduced pressure, and heated to 150 ° C. Then, ring-opening polymerization was performed. The reaction was terminated after 2 hours and cooled. The obtained polymer was dissolved in chloroform and reprecipitated in 10 times the amount of methanol required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 1.47 g of polymer. As a result of conducting NMR analysis under the same conditions as in Example 6 in order to specify the structure of the obtained polymer, it was a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (137) as a monomer unit. It was confirmed. Moreover, it was confirmed that the ratio of the monomer unit was 6 mol% of A unit and 94 mol% of B unit.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 46200 and the weight average molecular weight Mw = 61900. 1.00 g of the polyhydroxyalkanoate copolymer represented by the chemical formula (137) obtained here is dissolved in 100 ml of a mixed solvent of dioxane-ethanol (75:25), and 0.22 g of 5% palladium / carbon catalyst is added thereto. The reaction system was filled with hydrogen and stirred at room temperature for 1 day. After the reaction, in order to remove the catalyst, it was filtered through a 0.25 μm membrane filter, and the reaction solution was recovered. After the solution was concentrated, reprecipitation was performed in 10 times the amount of methanol dissolved in chloroform. The obtained polymer was collected and dried under reduced pressure to obtain 0.80 g of polymer. As a result of performing NMR analysis under the same conditions as in Example 6 in order to specify the structure of the obtained polymer, it is a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (138) as a monomer unit. It was confirmed. Moreover, it was confirmed that the ratio of the monomer unit was 6 mol% C unit and 94 mol% D unit.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 38100 and the weight average molecular weight Mw = 53700.

Example 83
[Polyester synthesis using L-3- (2-benzyloxycarbonyl) ethyl-1,4-dioxane-2,5-dione and L-lactide]

  L-3- (2-benzyloxycarbonyl) ethyl-1,4-dioxane-2,5-dione synthesized in Example 79 0.56 g (2.0 mmol), L-lactide 1.44 g (10.0 mmol), 0.01 mol / 5 ml of a toluene solution of tin octylate (tin 2-ethylhexanoate) was placed in a polymerization ampule, dried under reduced pressure for 1 hour, purged with nitrogen, sealed under reduced pressure, and heated to 150 ° C. Then, ring-opening polymerization was performed. The reaction was terminated after 2 hours and cooled. The obtained polymer was dissolved in chloroform and reprecipitated in 10 times the amount of methanol required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 1.70 g of polymer. As a result of performing NMR analysis under the same conditions as in Example 6 in order to specify the structure of the obtained polymer, it is a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (139) as a monomer unit. It was confirmed. Further, it was confirmed that the proportion of the monomer units was 12 mol% for the A unit and 88 mol% for the B unit.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 52100 and the weight average molecular weight Mw = 66700. 1.00 g of the polyhydroxyalkanoate copolymer represented by the chemical formula (139) obtained here was dissolved in 100 ml of a mixed solvent of dioxane-ethanol (75:25), and 0.22 g of 5% palladium / carbon catalyst was added thereto. The reaction system was filled with hydrogen and stirred at room temperature for 1 day. After the reaction, in order to remove the catalyst, it was filtered through a 0.25 μm membrane filter, and the reaction solution was recovered. After the solution was concentrated, reprecipitation was performed in 10 times the amount of methanol dissolved in chloroform. The obtained polymer was collected and dried under reduced pressure to obtain 0.68 g of polymer. As a result of conducting NMR analysis under the same conditions as in Example 6 in order to specify the structure of the obtained polymer, it was a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (140) as a monomer unit. It was confirmed. Moreover, it was confirmed that the ratio of the monomer unit was 12 mol% for C unit and 88 mol% for D unit.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 43700 and the weight average molecular weight Mw = 59400.

(Example 84)
[Polyester synthesis using L-3- (2-benzyloxycarbonyl) ethyl-1,4-dioxane-2,5-dione and L-lactide]

  L-3- (2-benzyloxycarbonyl) ethyl-1,4-dioxane-2,5-dione synthesized in Example 79 1.11 g (4.0 mmol), L-lactide 1.44 g (10.0 mmol), 0.01 mol / 6 ml of a toluene solution of tin octylate (tin 2-ethylhexanoate) was placed in a polymerization ampule, dried under reduced pressure for 1 hour, purged with nitrogen, sealed under reduced pressure, and heated to 150 ° C. Then, ring-opening polymerization was performed. The reaction was terminated after 2 hours and cooled. The obtained polymer was dissolved in chloroform and reprecipitated in 10 times the amount of methanol required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 2.23 g of polymer. As a result of performing NMR analysis under the same conditions as in Example 6 in order to specify the structure of the obtained polymer, it is a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (141) as a monomer unit. It was confirmed. Moreover, it was confirmed that the ratio of the monomer unit was 22 mol% of A unit and 78 mol% of B unit.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 47300 and the weight average molecular weight Mw = 69100.

  1.00 g of the polyhydroxyalkanoate copolymer represented by the chemical formula (141) obtained here was dissolved in 100 ml of a mixed solvent of dioxane-ethanol (75:25), and 0.22 g of 5% palladium / carbon catalyst was added thereto. The reaction system was filled with hydrogen and stirred at room temperature for 1 day. After the reaction, in order to remove the catalyst, it was filtered through a 0.25 μm membrane filter, and the reaction solution was recovered. The solution was concentrated, dissolved in chloroform, and reprecipitated in 10 times the amount of methanol. The obtained polymer was collected and dried under reduced pressure to obtain 0.58 g of polymer. As a result of performing NMR analysis under the same conditions as in Example 6 in order to specify the structure of the obtained polymer, it is a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (142) as a monomer unit. It was confirmed. Moreover, it was confirmed that the ratio of the monomer unit was 22 mol% C unit and 78 mol% D unit.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 40400 and the weight average molecular weight Mw = 59400.

Example 85
[Polyester synthesis using L-3- (3-benzyloxycarbonyl) propyl-1,4-dioxane-2,5-dione and L-lactide]

  L-3- (3-benzyloxycarbonyl) propyl-1,4-dioxane-2,5-dione synthesized in Example 80 0.58 g (2.0 mmol), L-lactide 1.44 g (10.0 mmol), 0.01 mol / 5 ml of a toluene solution of tin octylate (tin 2-ethylhexanoate) was placed in a polymer ampoule, dried under reduced pressure for 1 hour, purged with nitrogen, sealed under reduced pressure, and heated to 150 ° C. Then, ring-opening polymerization was performed. The reaction was terminated after 2 hours and cooled. The obtained polymer was dissolved in chloroform and reprecipitated in 10 times the amount of methanol required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 1.70 g of polymer. As a result of performing NMR analysis under the same conditions as in Example 6 to specify the structure of the obtained polymer, it is a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (143) as a monomer unit. It was confirmed. Moreover, it was confirmed that the ratio of the monomer unit was 10 mol% of A unit and 90 mol% of B unit.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 49600 and the weight average molecular weight Mw = 67500.

  1.00 g of the polyhydroxyalkanoate copolymer represented by the chemical formula (143) obtained here was dissolved in 100 ml of a mixed solvent of dioxane-ethanol (75:25), and 0.22 g of 5% palladium / carbon catalyst was added thereto. The reaction system was filled with hydrogen and stirred at room temperature for 1 day. After the reaction, in order to remove the catalyst, it was filtered through a 0.25 μm membrane filter, and the reaction solution was recovered. The solution was concentrated, dissolved in chloroform, and reprecipitated in 10 times the amount of methanol. The obtained polymer was collected and dried under reduced pressure to obtain 0.73 g of polymer. As a result of conducting NMR analysis under the same conditions as in Example 6 in order to specify the structure of the obtained polymer, it is a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (144) as a monomer unit. It was confirmed. Further, it was confirmed that the ratio of the monomer unit was 10 mol% C unit and 90 mol% D unit.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 44200 and the weight average molecular weight Mw = 64100.

Example 86
[Polyester synthesis using L-3- (3-benzyloxycarbonyl) propyl-1,4-dioxane-2,5-dione and L-lactide]

  L-3- (3-Benzyloxycarbonyl) propyl-1,4-dioxane-2,5-dione synthesized in Example 80 1.17 g (4.0 mmol), L-lactide 1.44 g (10.0 mmol), 0.01 mol / 6 ml of a toluene solution of tin octylate (tin 2-ethylhexanoate) was placed in a polymerization ampule, dried under reduced pressure for 1 hour, purged with nitrogen, sealed under reduced pressure, and heated to 150 ° C. Then, ring-opening polymerization was performed. The reaction was terminated after 2 hours and cooled. The obtained polymer was dissolved in chloroform and reprecipitated in 10 times the amount of methanol required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 2.07 g of polymer. As a result of conducting NMR analysis under the same conditions as in Example 6 in order to specify the structure of the obtained polymer, it is a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (145) as a monomer unit. It was confirmed. Further, it was confirmed that the proportion of the monomer units was 18 mol% for A unit and 82 mol% for B unit.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 49300 and the weight average molecular weight Mw = 69100.

  1.00 g of the polyhydroxyalkanoate copolymer represented by the chemical formula (145) obtained here was dissolved in 100 ml of a mixed solvent of dioxane-ethanol (75:25), and 0.22 g of 5% palladium / carbon catalyst was added thereto. The reaction system was filled with hydrogen and stirred at room temperature for 1 day. After the reaction, in order to remove the catalyst, it was filtered through a 0.25 μm membrane filter, and the reaction solution was recovered. The solution was concentrated, dissolved in chloroform, and reprecipitated in 10 times the amount of methanol. The obtained polymer was collected and dried under reduced pressure to obtain 0.65 g of polymer. As a result of performing NMR analysis under the same conditions as in Example 6 in order to specify the structure of the obtained polymer, it is a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (146) as a monomer unit. It was confirmed. Moreover, it was confirmed that the ratio of the monomer unit was 18 mol% of C unit and 82 mol% of D unit.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 42300 and the weight average molecular weight Mw = 59600.

Example 87
[Polyester synthesis using L-3- (3-benzyloxycarbonyl) propyl-1,4-dioxane-2,5-dione and mandelide]

  L-3- (3-benzyloxycarbonyl) propyl-1,4-dioxane-2,5-dione synthesized in Example 80 1.17 g (4.0 mmol), mandelide 2.68 g (10.0 mmol), 0.01 mol / L 6 ml of a toluene solution of tin octylate (tin 2-ethylhexanoate) was placed in a polymerization ampoule, dried under reduced pressure for 1 hour, purged with nitrogen, sealed under reduced pressure, heated to 150 ° C. and opened. Ring polymerization was performed. The reaction was terminated after 2 hours and cooled. The obtained polymer was dissolved in chloroform and reprecipitated in 10 times the amount of methanol required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 2.56 g of polymer. As a result of performing NMR analysis under the same conditions as in Example 6 in order to specify the structure of the obtained polymer, it is a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (147) as a monomer unit. It was confirmed. Moreover, it was confirmed that the ratio of the monomer unit was 22 mol% of A unit and 78 mol% of B unit.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 31000 and the weight average molecular weight Mw = 56100.

  1.00 g of the polyhydroxyalkanoate copolymer represented by the chemical formula (147) obtained here was dissolved in 100 ml of a mixed solvent of dioxane-ethanol (75:25), and 0.22 g of 5% palladium / carbon catalyst was added thereto. The reaction system was filled with hydrogen and stirred at room temperature for 1 day. After the reaction, in order to remove the catalyst, it was filtered through a 0.25 μm membrane filter, and the reaction solution was recovered. The solution was concentrated, dissolved in chloroform, and reprecipitated in 10 times the amount of methanol. The obtained polymer was collected and dried under reduced pressure to obtain 0.71 g of polymer. As a result of conducting NMR analysis under the same conditions as in Example 6 in order to specify the structure of the obtained polymer, it was a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (148) as a monomer unit. It was confirmed. Moreover, it was confirmed that the ratio of the monomer unit was 22 mol% C unit and 78 mol% D unit.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 27600 and the weight average molecular weight Mw = 49400.

Example 88
[Polyester synthesis using 3- (5-benzyloxycarbonyl) pentyl-1,4-dioxane-2,5-dione and L-lactide]

  3- (5-Benzyloxycarbonyl) pentyl-1,4-dioxane-2,5-dione synthesized in Example 81 1.28 g (4.0 mmol), L-lactide 1.44 g (10.0 mmol), 0.01 mol / L 6 ml of a toluene solution of tin octylate (tin 2-ethylhexanoate) was placed in a polymerization ampoule, dried under reduced pressure for 1 hour, purged with nitrogen, sealed under reduced pressure, heated to 150 ° C. and opened. Ring polymerization was performed. The reaction was terminated after 2 hours and cooled. The obtained polymer was dissolved in chloroform and reprecipitated in 10 times the amount of methanol required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 1.71 g of polymer.

  As a result of conducting NMR analysis under the same conditions as in Example 6 to specify the structure of the obtained polymer, it is a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (149) as a monomer unit. It was confirmed. Moreover, it was confirmed that the ratio of the monomer unit was 14 mol% of A unit and 86 mol% of B unit.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 22000 and the weight average molecular weight Mw = 34300.

  1.00 g of the polyhydroxyalkanoate copolymer represented by the chemical formula (149) obtained here was dissolved in 100 ml of a mixed solvent of dioxane-ethanol (75:25), and 0.22 g of 5% palladium / carbon catalyst was added thereto. The reaction system was filled with hydrogen and stirred at room temperature for 1 day. After the reaction, in order to remove the catalyst, it was filtered through a 0.25 μm membrane filter, and the reaction solution was recovered. The solution was concentrated, dissolved in chloroform, and reprecipitated in 10 times the amount of methanol. The obtained polymer was collected and dried under reduced pressure to obtain 0.66 g of polymer. As a result of performing NMR analysis under the same conditions as in Example 6 in order to specify the structure of the obtained polymer, it is a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (150) as a monomer unit. It was confirmed. Moreover, it was confirmed that the ratio of the monomer unit was 14 mol% C unit and 86 mol% D unit.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 19600 and the weight average molecular weight Mw = 29400.

Example 89
[Synthesis of polyester using 3- (5-benzyloxycarbonyl) pentyl-1,4-dioxane-2,5-dione and mandelide]

  3- (5-Benzyloxycarbonyl) pentyl-1,4-dioxane-2,5-dione synthesized in Example 81 1.28 g (4.0 mmol), mandelide 2.68 g (10.0 mmol), 0.01 mol / L octylic acid 6 ml of a toluene solution of tin (tin 2-ethylhexanoate) was placed in a polymerization ampoule, dried under reduced pressure for 1 hour, purged with nitrogen, sealed under reduced pressure, heated to 150 ° C., and ring-opening polymerization. Went. The reaction was terminated after 2 hours and cooled. The obtained polymer was dissolved in chloroform and reprecipitated in 10 times the amount of methanol required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 1.90 g of polymer.

  As a result of performing NMR analysis under the same conditions as in Example 6 in order to specify the structure of the obtained polymer, it is a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (151) as a monomer unit. It was confirmed. Moreover, it was confirmed that the ratio of the monomer unit was A unit 16 mol% and B unit 84 mol%.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 18000 and the weight average molecular weight Mw = 31500.

  1.00 g of the polyhydroxyalkanoate copolymer represented by the chemical formula (151) obtained here was dissolved in 100 ml of a mixed solvent of dioxane-ethanol (75:25), and 0.22 g of 5% palladium / carbon catalyst was added thereto. The reaction system was filled with hydrogen and stirred at room temperature for 1 day. After the reaction, in order to remove the catalyst, it was filtered through a 0.25 μm membrane filter, and the reaction solution was recovered. The solution was concentrated, dissolved in chloroform, and reprecipitated in 10 times the amount of methanol. The obtained polymer was collected and dried under reduced pressure to obtain 0.70 g of polymer. As a result of performing NMR analysis under the same conditions as in Example 6 in order to specify the structure of the obtained polymer, it is a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (152) as a monomer unit. It was confirmed. Moreover, it was confirmed that the ratio of the monomer unit was C unit 16 mol% and D unit 84 mol%.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 17600 and the weight average molecular weight Mw = 31900.

Example 90
[Polyester synthesis using β-malolactone benzyl ester and L-lactide]

  The β-malolactone benzyl ester represented by the chemical formula (153) was prepared by the same method as in US Pat. No. 4,265,247. β-malolactone benzyl ester 0.82 g (4.0 mmol), L-lactide 1.44 g (10.0 mmol), 2 mol / L diethylzinc in toluene 28 μl, 0.01 mol / L p-tert-butylbenzyl alcohol in toluene 11.2 ml Was placed in a polymerization ampule, dried under reduced pressure for 1 hour and purged with nitrogen, then sealed under reduced pressure and heated to 150 ° C. to perform ring-opening polymerization. The reaction was terminated after 10 hours and cooled. The obtained polymer was dissolved in chloroform and reprecipitated in 10 times the amount of methanol required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 1.09 g of polymer. As a result of conducting NMR analysis under the same conditions as in Example 6 in order to specify the structure of the obtained polymer, it is a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (154) as a monomer unit. It was confirmed. Moreover, it was confirmed that the ratio of the monomer unit was 8 mol% of A unit and 92 mol% of B unit.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 8200 and the weight average molecular weight Mw = 12,500.

  1.00 g of the polyhydroxyalkanoate copolymer represented by the chemical formula (154) obtained here was dissolved in 100 ml of a mixed solvent of dioxane-ethanol (75:25), and 0.22 g of 5% palladium / carbon catalyst was added thereto. The reaction system was filled with hydrogen and stirred at room temperature for 1 day. After the reaction, in order to remove the catalyst, it was filtered through a 0.25 μm membrane filter, and the reaction solution was recovered. The solution was concentrated, dissolved in chloroform, and reprecipitated in 10 times the amount of methanol. The obtained polymer was collected and dried under reduced pressure to obtain 0.76 g of polymer. As a result of performing NMR analysis under the same conditions as in Example 6 in order to specify the structure of the obtained polymer, it is a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (155) as a monomer unit. It was confirmed. Moreover, it was confirmed that the ratio of the monomer unit was 8 mol% C unit and 92 mol% D unit.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 7600 and the weight average molecular weight Mw = 11800.

Example 91
[Polyester synthesis using β-malolactone benzyl ester and mandelide]
β-malolactone benzyl ester 0.82g (4.0mmol), mandelide 2.68g (10.0mmol), 2mol / L diethylzinc toluene solution 28μl, 0.01mol / L p-tert-butylbenzyl alcohol toluene solution 11.2ml polymerized The ampule was charged, dried under reduced pressure for 1 hour and purged with nitrogen, then sealed under reduced pressure and heated to 150 ° C. to perform ring-opening polymerization. The reaction was terminated after 10 hours and cooled. The obtained polymer was dissolved in chloroform and reprecipitated in 10 times the amount of methanol required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 1.27 g of polymer.

  As a result of conducting NMR analysis under the same conditions as in Example 6 in order to specify the structure of the obtained polymer, it was a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (156) as a monomer unit. It was confirmed. Moreover, it was confirmed that the ratio of the monomer unit was 8 mol% of A unit and 92 mol% of B unit.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 6500 and the weight average molecular weight Mw = 11200.

  1.00 g of the polyhydroxyalkanoate copolymer represented by the chemical formula (156) obtained here was dissolved in 100 ml of a mixed solvent of dioxane-ethanol (75:25), and 0.22 g of 5% palladium / carbon catalyst was added thereto. The reaction system was filled with hydrogen and stirred at room temperature for 1 day. After the reaction, in order to remove the catalyst, it was filtered through a 0.25 μm membrane filter, and the reaction solution was recovered. The solution was concentrated, dissolved in chloroform, and reprecipitated in 10 times the amount of methanol. The obtained polymer was collected and dried under reduced pressure to obtain 0.81 g of polymer. As a result of performing NMR analysis under the same conditions as in Example 6 in order to specify the structure of the obtained polymer, it is a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (157) as a monomer unit. It was confirmed. Moreover, it was confirmed that the ratio of the monomer unit was 8 mol% C unit and 92 mol% D unit.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 6400 and the weight average molecular weight Mw = 10900.

(Example 92)
Condensation reaction of polyhydroxyalkanoate composed of the unit represented by the chemical formula (155) synthesized in Example 90 and 2-aminobenzenesulfonic acid phenyl ester

Under a nitrogen atmosphere, 0.40 g of a polymer synthesized with a polyhydroxyalkanoate copolymer (C: 8 mol%, D: 92 mol%) comprising the unit represented by the chemical formula (155) obtained in Example 90 was obtained. Benzenesulfonic acid phenyl ester 0.53 g was placed in a 100 ml three-necked flask, 15.0 ml of pyridine was added and stirred, and then 1.11 ml of triphenyl phosphite was added and heated at 120 ° C. for 6 hours. After completion of the reaction, it was recovered by reprecipitation in 150 ml of ethanol. The obtained polymer was washed with 1.0 mol / L (= 1.0 N) hydrochloric acid for 1 day, then washed by stirring in water for 1 day, and dried under reduced pressure to obtain 0.36 g of polymer. The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: heavy DMSO; measurement temperature: room temperature), Fourier transform-infrared absorption Analysis was performed by (FT-IR) spectrum (Nicolet AVATAR360FT-IR). As a result of IR measurement, the peak of 1695 cm ⁻¹ derived from carboxylic acid decreased, and a new peak derived from the amide group was observed at 1658 cm ⁻¹ .

^From the result of ¹ H-NMR, since the peak derived from the aromatic ring of the 2-aminobenzenesulfonic acid phenyl ester structure is shifted, the obtained polymer is represented by the following chemical formula (158) as a monomer unit. It was confirmed to be a polyhydroxyalkanoate containing unit.

Further, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (158) was a copolymer of 8 mol% for the E unit and 92 mol% for the F unit. The average molecular weight of the obtained polymer is gel permeation chromatography (GPC; Tosoh HLC-8120, column; Polymer Laboratories PLgel 5μ MIXED-C, solvent; DMF / LiBr 0.1% (w / v), polystyrene conversion) It was evaluated by. As a result, the number average molecular weight M _n = 7300 and the weight average molecular weight M _w = 11500.

(Example 93)
Condensation reaction of polyhydroxyalkanoate composed of the unit represented by the chemical formula (157) synthesized in Example 91 and 2-amino-2-methylpropanesulfonic acid

  Under a nitrogen atmosphere, 0.40 g of a polymer synthesized with a polyhydroxyalkanoate copolymer (C: 8 mol%, D: 92 mol%) comprising the unit represented by the chemical formula (157) obtained in Example 91 was obtained. After putting 0.18 g of -2-methylpropanesulfonic acid in a 100 ml three-necked flask and adding 15.0 ml of pyridine and stirring, 0.63 ml of triphenyl phosphite was added and heated at 120 ° C. for 6 hours. After completion of the reaction, it was recovered by reprecipitation in 150 ml of ethanol. The obtained polymer was washed with 1.0 mol / L (= 1.0 N) hydrochloric acid for 1 day, then washed by stirring in water for 1 day, and dried under reduced pressure to obtain 0.32 g of polymer.

The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: heavy DMSO; measurement temperature: room temperature), Fourier transform-infrared absorption Analysis was performed by (FT-IR) spectrum (Nicolet AVATAR360FT-IR). As a result of IR measurement, the peak at 1695 cm ⁻¹ derived from carboxylic acid decreased, and a new peak derived from the amide group was observed at 1668 cm ⁻¹ .

^From the result of ¹ H-NMR, since the peak derived from methylene having a 2-amino-2-methylpropanesulfonic acid structure is shifted, the obtained polymer is represented by the following chemical formula (159) as a monomer unit. It was confirmed that this was a polyhydroxyalkanoate containing unit.

Further, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (159) was a copolymer of 8 mol% for the E unit and 92 mol% for the F unit. The average molecular weight of the obtained polymer is gel permeation chromatography (GPC; Tosoh HLC-8120, column; Polymer Laboratories PLgel 5μ MIXED-C, solvent; DMF / LiBr 0.1% (w / v), polystyrene conversion) It was evaluated by. As a result, the number average molecular weight M _n = 6000 and the weight average molecular weight M _w = 10400.

  Example 94

[Polyester synthesis using 7- (2-propenyl) -2-oxepane represented by chemical formula (160) and L-lactide]
7- (2-propenyl) -2-oxepane represented by the chemical formula (160) used in Example 94 was prepared by referring to the method described in JP-A-5-310721.

  7- (2-propenyl) -2-oxepanone 0.31 g (2.0 mmol), L-lactide 1.15 g (8.0 mmol), 2 mol / L di-iso-propylzinc in toluene solution 20 μl, 0.01 mol / L p- 8 ml of a toluene solution of tert-butylbenzyl alcohol was placed in a polymerization ampule, dried under reduced pressure for 1 hour and purged with nitrogen, then sealed under reduced pressure and heated to 150 ° C. to perform ring-opening polymerization. The reaction was terminated after 10 hours and cooled. The obtained polymer was dissolved in chloroform and reprecipitated in 10 times the amount of methanol required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 1.09 g of polymer. As a result of performing NMR analysis under the same conditions as in Example 6 in order to specify the structure of the obtained polymer, it is a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (161) as a monomer unit. It was confirmed. Moreover, it was confirmed that the ratio of the monomer unit was 11 mol% of A unit and 89 mol% of B unit.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 56400 and the weight average molecular weight Mw = 91400.

  Example 95

[Polyester synthesis using 7- (3-butenyl) -2-oxepane represented by chemical formula (162) and L-lactide]
The 7- (3-butenyl) -2-oxepane represented by the chemical formula (162) used in Example 95 was prepared by referring to the method described in JP-A-5-310721. Specifically, 7- (3-butenyl) -2-oxepanone was prepared by using 2- (3-butenyl) cyclohexanone instead of the raw material 2-allylcyclohexanone described in Example 43 of the patent document.

  7- (3-Butenyl) -2-oxepane 0.34 g (2.0 mmol), L-lactide 1.15 g (8.0 mmol), 2 mol / L di-iso-propylzinc in toluene solution 20 μl, 0.01 mol / L p- 8 ml of a toluene solution of tert-butylbenzyl alcohol was placed in a polymerization ampule, dried under reduced pressure for 1 hour and purged with nitrogen, then sealed under reduced pressure and heated to 150 ° C. to perform ring-opening polymerization. The reaction was terminated after 10 hours and cooled. The obtained polymer was dissolved in chloroform and reprecipitated in 10 times the amount of methanol required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 1.05 g of polymer. As a result of performing NMR analysis under the same conditions as in Example 6 in order to specify the structure of the obtained polymer, it is a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (163) as a monomer unit. It was confirmed. Moreover, it was confirmed that the ratio of the monomer unit was 8 mol% of A unit and 92 mol% of B unit.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 43500 and the weight average molecular weight Mw = 67400.

Example 96
Oxidation reaction of polyhydroxyalkanoate composed of unit represented by chemical formula (161) synthesized in Example 94

  0.50 g of a polyhydroxyalkanoate copolymer (A: 11 mol%, B: 89 mol%) composed of the unit represented by the chemical formula (161) obtained in Example 94 was added to an eggplant flask, and dissolved by adding 30 ml of acetone. did. This was placed in an ice bath, and 5 ml of acetic acid and 0.54 g of 18-crown-6-ether were added and stirred. Next, 0.43 g of potassium permanganate was slowly added in an ice bath, stirred for 2 hours in an ice bath, and further stirred for 18 hours at room temperature. After completion of the reaction, 60 ml of ethyl acetate was added, and 45 ml of water was further added. Sodium bisulfite was then added until the peracid was removed. Thereafter, the liquidity was adjusted to pH = 1 with 1.0 mol / L (1.0 N) hydrochloric acid. The organic layer was extracted and washed 3 times with 1.0 mol / L hydrochloric acid. After recovering the organic layer, the solvent was distilled off to recover the crude polymer. Next, it was washed with 50 ml of water and 50 ml of methanol, and further washed with 50 ml of water three times, and then the polymer was recovered. Next, it was dissolved in THF and reprecipitated in 50 times the amount of THF required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 0.45 g of polymer. As a result of conducting NMR analysis under the same conditions as in Example 6 in order to specify the structure of the obtained polymer, it was confirmed that the monomer unit was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (164) It was done.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 41300 and the weight average molecular weight Mw = 67700.

  Furthermore, in order to calculate the unit of the obtained polyhydroxyalkanoate, it calculated by methyl-esterifying the carboxyl group in the side chain terminal of polyhydroxyalkanoate using trimethylsilyldiazomethane. 30 mg of the target polyhydroxyalkanoate was added to a 100 ml eggplant flask, and dissolved by adding 2.1 ml of chloroform and 0.7 ml of methanol. To this was added 0.5 ml of a 2 mol / L trimethylsilyldiazomethane-hexane solution, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the solvent was distilled off and the polymer was recovered. The polymer was recovered after washing with 50 ml of methanol. 29 mg of polyhydroxyalkanoate was obtained by drying under reduced pressure.

  NMR analysis was performed using the same method as in Example 6. As a result, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (164) was a copolymer of 11 mol% for the C unit and 89 mol% for the D unit.

Example 97
Oxidation reaction of polyhydroxyalkanoate composed of unit represented by chemical formula (163) synthesized in Example 95

  0.50 g of a polyhydroxyalkanoate copolymer (A: 8 mol%, B: 92 mol%) comprising the unit represented by the chemical formula (163) obtained in Example 95 was added to an eggplant flask, and dissolved by adding 30 ml of acetone. did. This was placed in an ice bath, and 5 ml of acetic acid and 0.40 g of 18-crown-6-ether were added and stirred. Next, 0.32 g of potassium permanganate was slowly added in an ice bath, stirred for 2 hours in an ice bath, and further stirred for 18 hours at room temperature. After completion of the reaction, 60 ml of ethyl acetate was added, and 45 ml of water was further added. Sodium bisulfite was then added until the peracid was removed. Thereafter, the liquidity was adjusted to pH = 1 with 1.0 mol / L (1.0 N) hydrochloric acid. The organic layer was extracted and washed 3 times with 1.0 mol / L hydrochloric acid. After recovering the organic layer, the solvent was distilled off to recover the crude polymer. Next, it was washed with 50 ml of water and 50 ml of methanol, and further washed with 50 ml of water three times, and then the polymer was recovered. Next, it was dissolved in THF and reprecipitated in 50 times the amount of THF required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 0.44 g of polymer. As a result of conducting NMR analysis under the same conditions as in Example 6 to identify the structure of the obtained polymer, it was confirmed that the monomer unit was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (165) It was done.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 37500 and the weight average molecular weight Mw = 59600.

  Furthermore, in order to calculate the unit of the obtained polyhydroxyalkanoate, it calculated by methyl-esterifying the carboxyl group in the side chain terminal of polyhydroxyalkanoate using trimethylsilyldiazomethane. 30 mg of the target polyhydroxyalkanoate was added to a 100 ml eggplant flask, and dissolved by adding 2.1 ml of chloroform and 0.7 ml of methanol. To this was added 0.5 ml of a 2 mol / L trimethylsilyldiazomethane-hexane solution, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the solvent was distilled off and the polymer was recovered. The polymer was recovered after washing with 50 ml of methanol. By drying under reduced pressure, 28 mg of polyhydroxyalkanoate was obtained.

  NMR analysis was performed using the same method as in Example 6. As a result, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (165) was a copolymer of 8 mol% for the C unit and 92 mol% for the D unit.

Example 98
Condensation reaction of polyhydroxyalkanoate composed of the unit represented by the chemical formula (164) synthesized in Example 96 and 2-aminobenzenesulfonic acid phenyl ester

Under a nitrogen atmosphere, 0.40 g of a polymer synthesized with a polyhydroxyalkanoate copolymer (C: 11 mol%, D: 89 mol%) composed of the unit represented by the chemical formula (164) obtained in Example 96 was obtained. 0.66 g of benzenesulfonic acid phenyl ester was placed in a 100 ml three-necked flask, and 15.0 ml of pyridine was added and stirred. Then, 1.38 ml of triphenyl phosphite was added and heated at 120 ° C. for 6 hours. After completion of the reaction, it was recovered by reprecipitation in 150 ml of ethanol. The obtained polymer was washed with 1.0 mol / L (= 1.0 N) hydrochloric acid for 1 day, then washed by stirring in water for 1 day, and dried under reduced pressure to obtain 0.36 g of polymer. The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: heavy DMSO; measurement temperature: room temperature), Fourier transform-infrared absorption Analysis was performed by (FT-IR) spectrum (Nicolet AVATAR360FT-IR). As a result of IR measurement, the peak of 1695 cm ⁻¹ derived from carboxylic acid decreased, and a new peak derived from the amide group was observed at 1658 cm ⁻¹ .

^From the result of ¹ H-NMR, since the peak derived from the aromatic ring of 2-aminobenzenesulfonic acid phenyl ester structure is shifted, the obtained polymer is represented by the following chemical formula (166) as a monomer unit. It was confirmed to be a polyhydroxyalkanoate containing unit.

Further, it was confirmed that the unit of polyhydroxyalkanoate represented by the chemical formula (166) was a copolymer of 11 mol% for E unit and 89 mol% for F unit. The average molecular weight of the obtained polymer is gel permeation chromatography (GPC; Tosoh HLC-8120, column; Polymer Laboratories PLgel 5μ MIXED-C, solvent; DMF / LiBr 0.1% (w / v), polystyrene conversion) It was evaluated by. As a result, the number average molecular weight M _n = 41300 and the weight average molecular weight M _w = 67700.

Example 99
Condensation reaction between a polyhydroxyalkanoate composed of the unit represented by the chemical formula (165) synthesized in Example 97 and 2-amino-2-methylpropanesulfonic acid

  Under a nitrogen atmosphere, 0.40 g of a polymer synthesized with a polyhydroxyalkanoate copolymer (C: 8 mol%, D: 92 mol%) comprising the unit represented by the chemical formula (165) obtained in Example 97 was obtained. After putting 0.30 g of -2-methylpropanesulfonic acid in a 100 ml three-necked flask and adding 15.0 ml of pyridine and stirring, 1.03 ml of triphenyl phosphite was added and heated at 120 ° C. for 6 hours. After completion of the reaction, it was recovered by reprecipitation in 150 ml of ethanol. The obtained polymer was washed with 1.0 mol / L (= 1.0 N) hydrochloric acid for 1 day, then washed by stirring in water for 1 day, and dried under reduced pressure to obtain 0.32 g of polymer.

The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: heavy DMSO; measurement temperature: room temperature), Fourier transform-infrared absorption Analysis was performed by (FT-IR) spectrum (Nicolet AVATAR360FT-IR). As a result of IR measurement, the peak at 1695 cm ⁻¹ derived from carboxylic acid decreased, and a new peak derived from the amide group was observed at 1668 cm ⁻¹ .

^From the result of ¹ H-NMR, since the peak derived from methylene having a 2-amino-2-methylpropanesulfonic acid structure is shifted, the obtained polymer is represented by the following chemical formula (167) as a monomer unit. It was confirmed that this was a polyhydroxyalkanoate containing unit.

Further, it was confirmed that the unit of polyhydroxyalkanoate represented by the chemical formula (167) was a copolymer of 8 mol% for the E unit and 92 mol% for the F unit. The average molecular weight of the obtained polymer is gel permeation chromatography (GPC; Tosoh HLC-8120, column; Polymer Laboratories PLgel 5μ MIXED-C, solvent; DMF / LiBr 0.1% (w / v), polystyrene conversion) It was evaluated by. As a result, the number average molecular weight M _n = 37500 and the weight average molecular weight M _w = 59600.

(Example 100)
[Polyester synthesis using glycolide]
Glycolide 11.61g (100.0mmol), 0.1mol / L tin octylate (tin 2-ethylhexanoate) in toluene 4.0ml, 0.1mol / L p-tert-butylbenzyl alcohol in toluene 4.0ml polymerization ampoule Then, after drying under reduced pressure and purging with nitrogen for 1 hour, it was sealed under reduced pressure and heated to 150 ° C. to perform ring-opening polymerization. The reaction was terminated after 10 hours and cooled. The obtained polymer was dissolved in chloroform and reprecipitated in 10 times the amount of methanol required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 9.63 g of polymer. As a result of conducting NMR analysis under the same conditions as in Example 6 in order to specify the structure of the obtained polymer, it was confirmed that the monomer unit was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (178) It was done.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 73000 and the weight average molecular weight Mw = 130100.

(Example 101)
2.00 g of a polyhydroxyalkanoate composed of the unit represented by the chemical formula (178) obtained in Example 100 was added to an eggplant flask, and dissolved by adding 100 ml of THF. This was placed under a nitrogen atmosphere and stirred at -78 ° C. Next, 18.9 ml of 2 mol / L lithium diisopropylamide in THF was slowly added and stirred at −78 ° C. for 30 minutes. Next, 12.86 g of benzyl chloroformate was added, followed by stirring at room temperature for 30 minutes. After completion of the reaction, the reaction solution was poured into 400 ml of an aqueous ammonium chloride solution, and 200 ml of dichloromethane was added to extract the organic layer. After washing three times with 100 ml of water, the organic layer was recovered. The crude polymer was recovered by distilling off the solvent. Next, it was dissolved in 12 ml of THF, then dissolved in THF, and reprecipitated in 50 times the amount of THF required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 1.22 g of polymer. As a result of conducting NMR analysis under the same conditions as in Example 6 in order to specify the structure of the obtained polymer, it was confirmed that the monomer unit was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (179) It was. Moreover, it was confirmed that the ratio of the monomer unit was 8 mol% of A unit and 92 mol% of B unit.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 42100 and the weight average molecular weight Mw = 85500.

  1.00 g of the polyhydroxyalkanoate copolymer represented by the chemical formula (chemical formula 179) obtained here was dissolved in 100 ml of a mixed solvent of dioxane-ethanol (75:25), and 0.22 g of 5% palladium / carbon catalyst was added thereto. In addition, the reaction system was filled with hydrogen and stirred at room temperature for 1 day. After the reaction, in order to remove the catalyst, it was filtered through a 0.25 μm membrane filter, and the reaction solution was recovered. The solution was concentrated, dissolved in chloroform, and reprecipitated in 10 times the amount of methanol. The obtained polymer was collected and dried under reduced pressure to obtain 0.60 g of polymer. As a result of conducting NMR analysis under the same conditions as in Example 6 in order to specify the structure of the obtained polymer, it was a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (180) as a monomer unit. It was confirmed. Moreover, it was confirmed that the ratio of the monomer unit was 8 mol% C unit and 92 mol% D unit.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 37400 and the weight average molecular weight Mw = 78500.

(Example 102)
2.00 g of a polyhydroxyalkanoate composed of the unit represented by the chemical formula (178) obtained in Example 100 was added to an eggplant flask, and dissolved by adding 100 ml of THF. This was placed under a nitrogen atmosphere and stirred at -78 ° C. Next, 18.9 ml of 2 mol / L lithium diisopropylamide in THF was slowly added and stirred at −78 ° C. for 30 minutes. Next, 14.41 g of ethyl 5-bromovalerate was added, followed by stirring at room temperature for 30 minutes. After completion of the reaction, the reaction solution was poured into 400 ml of an aqueous ammonium chloride solution, and 200 ml of dichloromethane was added to extract the organic layer. After washing three times with 100 ml of water, the organic layer was recovered. The crude polymer was recovered by distilling off the solvent. Next, it was dissolved in 12 ml of THF, then dissolved in THF, and reprecipitated in 50 times the amount of THF required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 1.31 g of polymer. As a result of conducting NMR analysis under the same conditions as in Example 6 to identify the structure of the obtained polymer, it was confirmed that the monomer unit was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (181) It was. Moreover, it was confirmed that the ratio of the monomer unit was 9 mol% A unit and 91 mol% B unit.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 41500 and the weight average molecular weight Mw = 93400.

  1.00 g of the polyhydroxyalkanoate copolymer represented by the chemical formula (181) obtained here was dissolved in 100 ml of a mixed solvent of dioxane-ethanol (75:25), and 0.22 g of 5% palladium / carbon catalyst was added thereto. The reaction system was filled with hydrogen and stirred at room temperature for 1 day. After the reaction, in order to remove the catalyst, it was filtered through a 0.25 μm membrane filter, and the reaction solution was recovered. The solution was concentrated, dissolved in chloroform, and reprecipitated in 10 times the amount of methanol. The obtained polymer was collected and dried under reduced pressure to obtain 0.66 g of polymer. As a result of performing NMR analysis under the same conditions as in Example 6 in order to specify the structure of the obtained polymer, it is a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (182) as a monomer unit. It was confirmed. Moreover, it was confirmed that the ratio of the monomer unit was 9 mol% for C unit and 91 mol% for D unit.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 35800 and the weight average molecular weight Mw = 81600.

(Example 103)
2.00 g of a polyhydroxyalkanoate composed of the unit represented by the chemical formula (178) obtained in Example 100 was added to an eggplant flask, and 100 ml of THF was added and dissolved. This was placed under a nitrogen atmosphere and stirred at -78 ° C. Next, 18.9 ml of 2 mol / L lithium diisopropylamide in THF was slowly added and stirred at −78 ° C. for 30 minutes. Next, 16.68 g of methyl 2-acrylamido-2-methylpropanesulfonate was added, followed by stirring at room temperature for 30 minutes. After completion of the reaction, the reaction solution was poured into 400 ml of an aqueous ammonium chloride solution, and 200 ml of dichloromethane was added to extract the organic layer. After washing three times with 100 ml of water, the organic layer was recovered. The crude polymer was recovered by distilling off the solvent. Next, it was dissolved in 12 ml of THF, then dissolved in THF, and reprecipitated in 50 times the amount of THF required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 1.22 g of polymer. The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: heavy DMSO; measurement temperature: room temperature). As a result, it was confirmed that the monomer unit was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (183). Moreover, it was confirmed that the ratio of the monomer unit was 6 mol% E unit and 94 mol% F unit.

  The average molecular weight of the obtained polyhydroxyalkanoate was determined by gel permeation chromatography (GPC; Tosoh HLC-8120, column; Polymer Laboratories PLgel 5μ MIXED-C, solvent; DMF / LiBr 0.1% (w / v ), Polystyrene conversion). As a result, the number average molecular weight Mn = 37400 and the weight average molecular weight Mw = 78500.

(Example 104)
[L-3- (2-Benzyloxycarbonyl) ethyl-1,4-dioxane-2,5-dione and phenyl lactide (3,6-bis (phenylmethyl) -1,4-dioxane-2,5-dione Polyester synthesis using
L-3- (2-benzyloxycarbonyl) ethyl-1,4-dioxane-2,5-dione represented by the chemical formula (46) synthesized in Example 79 0.56 g (2.0 mmol), phenyl lactide 2.96 g (10.0 mol), 0.01 mol / L tin octylate (tin 2-ethylhexanoate) in toluene solution 4.8 ml, 0.01 mol / L p-tert-butylbenzyl alcohol in toluene solution 4.8 ml were charged into the polymerization ampule, After drying under reduced pressure and purging with nitrogen for 1 hour, it was sealed under reduced pressure and heated to 180 ° C. to perform ring-opening polymerization. The reaction was terminated after 2 hours and cooled. The obtained polymer was dissolved in chloroform and reprecipitated in 10 times the amount of methanol required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 2.98 g. As a result of conducting NMR analysis under the same conditions as in Example 6 in order to specify the structure of the obtained polymer, it was a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (184) as a monomer unit. It was confirmed. Further, it was confirmed that the proportion of the monomer units was 12 mol% for the A unit and 88 mol% for the B unit.

  Further, the average molecular weight of the obtained polyhydroxyalkanoate was evaluated by the same method as in Example 1. As a result, the number average molecular weight Mn = 37500 and the weight average molecular weight Mw = 53300.

  1.00 g of the polyhydroxyalkanoate copolymer represented by the chemical formula (184) obtained here was dissolved in 100 ml of a mixed solvent of dioxane-ethanol (75:25), and 0.22 g of 5% palladium / carbon catalyst was added thereto. The reaction system was filled with hydrogen and stirred at room temperature for 1 day. After the reaction, in order to remove the catalyst, it was filtered through a 0.25 μm membrane filter, and the reaction solution was recovered. After the solution was concentrated, reprecipitation was performed in 10 times the amount of methanol dissolved in chloroform. The obtained polymer was collected and dried under reduced pressure to obtain 0.75 g of polymer. As a result of conducting NMR analysis under the same conditions as in Example 6 in order to specify the structure of the obtained polymer, it is a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (185) as a monomer unit. It was confirmed. Moreover, it was confirmed that the ratio of the monomer unit was 12 mol% for C unit and 88 mol% for D unit.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 31200 and the weight average molecular weight Mw = 46800.

(Example 105)
[3,6-di (2-propenyl) -1,4-dioxane-2,5-dione and phenyl lactide (3,6-bis (phenylmethyl) -1,4-dioxane-2,5-dione) Polyester synthesis used]
3,6-di (2-propenyl) -1,4-dioxane-2,5-dione 0.10 g (0.5 mmol), phenyl lactide 1.33 g (4.5 mmol), 0.01 mol / L tin octylate (2-ethyl) 2 ml of toluene solution of tin hexanoate) and 2 ml of 0.01 mol / L toluene solution of p-tert-butylbenzyl alcohol were placed in a polymerization ampule, dried under reduced pressure for 1 hour and purged with nitrogen, and then dissolved under reduced pressure. Sealed and heated to 180 ° C. to perform ring-opening polymerization. The reaction was terminated after 1 hour and cooled. The obtained polymer was dissolved in chloroform and reprecipitated in 10 times the amount of methanol required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 1.07 g of polymer. As a result of conducting NMR analysis under the same conditions as in Example 6 in order to specify the structure of the obtained polymer, it is a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (186) as a monomer unit. It was confirmed. Moreover, it was confirmed that the ratio of the monomer unit was 9 mol% A unit and 91 mol% B unit.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 16500 and the weight average molecular weight Mw = 24800.

(Example 106)
Oxidation reaction of polyhydroxyalkanoate composed of unit represented by chemical formula (186) synthesized in Example 105

  0.50 g of a polyhydroxyalkanoate copolymer (A: 9 mol%, B: 91 mol%) composed of the unit represented by the chemical formula (186) obtained in Example 105 was added to an eggplant flask and dissolved by adding 30 ml of acetone. did. This was placed in an ice bath, 5 ml of acetic acid and 0.25 g of 18-crown-6-ether were added and stirred. Next, 0.20 g of potassium permanganate was slowly added in an ice bath, stirred for 2 hours in an ice bath, and further stirred for 18 hours at room temperature. After completion of the reaction, 60 ml of ethyl acetate was added, and 45 ml of water was further added. Sodium bisulfite was then added until the peracid was removed. Thereafter, the liquidity was adjusted to pH = 1 with 1.0 mol / L (1.0 N) hydrochloric acid. The organic layer was extracted and washed 3 times with 1.0 mol / L hydrochloric acid. After recovering the organic layer, the solvent was distilled off to recover the crude polymer. Next, the polymer was recovered after washing with 50 ml of water and 50 ml of methanol, and further 3 times with 50 ml of water. Next, it was dissolved in THF and reprecipitated in 50 times the amount of THF required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 0.44 g of polymer. As a result of conducting NMR analysis under the same conditions as in Example 6 in order to specify the structure of the obtained polymer, it was confirmed that the monomer unit was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (187) It was.

  The average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). . As a result, the number average molecular weight Mn = 14500 and the weight average molecular weight Mw = 23100.

  Furthermore, in order to calculate the unit of the obtained polyhydroxyalkanoate, it calculated by methyl-esterifying the carboxyl group in the side chain terminal of polyhydroxyalkanoate using trimethylsilyldiazomethane. 30 mg of the target polyhydroxyalkanoate was added to a 100 ml eggplant flask, and dissolved by adding 2.1 ml of chloroform and 0.7 ml of methanol. To this was added 0.5 ml of a 2 mol / L trimethylsilyldiazomethane-hexane solution, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the solvent was distilled off and the polymer was recovered. The polymer was recovered after washing with 50 ml of methanol. 29 mg of polyhydroxyalkanoate was obtained by drying under reduced pressure.

  NMR analysis was performed using the same method as in Example 6. As a result, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (187) was a copolymer of 8 mol% for the C unit and 92 mol% for the D unit.

(Example 107)
Condensation reaction between 2-hydroxybenzenesulfonic acid and a polyhydroxyalkanoate composed of the unit represented by the chemical formula (185) synthesized in Example 104

In a nitrogen atmosphere, 0.40 g of a polymer synthesized with a polyhydroxyalkanoate copolymer (C: 12 mol%, D: 88 mol%) composed of the unit represented by the chemical formula (185) obtained in Example 104 was obtained. After adding 0.27 g of benzenesulfonic acid to a 100 ml three-necked flask and adding 15.0 ml of pyridine and stirring, 0.82 ml of triphenyl phosphite was added and heated at 120 ° C. for 6 hours. After completion of the reaction, it was recovered by reprecipitation in 150 ml of ethanol. The obtained polymer was washed with 1.0 mol / L (= 1.0 N) hydrochloric acid for 1 day, then washed by stirring in water for 1 day, and dried under reduced pressure to obtain 0.36 g of polymer. The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: heavy DMSO; measurement temperature: room temperature), Fourier transform-infrared absorption Analysis was performed by (FT-IR) spectrum (Nicolet AVATAR360FT-IR). As a result of IR measurement, the peak of 1695 cm ⁻¹ derived from carboxylic acid decreased, and a new peak derived from the amide group was observed at 1658 cm ⁻¹ .

^From the result of ¹ H-NMR, since the peak derived from the aromatic ring having a 2-aminobenzenesulfonic acid structure is shifted, the obtained polymer has a unit represented by the following chemical formula (188) as a monomer unit. It was confirmed to be a polyhydroxyalkanoate containing.

Further, it was confirmed that the unit of polyhydroxyalkanoate represented by the chemical formula (188) was a copolymer of 11 mol% for E unit and 89 mol% for F unit. The average molecular weight of the obtained polymer is gel permeation chromatography (GPC; Tosoh HLC-8120, column; Polymer Laboratories PLgel 5μ MIXED-C, solvent; DMF / LiBr 0.1% (w / v), polystyrene conversion) It was evaluated by. As a result, the number average molecular weight M _n = 26800 and the weight average molecular weight M _w = 42900.

(Example 108)
Condensation reaction between polyhydroxyalkanoate composed of the unit represented by the chemical formula (187) synthesized in Example 106 and 4-methoxyaniline-2-sulfonic acid

Under a nitrogen atmosphere, 0.40 g of a polymer synthesized with a polyhydroxyalkanoate copolymer (C: 8 mol%, D: 92 mol%) composed of the unit represented by the chemical formula (187) obtained in Example 106 was obtained. After putting 0.22 g of aniline-2-sulfonic acid in a 100 ml three-necked flask and adding 15.0 ml of pyridine and stirring, 0.56 ml of triphenyl phosphite was added and heated at 120 ° C. for 6 hours. After completion of the reaction, it was recovered by reprecipitation in 150 ml of ethanol. The obtained polymer was washed with 1.0 mol / L (= 1.0 N) hydrochloric acid for 1 day, then washed by stirring in water for 1 day, and dried under reduced pressure to obtain 0.34 g of polymer. The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: heavy DMSO; measurement temperature: room temperature), Fourier transform-infrared absorption Analysis was performed by (FT-IR) spectrum (Nicolet AVATAR360FT-IR). As a result of IR measurement, the peak of 1695 cm ⁻¹ derived from carboxylic acid decreased, and a new peak derived from the amide group was observed at 1658 cm ⁻¹ .

^From the result of ¹ H-NMR, since the peak derived from the aromatic ring of 4-methoxyaniline-2-sulfonic acid structure is shifted, the obtained polymer is represented by the following chemical formula (189) as a monomer unit. It was confirmed that this was a polyhydroxyalkanoate containing unit.

Further, it was confirmed that the unit of polyhydroxyalkanoate represented by the chemical formula (189) was a copolymer of 7 mol% for E unit and 93 mol% for F unit. The average molecular weight of the obtained polymer is gel permeation chromatography (GPC; Tosoh HLC-8120, column; Polymer Laboratories PLgel 5μ MIXED-C, solvent; DMF / LiBr 0.1% (w / v), polystyrene conversion) It was evaluated by. As a result, the number average molecular weight M _n = 13000 and the weight average molecular weight M _w = 21500.

  According to the present invention, the side chain has a novel polyhydroxyalkanoate containing a vinyl group which is a reactive group in the molecule, a novel polyhydroxyalkanoate containing a carboxyl group in the molecule, and an amide group and a sulfonic acid group. A novel polyhydroxyalkanoate containing a unit in the molecule and a method for producing the same are provided. As a result, a novel polyhydroxyalkanoate having a vinyl group or a carboxyl group can be introduced into a functional material because a functional functional group can be introduced using the reactive group. Furthermore, polyhydroxyalkanoates that contain a carboxyl group or a unit having an amide group and a sulfonic acid group in the molecule are excellent in melt processability and are also excellent in biocompatibility due to their hydrophilicity. It can be expected to be used as a soft member for use.

Claims (4)

A polyhydroxyalkanoate comprising one or more units represented by the chemical formula (1) in a molecule.

(Wherein, R .R ₁ representing a -A ₁ -SO ₂ R ₁ represents OH, a halogen atom, ONa, .R _1a and A ₁ is OK or OR _1a are each independently substituted or unsubstituted Represents a group having an aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure, and n is an integer selected from 0 to 4. n is 0. M is an integer selected from 0 to 8, when m is an integer selected from 2, 3, and 4. When n is 1, m is 0. When there are a plurality of units, R, R ₁ , R _1a , A ₁ , m, and n represent the above meanings independently for each unit.) 2. The polyhydroxyalkano according to claim 1, wherein at least one unit represented by the chemical formula (2), the chemical formula (3), the chemical formula (4A) or (4B) is contained in the molecule as the unit of the chemical formula (1). Eight.

(Wherein R ₂ is OH, a halogen atom, ONa, OK or OR _2a . R _2a is a linear or branched alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted phenyl group. A ₂ represents a linear or branched alkylene group having 1 to 8 carbon atoms, and n is an integer selected from 0 to 4. n is selected from 0, 2, 3, 4 M is an integer selected from 0 to 8. When n is 1, m is 0. When a plurality of units are present, A ₂ , R ₂ , R _2a , m and n represent the above meanings independently for each unit.)

(In the formula, R _3a , R _3b , R _3c , R _3d and R _3e are each independently SO ₂ R _3f (R _3f is OH, a halogen atom, ONa, OK or OR _3f1 . (R _3f1 Is a linear or branched alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted phenyl group.)), Hydrogen atom, halogen atom, alkyl group having 1 to 20 carbon atoms, 1 to 20 carbon atoms Alkoxy group, OH group, NH ₂ group, NO ₂ group, COOR _3g (R _3g represents any of H atom, Na atom, K atom), acetamide group, OPh group, NHPh group, CF ₃ group, Represents a C ₂ F ₅ group or a C ₃ F ₇ group (Ph represents a phenyl group), at least one of these groups is SO ₂ R _3f , and n is an integer selected from 0 to 4 When n is an integer selected from 0, 2, 3, and 4, m is an integer selected from 0 to 8. n is 1. If, m is 0. When multiple units _{exist, R 3a, R 3b, R} 3c, R 3d, R 3e, R 3f, R 3f1, R 3g, m and n are, independently for each unit The above meanings.)

Wherein R _4a , R _4b , R _4c , R _4d , R _4e , R _4f and R _4g are each independently SO ₂ R _4o (R _4o is OH, halogen atom, ONa, OK or OR _4o1 (R _4o1 is a linear or branched alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted phenyl group)), a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, An alkoxy group having 1 to 20 carbon atoms, OH group, NH ₂ group, NO ₂ group, COOR _4p (R _4p represents any one of H atom, Na atom and K atom), acetamide group, OPh group, NHPh group, Represents a CF ₃ group, a C ₂ F ₅ group or a C ₃ F ₇ group (Ph represents a phenyl group), and at least one of these groups is SO ₂ R _4o , and n is from 0 to 4 When n is an integer selected from 0, 2, 3, and 4, m is an integer selected from 0 to 8. n is If it is 1, m is 0. When multiple units _{exist, R 4a, R 4b, R} 4c, R 4d, R 4e, R 4f, R 4g, R 4o, R 4o1, R 4p, m And n represent the above meanings independently for each unit.)

Wherein R _4h , R _4i , R _4j , R _4k , R _4l , R _4m and R _4n are each independently SO ₂ R _4o (R _4o is OH, halogen atom, ONa, OK or OR _4o1 (R _4o1 is a linear or branched alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted phenyl group)), a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, An alkoxy group having 1 to 20 carbon atoms, OH group, NH ₂ group, NO ₂ group, COOR _4p (R _4p represents any one of H atom, Na atom and K atom), acetamide group, OPh group, NHPh group, Represents a CF ₃ group, a C ₂ F ₅ group or a C ₃ F ₇ group (Ph represents a phenyl group), and at least one of these groups is SO ₂ R _4o , and n is from 0 to 4 When n is an integer selected from 0, 2, 3, and 4, m is an integer selected from 0 to 8. If it is, m is 0. When multiple units _{exist, R 4h, R 4i, R} 4j, R 4k, R 4l, R 4m, R 4n, R 4o, R 4o1, R 4p, m and n represents the above meaning independently for each unit.) The polyhydroxyalkanoate according to claim 1 or 2 , further comprising a unit represented by the chemical formula (7) in the molecule.

(R ₇ is an alkylene group having a linear or branched alkylene group having 1 to 11 carbon atoms, alkylene oxyalkylene group (each alkylene group are each independently a carbon number 1-2), 1 carbon atoms 11 linear or branched alkenyl groups, or alkylidene groups having 1 to 5 carbon atoms which may be substituted with aryl, and when there are a plurality of units, R ₇ is independently selected for each unit. Represents the above meaning.) It includes a unit represented by chemical formula (1), characterized by comprising a step of subjecting a polyhydroxyalkanoate comprising a unit represented by chemical formula (20) to at least one amine compound represented by chemical formula (21) to a condensation reaction Process for producing polyhydroxyalkanoate.

(In the formula, R ₂₀ is hydrogen or a group that forms a salt. N is an integer selected from 0 to 4. When n is 0, 2, 3, or 4, m is 0. It is an integer selected from ~ 8. When n is 1, m is 0. When there are a plurality of units, m, n and R ₂₀ independently represent the above meaning for each unit. .)

(Wherein R ₂₁ is OH, a halogen atom, ONa, OK or OR _21a . R _21a and A ₃ are each independently a substituted or unsubstituted aliphatic hydrocarbon structure, substituted or unsubstituted. When a plurality of units are present, R ₂₁ , R _21a and A ₃ are independently selected from the above meanings when selected from the group having an aromatic ring structure or a substituted or unsubstituted heterocyclic structure. Represents.)

(Wherein, R .R ₁ representing a -A ₁ -SO ₂ R ₁ represents OH, a halogen atom, ONa, .R _1a and A ₁ is OK or OR _1a are each independently substituted or unsubstituted Represents a group having an aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure, and n is an integer selected from 0 to 4, and n is 0 In the case of 2, 3, 4, m is an integer selected from 0 to 8. When n is 1, m is 0. When a plurality of units are present, R, R ₁ , R _1a , A ₁ , m and n represent the above meanings independently for each unit.)