JP2001302771A - Compound functionalized at both terminals and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a compound functionalized at both terminals having an alicyclic structure or a heterocyclic structure in the main chain with high mechanical strength and high heat resistance, and to provide a manufacturing method which can obtain the compound functionalized at both the terminals. SOLUTION: The compound functionalized at both terminals having an alicyclic structure or a heterocyclic structure in the main chain can be obtained by hydrogenating a compound obtained by subjecting a polycyclic unsaturated compound to ring opening polymerization in the presence of a chain unsaturated compound having functional groups at both terminals.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel compound having both ends functionalized and a method for producing the same. More specifically, the present invention relates to a compound having a terminal at both ends and having an alicyclic structure or a heterocyclic structure in a main chain, which is useful as a raw material for a resin modifier, a plasticizer, and a condensation polymerized polymer.

[0002]

2. Description of the Related Art Both terminal functional compounds can be used as raw materials for plasticizers and polycondensation polymers. One example of such a compound having both terminal functional groups is a polymer polyol. Polyether polyols such as polyethylene glycol and polypropylene glycol, polyester polyols such as polyethylene adipate, polycarbonate polyols such as polyhexamethylene carbonate, hydrogenated polybutadiene polyol, and the like have been known. Polyether polyols have high water absorption and low mechanical strength. Polyester polyols and polycarbonate polyols have high hydrolyzability. Hydrogenated polybutadiene polyol has only about 90% functional groups at both ends due to synthesis restrictions. The conventional polymer polyols had various problems such as lack of mechanical strength and insufficient mechanical strength. Therefore, there has been a demand for a polymer polyol having a compound in which a functional group is reliably introduced at both ends, having high water resistance, high heat stability, and high mechanical strength.

[0003] In recent years, the synthesis of polyolefins in which functional groups are reliably introduced at both ends has been reported. According to a report by Grubbs et al., Polybutadiene polyol in which OH groups are surely introduced into both terminals by ring-opening polymerization, hydrogenation and hydrolysis of cyclooctadiene in the presence of cis-4,7-dihydro-1,3-dioxepin Obtained hydrogenated products (Ma
cromolecules, Vol. 28, 7256 (1995)). Also, Henri
Cramail et al., As both ends functional compounds having an alicyclic structure or a heterocyclic structure in the main chain, a cyclic unsaturated compound such as norbornene and a chain having a functional group at both terminals such as 1,4-diacetoxy-2-butene. A method of producing an unsaturated compound by ring-opening polymerization using a catalyst comprising tungsten chloride and a tin compound has been reported (J. Mol.
Cat., Vol. 65, 193 (1991)).

[0004] Also, German Patent DE-196 54 074
According to Japanese Unexamined Patent Publication (Kokai) No. 10-195182, it has not been confirmed whether a functional group is introduced into both terminals, but Gr.
Using the catalyst used by Ubbs et al.
It has been reported that a polymer is obtained by ring-opening polymerization in the presence of 4-dimethoxy-2-butene, followed by hydrogenation.

[0005]

In the presence of cis-4,7-dihydro-1,3-dioxepin, cyclooctadiene is subjected to ring-opening polymerization, hydrogenation and hydrolysis to reliably introduce OH groups at both ends. Although the hydrogenated polybutadiene polyol has functional groups introduced at both ends, the hydrogenated polybutadiene polyol has the same skeleton as that of the conventional hydrogenated polybutadiene polyol, and has a disadvantage that the mechanical strength is slightly insufficient. In addition, the functional group at both ends having an alicyclic structure or a heterocyclic structure in the main chain obtained by ring-opening polymerization using a catalyst composed of tungsten chloride and a tin compound is surely introduced with functional groups at both ends. Since the double bond remains, it is susceptible to oxidation by oxygen, and has a disadvantage of poor heat resistance. Further, German Patent DE-19654074 (Japanese Patent Application Laid-Open No. H10-195182) does not intend to introduce a functional group into both ends, and does not confirm whether a functional group is introduced into both ends. In fact, even if ring-opening polymerization is performed in the same manner, the molecular weight is extremely high, and it is difficult to confirm the introduction of a functional group.

An object of the present invention is to solve the above-mentioned problems of the prior art. More specifically, it is possible to provide a double-terminal functional compound having an alicyclic structure or a heterocyclic structure in the main chain having high mechanical strength and high thermal stability, and a production method capable of obtaining the both-terminal functional compound. It is an object to provide a method.

[0007]

Means for Solving the Problems As a result of intensive studies on the above-mentioned problems, the present inventors have found that ring-opening polymerization of a cyclic unsaturated compound is carried out in the presence of a linear unsaturated compound having functional groups at both ends. By hydrogenating the compound thus obtained, a compound having both terminal functional groups having an alicyclic structure or a heterocyclic structure in the main chain was successfully obtained, and the present invention was achieved. That is, the present invention relates to a compound having a functional group at both ends represented by the following (1) to (13) and a method for producing the same. (1) Both terminals are each independently represented by the general formula (I), and between the two terminals, a repeating unit represented by the general formula (II):
Or a compound having both ends functional groups comprising a repeating unit represented by the general formula (II) and the general formula (III).

X _1- (CH ₂ ) _m -CH _2- , X _2- (CH ₂ ) _n -CH _2- (I) wherein X ₁ and X ₂ are independently OR, COOR or OCO
R (R represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms), and m and n each independently represent an integer of 0 to 5. ]

[0009]

Embedded image (II)

Embedded image (II ') wherein, A represents the general formula (II') or an oxygen atom, R ₁ ~
R ₈ is independently a halogen atom, a hydrogen atom, or an optionally substituted hydrocarbon group having 1 to 20 carbon atoms (two or more of R _{1 to} R ₈ may be linked to form a ring .), A cyano group, a hydroxyl group, an alkoxyl group, an acyloxy group, a formyl group, a carboxyl group (an acid anhydride may be formed from its ester or two carboxyl groups) or a silyl group. -Y- (III) [wherein, Y represents an alkylene group having 4 to 12 carbon atoms. (2) The both-terminal functional compound according to (1), wherein both terminals are independently represented by the general formula (I), and a portion between the both terminals is a repeating unit represented by the general formula (II). (3) R _{1 to} R _{8 in} the general formula (II) are independently a halogen atom, a hydrogen atom, and a carbon atom of 1 to 1 which may have a substituent.
(1) or (2), which is a hydrocarbon group of 20 (two or more of R _{1 to} R ₈ may be linked to form a ring). (4) Both terminals are each independently represented by the general formula (IV), and a carbon-carbon double bond of the compound (a) containing a repeating unit represented by the general formula (V) is hydrogenated between the two terminals. The method is characterized in that both ends are independently represented by the general formula (I), and the main chain structure forming the both ends comprises a repeating unit including a repeating unit represented by the general formula (II). A method for producing a terminal functional compound.

X _1- (CH ₂ ) _m -CH =, X _2- (CH ₂ ) _n -CH = (IV) wherein X ₁ and X ₂ are independently OR, COOR or OCO
R (R represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms), and m and n each independently represent an integer of 0 to 5. ]

[0011]

Embedded image (V)

Embedded image(V ′) wherein A represents the general formula (V ′) or an oxygen atom, R₉~ R
₁₆Has independently a halogen atom, a hydrogen atom and a substituent
And a hydrocarbon group having 1 to 20 carbon atoms (R₁₁And R ₁₂, R
₁₃And R₁₄Is an independent alkylide
R may be a group ₉~ R₁₆Two or more of
It may be formed. ), Cyano group, hydroxyl group, alkoxyl
Group, acyloxy group, formyl group, carboxyl group
An acid anhydride from an ester or two carboxyl groups
It may be formed. ) Or a silyl group. X₁− (CH_Two)_m-CH_Two-, X_Two− (CH_Two)_n-CH_Two-(I) wherein X₁, X_TwoAre independently OR, COOR or OCO
R (R represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms
Represent. ), And m and n independently represent an integer of 0 to 5
You. ]

[0012]

Embedded image (II)

Embedded image (II ') wherein, A represents the general formula (II') or an oxygen atom, R ₁ ~
R ₈ is independently a halogen atom, a hydrogen atom, or an optionally substituted hydrocarbon group having 1 to 20 carbon atoms (two or more of R _{1 to} R ₈ may be linked to form a ring .), A cyano group, a hydroxyl group, an alkoxyl group, an acyloxy group, a formyl group, a carboxyl group (an acid anhydride may be formed from its ester or two carboxyl groups) or a silyl group. (5) R _{9 to} R _{16 in} the general formula (V) are each independently a halogen atom, a hydrogen atom, or a carbon atom having 1 to 1 carbon atoms which may have a substituent.
A hydrocarbon group (R ₁₁ and R ₁₂ of 20, R ₁₃ and R ₁₄ are independently each set may be an alkylidene group together, R ₉
And two or more of R ₁₆ to R ₁₆ may be linked to form a ring. )
(4) The method for producing a compound having functional groups at both ends according to (4). (6) Ring-opening polymerization using a catalyst from a cyclic unsaturated compound (b) containing at least a compound represented by the general formula (VI) and a chain unsaturated compound (c) having a functional group at both ends. (4) The method for producing a compound having both terminal functional groups according to (4), wherein the compound (a) having an alicyclic structure or heterocyclic structure in its main chain is hydrogenated.

[0013]

Embedded image (VI)

Embedded image (VI ') wherein, A represents the general formula (VI') or an oxygen atom, R ₉ ~
R ₁₆ is independently a halogen atom, a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 20 carbon atoms (R ₁₁ and R ₁₂ ,
R ₁₃ and R ₁₄ may be independently an alkylidene group in each group, or two or more of R _{9 to} R ₁₆ may be linked to form a ring. ), A cyano group, a hydroxyl group, an alkoxyl group, an acyloxy group, a formyl group, a carboxyl group (an acid anhydride may be formed from its ester or two carboxyl groups) or a silyl group. (7) a chain unsaturated compound having functional groups at both ends (c)
Is the general formula (VII):

[0014]

Embedded image (VII) [wherein, m and n are each independently an integer of 0 to 5, X ₁ and X ₂ are each independently OR, COOR or OCOR (R represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms). ). [6] The method for producing a compound having functional groups at both ends according to (6). (8) The compound having both ends functionalized according to (6) or (7), wherein the cyclic unsaturated compound (b) is a combination of the compound represented by the general formula (VI) and a monocycloalkene having 4 to 12 carbon atoms. Manufacturing method. (9) The method for producing a compound having functional groups at both ends according to any of (4) to (8), wherein the ring-opening polymerization catalyst is a ruthenium complex. (10) The method for producing a compound having functional groups at both ends according to (9), wherein the compound is hydrogenated with hydrogen continuously after the ring-opening polymerization. (11) The method for producing a compound having functional groups at both ends according to any one of (4) to (10), wherein the catalyst for hydrogenation contains a ring-opening polymerization catalyst. (12) The number average molecular weight of the both-end functional compound is 300 to 300
The both-terminal functional compound according to any one of (1) to (3), wherein the compound is 30,000. (13) The number-average molecular weight of the both-end functional compound is 300 to
The method for producing a double-terminal functional compound according to any one of (4) to (11), which is 30,000

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. According to the present invention, there is provided a compound having a functional compound at both terminals, wherein both terminals are each independently represented by the general formula (I), and a repeating unit containing at least one kind of the repeating unit represented by the general formula (II). Is done. The repeating unit represented by the general formula (II) may be a combination of two or more types of repeating units satisfying the general formula (II). Further, a unit represented by the general formula (III) may be included as a repeating unit.

X _1- (CH ₂ ) _m -CH-, X _2- (CH ₂ ) _n -CH- (I) wherein X ₁ and X ₂ are independently OR, COOR or OCO
R (R represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms), and m and n each independently represent an integer of 0 to 5. ]

[0017]

Embedded image (II)

Embedded image (II ') wherein, A represents the general formula (II') or an oxygen atom, R ₁ ~
R ₈ is independently a halogen atom, a hydrogen atom, or an optionally substituted hydrocarbon group having 1 to 20 carbon atoms (two or more of R _{1 to} R ₈ may be linked to form a ring .), A cyano group, a hydroxyl group, an alkoxyl group, an acyloxy group, a formyl group, a carboxyl group (an acid anhydride may be formed from its ester or two carboxyl groups) or a silyl group. -Y- (III) [wherein, Y represents an alkylene group having 4 to 12 carbon atoms. Specifically, R is a hydrogen atom; an alkyl group having 1 to 6 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, amyl, and hexyl; aryl such as phenyl, tolyl, mesityl, and naphthyl And the like.

More specifically, the functional groups X ₁ and X ₂ forming both ends of the compound having both ends functional groups in the present invention include methoxy, ethoxy, propoxy, isobutoxy,
alkoxyl groups such as tert-butoxy; acetoxy;
Acyloxy groups such as propionyloxy, benzoyloxy, and toluoyloxy; hydroxyl groups; and carboxyl groups. Of these, a hydroxyl group and an acyloxy group are preferred, and a hydroxyl group and an acetoxy group are more preferred.

R _{1 to} R ₈ in the general formula (II) will be described below with specific examples. Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom. Examples of the hydrocarbon group having 1 to 20 carbon atoms which may have a substituent include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, amyl, hexyl, octyl, decyl, dodecyl, octadecyl and the like. Alkyl groups, cycloalkyl groups such as cyclopentyl and cyclohexyl, aryl groups such as phenyl, tolyl, mesityl, and naphthyl; and rings in which two or more of R _{1 to} R ₈ are linked, substitution bonded to one common carbon atom A group, that is, ₃ to _{4 in which} R ₁ and R ₂ , R ₃ and R ₄ or R ₅ and R ₆ are linked;
A 6-membered spiro ring, a 5- to 8-membered condensed ring sharing carbon atoms represented by α and β in the general formula (II), hydroxymethyl, hydroxyethyl, chloromethyl, methoxymethyl, acetoxymethyl and the like. And a substituted alkyl group. Further, a cyano group; a hydroxyl group; an alkoxyl group such as methoxy, ethoxy, propoxy, isobutoxy, and tert-butoxy; an acyloxy group such as acetoxy and propionyloxy; a formyl group; a carboxyl group or its carboxyl group such as methyl, ethyl, propyl, butyl, and phenyl; Esters or acid anhydrides that can be formed from two carboxyl groups; silyl groups such as trimethylsilyl;

Among these R _{1 to} R _8, a hydrogen atom, a hydrocarbon group and a hydroxyl group are preferred, and a hydrogen atom and a hydrocarbon group having 1 to 10 carbon atoms are more preferred.

In formula (III), Y represents a tetramethylene group, a pentamethylene group, a hexamethylene group,
Examples thereof include a linear alkylene group such as an octamethylene group and an alkylene group having a side chain such as a 3-methylhexamethylene group. Preferably it is a C6-C10 alkylene group.

The both-terminal functional compound of the present invention has a compound represented by the general formula (IV) at both ends and a carbon-containing compound (a) containing a repeating unit represented by the general formula (V). It is produced by hydrogenating a carbon double bond. The repeating unit represented by the general formula (V) can be a combination of two or more types of repeating units satisfying the general formula (V).

X _1- (CH ₂ ) _m -CH =, X _2- (CH ₂ ) _n -CH = (IV) wherein X ₁ and X ₂ are independently OR, COOR or OCO
R (R represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms), and m and n each independently represent an integer of 0 to 5. ]

[0024]

Embedded image (V)

Embedded image(V ′) wherein A represents the general formula (V ′) or an oxygen atom, R₉~ R
₁₆Has independently a halogen atom, a hydrogen atom and a substituent
And a hydrocarbon group having 1 to 20 carbon atoms (R₁₁And R ₁₂, R
₁₃And R₁₄Is an independent alkylide
R may be a group ₉~ R₁₆Two or more of
It may be formed. ), Cyano group, hydroxyl group, alkoxyl
Group, acyloxy group, formyl group, carboxyl group
An acid anhydride from an ester or two carboxyl groups
It may be formed. ) Or a silyl group. ]

Specifically, R is a hydrogen atom; methyl, ethyl, propyl, isopropyl, butyl, isobutyl,
C 1-6 such as tert-butyl, amyl, hexyl, etc.
And an aryl group such as phenyl, tolyl, mesityl, and naphthyl. Also, more specifically, X
₁ and X ₂ are alkoxyl groups such as methoxy, ethoxy, propoxy, isobutoxy and tert-butoxy;
Acetoxy, propionyloxy, benzoyloxy,
Acyloxy groups such as toluoyloxy; hydroxyl groups; carboxyl groups and the like. Of these, a hydroxyl group and an acyloxy group are preferred, and a hydroxyl group and an acetoxy group are more preferred.

R _{9 to} R ₁₆ in the general formula (V) will be described below with specific examples. Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom. Examples of the hydrocarbon group having 1 to 20 carbon atoms which may have a substituent include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, amyl, hexyl, octyl, decyl, dodecyl, octadecyl and the like. An alkyl group, a cycloalkyl group such as cyclopentyl and cyclohexyl, an aryl group such as phenyl, tolyl, mesityl, and naphthyl; and a divalent unsaturated formed independently from each set of R ₁₁ and R ₁₂ , and R ₁₃ and R _14. the hydrocarbon groups include methylene (= CH _2), ethylidene, propylidene, alkylidene group isopropylidene, R ₉ to R ₁₆
The ring in which two or more are connected to each other is a substituent bonded to one common carbon atom, that is, a 3- to 6-membered ring in which R ₉ and R ₁₀ , R ₁₁ and R ₁₂ or R ₁₃ and R ₁₄ are connected. A spiro ring, a condensed 5- to 8-membered ring sharing carbon atoms represented by α and β in the general formula (I), and substituted alkyl groups such as hydroxymethyl, hydroxyethyl, chloromethyl, methoxymethyl, and acetoxymethyl. Is mentioned.

Further, a cyano group; a hydroxyl group;
Toxic, propoxy, isobutoxy, tert-butoxy
Alkoxyl groups such as acetoxy; propionyloxy
Acyloxy groups such as silicon; formyl groups; carboxyl groups
Or its methyl, ethyl, propyl, butyl, phenyl
Formed from esters or two carboxyl groups
Acid anhydrides that can be used; silyl groups such as trimethylsilyl, etc.
No. These R ₉~ R₁₆Of which is preferably hydrogen
Atom, hydrocarbon group, hydroxyl group, more preferably hydrogen atom
And a hydrocarbon group having 1 to 10 carbon atoms.

The compound having a functional group at both terminals of the present invention comprises a cyclic unsaturated compound (b) containing at least a compound represented by the general formula (VI) and a chain unsaturated compound (c) having a functional group at both terminals. The compound (a) having an alicyclic structure or a heterocyclic structure in its main chain, which is produced by ring-opening polymerization using a catalyst, is hydrogenated.

At least one of the cyclic unsaturated compounds (b) has the general formula (VI):

[0030]

Embedded image (VI)

Embedded image (VI ') wherein, A represents the general formula (VI') or an oxygen atom, R ₉ ~
R ₁₆ is independently a halogen atom, a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 20 carbon atoms (R ₁₁ and R ₁₂ ,
R ₁₃ and R ₁₄ may be independently an alkylidene group in each group, or two or more of R _{9 to} R ₁₆ may be linked to form a ring. ), A cyano group, a hydroxyl group, an alkoxyl group, an acyloxy group, a formyl group, a carboxyl group (an acid anhydride may be formed from its ester or two carboxyl groups) or a silyl group. And a norbornene-based compound represented by the formula: These norbornene compounds can be used alone or in combination of two or more.

More specifically, the monomer compounds forming the repeating unit represented by the general formula (VI) include norbornene, 2,5-norbornadiene, and 5-ethylidene-2.
-Norbornene, 2-methyl-5-norbornene, 2-
Hexyl-5-norbornene, 2-cyclohexyl-5
-Norbornenes formed only from hydrocarbons such as norbornene, dicyclopentadiene, benzonorbornadiene, 5-norbornene-2-carbonitrile, 5-norbornene-2-carbaldehyde, 5-norbornene-
2,3-dicarboxylic anhydride, 2-trimethylsilyl-
5-norbornene, 2-chloro-5-norbornene, 2
-Methoxycarbonyl-5-norbornene, 2-methyl-5-norbornene-3-carbaldehyde, 2-methyl-5-norbornene-3-methanol and the like, norbornenes having a substituent other than a hydrocarbon group, 8-ethylidenetetra Cyclo [4.4.0.1 ^2,5 . 1 ^7,10] -3-dodecene, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^{2, 5. Examples} thereof include norbornene-based compounds such as norbornenes having a condensed ring such as [ ^1,7,10 ] -3-dodecene.

As the heterocyclic compound, benzooxanorbornadiene, 2,3-bis (methoxymethyl)
And oxonorbornenes such as -7-oxa-5-norbornene and 2,3-trifluoromethyl-7-oxa-5-norbornene. These norbornene compounds may be used alone or in combination of two or more. Of these norbornene-based compounds, preferred are norbornenes formed of only hydrocarbons, and more preferred are norbornene and 5-ethylidene-
2-norbornene.

As the cyclic unsaturated compound (b), a norbornene compound represented by the general formula (VI) is indispensable, but other cyclic unsaturated compounds can be combined. However, the cyclic unsaturated compound must not inhibit ring-opening polymerization of the norbornene-based compound. Examples thereof include cycloalkenes such as cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, and cyclodecene; substituted cycloalkenes such as 4-methyl-1-cyclohexene; cyclopentadiene; methylcyclopentadiene;
Cycloalkadienes such as cyclooctadiene, 3-cyclohexene-1-methanol, 3-cyclohexene-
Cyclic unsaturated compounds such as cycloalkenes having a hydroxyl group such as 1,1-dimethanol and 6-methyl-3-cyclohexene-1,1-dimethanol, and halogenated cycloalkenes such as 3-bromocyclohexene. . These cyclic unsaturated compounds may be used alone or in combination of two or more. Of these cyclic unsaturated compounds, preferred are cycloalkenes.

The compound (a) having an alicyclic structure or a heterocyclic structure in the main chain, which is a precursor of the compound having both terminal functional groups of the present invention, is at least a cyclic unsaturated compound containing a compound represented by the general formula (VI). The compound (b) and the chain unsaturated compound (c) having a functional group at both terminals can be produced by ring-opening polymerization using a catalyst. As a specific production method, to a mixture of a chain unsaturated compound having a functional group at both terminals and a ring-opening polymerization catalyst, a so-called metathesis catalyst, a part or the whole amount of the cyclic unsaturated compound is added little by little and polymerized. There is a method. More specifically, after the reaction is started by adding a catalyst to a mixture containing a chain unsaturated compound having a functional group at both terminals and a solvent, or in some cases, a cyclic unsaturated compound as well,
This is a production method in which a cyclic unsaturated compound is added to the mixture and reacted.

A chain unsaturated compound having a functional group at both terminals used in the process for producing the compound (a) having an alicyclic structure or a heterocyclic structure in the main chain, which is a precursor of the compound having a functional group at both terminals of the present invention. (C) has the general formula (VII):

[0036]

Embedded image (VII) [wherein, m and n are each independently an integer of 0 to 5, X ₁ and X ₂ are each independently OR, COOR or OCOR (R represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms). ). And a compound for introducing a functional group into both terminals as well as a molecular weight regulator.

Specifically, R is a hydrogen atom; methyl, ethyl, propyl, isopropyl, butyl, isobutyl,
C 1-6 such as tert-butyl, amyl, hexyl, etc.
And an aryl group such as phenyl, tolyl, mesityl, and naphthyl. More specifically, the functional groups X ₁ and X ₂ forming both ends of the compound having both ends functional groups in the present invention are alkoxyl groups such as methoxy, ethoxy, propoxy, isobutoxy, tert-butoxy, etc .; acetoxy, propionyloxy, Acyloxy groups such as benzoyloxy and toluoyloxy; hydroxyl groups;
And a carboxyl group. Of these, a hydroxyl group and an acyloxy group are preferred, and a hydroxyl group and an acetoxy group are more preferred.

Examples of the chain unsaturated compound represented by the general formula (VII) include 1,4-dihydroxy-2-butene,
Diol compounds at both ends such as 6-dihydroxy-3-hexene and 1,8-dihydroxy-4-octene;
Diacetoxy-2-butene, 1,6-diacetoxy-3
-Hexene, 1,8-diacetoxy-4-octene and other terminal diol carboxylic acid ester compounds, maleic acid, fumaric acid and other terminal carboxylic acid compounds, dimethyl maleate, diethyl maleate, dimethyl fumarate, fumaric acid Carboxylic acid ester compounds such as diethyl at both ends are exemplified. Of these, preferably used are diol compounds at both ends and carboxylic acid ester compounds of diols at both ends, and more preferably 1,4-dihydroxy-2-butene and 1,4-diacetoxy-2-butene.

The amount of the chain unsaturated compound having a functional group at both terminals is 0.1 mol per mole of the cyclic unsaturated compound.
Desirably, it is 100. The molar ratio may be reduced when a high molecular weight bifunctional compound is desired, and the molar ratio may be increased when a low molecular weight bifunctional compound is desired.

The ring-opening polymerization catalyst used in the present invention is a catalyst capable of causing a so-called metathesis reaction to proceed, and includes titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, rhenium, ruthenium, Osmium, rhodium,
It is a metal catalyst such as iridium. As the catalyst, a catalyst supported on a carrier or a complex catalyst can be used, but a complex catalyst is preferable.

Specific examples are described below. (C_FiveH_Five) T
i (CH_Three)_TwoOr (C_FiveH_FiveN)_TwoTiCl_FourTo C_TwoH_FiveA
lCl_TwoAnd CH_ThreeAlCl_Two, A titanium-based catalyst mixed with
l_ThreeTa = CHSi (CH_Three)_ThreeSuch as tantalum-based catalysts,
(N-C_FourH₉)_FourSn or (C_TwoH_Five)_ThreeTan mixed with Al
Gusten-based catalyst, ((CH_Three)_ThreeCCH_TwoO)_Two(O, P-
(Iso-C_ThreeH₇)_TwoC₆H_Three) -N = Mo = CH (te
r-C_FourH₉), MoCl _FiveTo C_TwoH_FiveAlCl_TwoMixed
Molybdenum based catalyst, ReCl_FiveN-C_FourH ₉)_FourS
n and (C_TwoH_Five)_ThreeRhenium-based catalyst mixed with Al
Ru and osmium catalysts include RuCl_Three,
OsCl_ThreeAnd the following carbene
Complex, wherein Me is a ruthenium atom or osmium
Represents an atom. ), Cl_Two[P (iso-C_ThreeH₇)_Three]_Two
Me = CH-C₆H_Five, BrCl [P (iso-C_ThreeH₇)
_Three]_TwoMe = CH-C₆H_Five, Cl_Two[P (iso-C
_ThreeH₇)_Three]_TwoMe = CH- [C₆H_Four(CH_Three)], Cl
_Two[P (iso-C_ThreeH₇)_Three]_TwoMe = CH- [C₆H
_Four(Ter-C_FourH₉)], BrCl [P (iso-C_ThreeH
₇)_Three]_TwoMe = CH-CH_TwoC₆H_Five, Cl_Two[P (sec
-C_FourH₉)_Three]_TwoMe = CH-C₆H_FiveTo phosphorus atoms such as
A carbene complex having a ligand to which a kill group is bonded, Cl_Two
[P (C_FiveH₉)_Three]_TwoMe = CH_Two, Cl_Two[P (C_FiveH₉)
_Three]_TwoMe = CH-CH_Three, Br_Two[P (C_FiveH₉)_Three]_TwoMe
= CH-iso-C_ThreeH₇, Cl_Two[P (C_FiveH₉)_Three]_TwoM
e = CH-nC_FourH₉, Cl_Two[P (C_FiveH₉)_Three]_TwoMe
= CH-C_FiveH₉, Cl_Two[P (C_FiveH₉)_Three]_TwoMe = CH
-C₆H₁₁, F_Two[P (C_FiveH₉)_Three]_TwoMe = CH-C
₆H_Five, Cl_Two[P (C_FiveH₉)_Three]_TwoMe = CH-C₆H_Five,
Br_Two[P (C_FiveH₉)_Three]_TwoMe = CH-C₆H_Five, Br
_Two[P (C_FiveH₉)_Three]_TwoMe = CH- (C₆H_Four-OC
_TwoH _Five), Cl_Two[P (C_FiveH₉)_Three]_TwoMe = CH- (C₆H
_Four-Br), Cl_Two[P (C_FiveH₉)_Three]_TwoMe = CH- [C
₆H_Three− (CH_Three)_Two], F_Two[P (C_FiveH₉)_Three]_TwoMe = C
H- [C₆H_Three− (CH_Three)_Two], Br_Two[P (C_FiveH₉)_Three]
_TwoMe = CH-CH_TwoC ₆H_FiveCyclopentic to phosphorus atom
Carbene complex having a ligand to which
_Two[P (C₆H₁₁)_Two-CH_TwoCH_Two−P (C₆H₁₁)_Two] M
e = CH-C₆H_Five, Cl_Two[P (C₆H₁₁)_Three]_TwoMe = C
H_Two, Cl_Two[P (C₆H₁₁)_Three]_TwoMe = CH-CH_Three, C
l_Two[P (C₆H₁₁)_Three]_TwoMe = CH-n-C_FourH₉, Cl
_Two[P (C₆H₁₁)_Three]_TwoMe = CH-ter-C_FourH₉, C
l_Two[P (C₆H₁₁)_Three]_TwoMe = CH-C_TenH₉, F_Two[P
(C₆H₁₁)_Three]_TwoMe = CH-C₆H_Five, Cl_Two[P (C₆
H₁₁)_Three]_TwoMe = CH-C₆H_Five, Br_Two[P (C₆H₁₁)
_Three]_TwoMe = CH-C₆H_Five, Cl_Two[P (C₆H₁₁)_Three]_TwoM
e = CH (C₆H_Four-CH_Three), Cl_Two[P (C₆H₁₁)_Three]
_TwoMe = CH-C₆H_Four-CH (CH_Three)_Two, Cl_Two[P (C
₆H₁₁)_Three]_TwoMe = CH- [C₆H_Four(Ter-C
_FourH₉)], Br_Two[P (C₆H₁₁)_Three]_TwoMe = CH-C ₆
H_Two− (CH_Three)_Three, Cl_Two[P (C₆H₁₁)_Three]_TwoMe = C
HC₆H_Four-OCH_Three, Br_Two[P (C₆H₁₁)_Three]_TwoMe
= CH- (C₆H_Four-NO_Two), Cl_Two[P (C₆H_{1 1})_Three]
_TwoMe = CH- (C₆H_Four-Cl), BrCl [P (C₆H
₁₁)_Three]_TwoMe = CH-CH_TwoC₆H_Five, BrCl [P (C₆
H₁₁)_Three]_TwoMe = CH-CH_TwoC₆H_Five, Cl_Two[P (C₆
H₁₁)_Two(C (CH_TwoCH_Two)_TwoN (CH_Three)_TwoCl)]_TwoM
e = CH-C₆H_Five, Cl_Two[P (C₆H₁₁)_Two(CH_TwoCH
_TwoSO_ThreeNa)]_TwoMe = CH-C₆H _Five, Cl_Two[P (C₆
H₁₁)_Two(CH_TwoCH_TwoN (CH_Three)_ThreeCl)]_TwoMe = CH
-C₆H_FiveWith a cyclohexyl group bonded to a phosphorus atom such as
Carbene complex with ligand, Cl_Two[P (C₆H_Five)_Three]_Two
Me = CH-C₆H_Five, Cl_Two[P (C₆H_Four-CH_Three)_Three] _Two
Me = CH-C₆H_Five, Br_Two[P (C₆H_Three− (C
H_Three)_Two)_Three]_TwoMe = CH-C₆H_Five, Cl_Two[P (C₆H_Two
− (CH_Three)_Three)_Three]_TwoMe = CH-C₆H_FiveSuch as phosphorus atom
Carbene complex having a ligand to which an aromatic group is bonded, WO
 98/21214 of ruthenium and osmium
Carbene complexes, Thomas Weskamp et al., Angew. Chem. Int.
 Ed., Vol. 37, 2490 (1998)
-Dialkyl-imidazoline-2-ylidene coordinated
Carbene complex or Cl_Two[P (C₆H₁₁) _Three]_TwoRu = C =
CH (ter-C_FourH₉) And the like.

These catalysts can be used alone or in combination of two or more. Of these, a tungsten atom, a molybdenum atom, a ruthenium atom, a complex having an osmium atom, more preferably a complex having a ruthenium atom, a carbene complex having a ligand of a phosphorus-based or nitrogen-based compound is Used.

The catalyst is used in a molar ratio of 1 to 0.00001, preferably 0.1 to 0.000, relative to the cyclic unsaturated compound.
1, more preferably in the range of 0.01 to 0.0002. If it exceeds 1, the cost increases, and if it is too small, the reaction rate tends to decrease, which is not preferable.

The reaction mode of the ring-opening polymerization of the present invention is not particularly limited, but it is preferable to carry out the reaction by a homogeneous reaction. The homogeneous reaction may be a solventless reaction, but is preferably performed in a solvent.

There are no particular restrictions on the use of the solvent,
Desirable solvents include methanol, ethanol, n-
Propanol, isopropanol, n-butanol, s
ec-butanol, ter-butanol, isobutanol, cyclohexanol, alcohols such as propylene glycol monomethyl ether, pentane, hexane, heptane, octane, nonane, cyclohexane, cycloheptane, cyclooctane and other aliphatic hydrocarbons, benzene, Toluene, xylene, ethylbenzene,
Aromatic hydrocarbons such as cumene, halogenated hydrocarbons such as chlorobutane, bromohexane, methylene chloride, chloroform, dichloroethane, chlorobenzene, and dichlorobenzene, and halogenated aromatic hydrocarbons, ethyl acetate, isopropyl acetate, and n-butyl acetate , Methyl propionate, propylene glycol monomethyl ether acetate, ethyl lactate, saturated carboxylic esters such as methyl 3-methoxypropionate, diethyl ether,
Dibutyl ether, tetrahydrofuran, dioxane,
Ethers such as dimethoxyethane, ketones such as acetone and methyl ethyl ketone, dimethylformamide,
Aprotic polar solvents such as dimethylacetamide, N-methylpyrrolidone, and dimethylsulfoxide;

These solvents can be used alone or in combination of two or more. These solvents do not necessarily need to be used after being dehydrated and purified, and can be reacted in the presence of water. For example, in the catalyst system of the present invention, emulsion polymerization can be performed in an aqueous solution in the presence of a surfactant or in a mixed system of water and a solvent such as methylene chloride or toluene.

Although the dissolution of oxygen in the solvent does not cause a serious problem, if the reaction time is long, the catalyst may be gradually deactivated.

The reaction can be carried out at a temperature ranging from 0 to 200 ° C. Desirably, it is 15 to 100 ° C. The reaction is generally carried out at normal pressure, but may be carried out under reduced pressure or under a pressure of 5 MPa or less.

As a method for producing a compound having both terminal functional groups of the present invention by hydrogenating a compound (a) having an alicyclic structure or a heterocyclic structure as a precursor in the main chain, a carbon-carbon compound is basically used.
All methods capable of hydrogenating a carbon double bond can be mentioned.
For example, a stoichiometric method using a metal hydride, a metal hydride complex compound, a reagent such as borane or hydrazine, or a catalytic method using hydrogen is used. It is difficult to select one of these methods, but catalytic hydrogenation with hydrogen is desirable from the viewpoint of economy and mass productivity. However, when it is necessary to leave a substituent such as an aldehyde or a nitrile group without hydrogenation, a method of selectively hydrogenating only a carbon-carbon double bond is used instead of a hydrogenation method using hydrogen. There is a need.

The catalyst for hydrogenation with hydrogen in the method for producing a compound having both terminal functional groups according to the present invention is classified into a heterogeneous catalyst and a homogeneous catalyst.

As the heterogeneous catalyst, palladium, platinum,
Examples of the catalyst include a catalyst in which ruthenium, rhodium and the like are supported on activated carbon, alumina and silica, a Raney metal catalyst such as nickel and ruthenium, and a metal oxide catalyst such as palladium oxide and platinum oxide.

As a homogeneous catalyst, Ni (CH ₃ COC)
_{HCOCH 3) 2 / (C 2} H 5) 3 Al, (C 5 H 5) 2 TiC
l ₂ / (C ₂ H ₅ ) ₂ AlCl, [(C ₆ H ₅ ) ₃ P] ₃ RhC
1, [(C ₆ H ₅ ) ₃ P] ₃ RuCl ₂ , [(C ₆ H ₅ ) ₃ P]
₃ RuH ₂ , [(C ₆ H ₅ ) ₃ P] ₃ (CO) RuCl ₂ ,
[(C ₆ H ₅ ) ₃ P] ₃ (CO) RuHCl or a ruthenium or osmium metathesis catalyst used in ring-opening polymerization can be used.

These hydrogenation catalysts are composed of a compound (a) having an alicyclic structure or a heterocyclic structure as a precursor in the main chain and a hydrogenation catalyst (weight) of 1: 1 × 10 ^-6 to 1: 2. Can be used in a range. When a ruthenium or osmium metathesis catalyst is used for ring-opening polymerization, the ring-opening polymerization catalyst can be used as it is as a hydrogenation catalyst.
It is also possible to react by adding a solid catalyst such as / C or a new hydrogenation catalyst such as a rhodium complex.

The hydrogen pressure in the hydrogenation reaction can be in the range from normal pressure to 30 MPa. If the pressure is too low, the reaction does not proceed, and if the pressure is too high, there is a problem in equipment and safety. Desirably, it is in the range of 0.2 to 15 MPa. The temperature of the hydrogenation reaction can be in the range of −20 to 300 ° C., preferably from 10 ° C. to 20 ° C.
It is in the range of 0 ° C.

A method for obtaining the compound having both functional groups at both ends of the present invention by hydrogenating a compound (a) having a main chain having an alicyclic structure or a heterocyclic structure as a precursor (hereinafter referred to as "ring-opened polymer"). In the above method, the ring-opening polymer is once isolated, then dissolved again in a solvent, and a reaction is performed by adding a hydrogenation catalyst. After the ring-opening polymerization, the ring-opening polymer is continuously isolated without isolation. A method of hydrogenating the reaction solution may be mentioned. In consideration of economy and the like, it is preferable to hydrogenate the reaction solution directly after the ring-opening polymerization. In particular, when ring-opening polymerization is carried out using a complex such as ruthenium or osmium as a catalyst, the complex also becomes a hydrogenation catalyst for the ring-opening polymer, which is advantageous. In such a case, another hydrogenation catalyst such as a solid hydrogenation catalyst such as Pd / C or Raney nickel or a homogeneous hydrogenation catalyst such as a ruthenium complex or a rhodium complex may be additionally used.

The both-terminal functional compound of the present invention is a compound in which the carbon-carbon double bond of the ring-opening polymer is hydrogenated by 50% or more. In consideration of prevention of deterioration due to light or oxygen oxidation, preferably, 70% or more is hydrogenated, and more preferably, 90% or more is hydrogenated.

The form of the hydrogenation reaction of the present invention is not particularly limited, but is preferably carried out in a solvent. The solvent is not particularly limited as long as it does not inhibit the reaction, but preferable solvents include methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, ter-butanol, isobutanol, and the like. Alcohols such as cyclohexanol and propylene glycol monomethyl ether, pentane,
Aliphatic hydrocarbons such as hexane, heptane, octane, nonane, cyclohexane, cycloheptane, and cyclooctane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and cumene; ethyl acetate, isopropyl acetate, and n-butyl acetate , Methyl propionate,
Propylene glycol monomethyl ether acetate,
Saturated carboxylic esters such as ethyl lactate and methyl 3-methoxypropionate; ethers such as diethyl ether, dibutyl ether, tetrahydrofuran, dioxane, and dimethoxyethane; ketones such as acetone and methyl ethyl ketone; dimethylformamide; dimethylacetamide; Aprotic polar solvents such as methylpyrrolidone and dimethylsulfoxide; and amines such as triethylamine, tributylamine and pyridine.

These can be used alone or as a mixture of two or more. These solvents do not necessarily need to be purified and used.

The both-terminal functional compound obtained by the present invention is useful as a resin modifier, a plasticizer and a raw material for polycondensation.
In these applications where a compound having both terminal functional groups is used as a reaction raw material, a compound having both terminal functional groups having a molecular weight in a so-called oligomer region, as represented by polybutadiene polyol, is preferable. The molecular weight at that time is 300 to 30,000 as the number average molecular weight in terms of polystyrene measured by gel permeation chromatography (hereinafter referred to as GPC). Preferred number average molecular weight is from 300 to 28,000, more preferably from 300 to 28,000.
25,000.

The method for recovering a compound having both terminal functional groups from the reaction solution produced by the method of the present invention is not particularly limited. For example, the reaction solution can be precipitated by dropping it into a poor solvent, and the compound having functional groups at both ends can be recovered by filtration or the like.

The method for removing the catalyst is not particularly limited. For example, in a method of recovering a compound having both terminal functional groups by dropping a reaction solution into a poor solvent, the compound having both terminal functional groups is insoluble as a poor solvent, but if a solvent that dissolves a catalyst is used, the compound having both terminal functional groups is used. At the stage of recovering the catalyst, the catalyst can be removed at the same time.

The compound having a functional group at both terminals obtained by the present invention may be a known antioxidant such as hydroquinone, methoxyphenol, 2,6-di-tert-butyl-4-methylphenol, 2,2'-dioxy- 3,3'-di-t
phenol-based antioxidants such as er-butyl 5,5'-dimethyldiphenylmethane; sulfur-based antioxidants such as dilauryl 3,3'-thiodipropionate and dimyristyl 3,3'-thiodipropionate; Phosphorus antioxidants such as phyt and diphenylisodecyl phosphite can be added and stabilized by a known method. Also, known UV absorbers, for example, 2,
4-dihydroxybenzophenone, 2-hydroxy-4
It is also possible to stabilize by adding -methoxybenzophenone or the like.

[0063]

EXAMPLES The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to the following examples.

The reagents and solvents used in the examples were used as purchased without any purification such as dehydration. However, degassing by inert gas replacement was performed before use.

The term “room temperature” in the examples indicates a temperature range of 10 to 25 ° C. unless otherwise specified.

The obtained both-end functional compounds were analyzed as follows.

Gel Permeation Chromatography (GPC) The number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) in terms of polystyrene were measured using tetrahydrofuran or xylene as an eluent.

The proton nuclear magnetic resonance spectrum ( ¹ H-
NMR) The structure and the functional groups at both terminals were confirmed and quantified by ¹ H-NMR in Example 1 in deuterated chloroform and Examples 2, 3 and 7 in tricyclobenzene / deuterated benzene.

Vapor pressure osmotic pressure measurement (VPO) The number average molecular weight (Mn) was measured in chloroform.

Differential scanning calorimetry (DSC) Heating rate: 10 ° C./min Measurement range: room temperature to 250
° C

(Example 1) A 50-ml three-necked flask equipped with a cooling tube and a dropping funnel was replaced with nitrogen, and 5.16 g (30 mmol) of 1,4-diacetoxy-2-butene and 10 ml of toluene were added. The catalyst (Cl ₂ [P (C ₆ H
₁₁ ) ₃ ] ₂ Ru = CH—C ₆ H ₅ ) 0.06 g (0.07 m)
mol) was dissolved and stirred with a mechanical stirrer.
Place the flask in an oil bath, raise the bath temperature to 40 ° C,
9.0 g of ethylidene norbornene adjusted separately (75 g
(mmol) in 10 ml of toluene was dropped from the dropping funnel over 1 hour. After completion of dropping, 2 at 40 ° C
Reacted for hours.

The solution after the reaction was cooled to room temperature. The reaction solution was placed in a 100 ml stainless steel autoclave, and stirred at a hydrogen pressure of 6 MPa and a temperature of 155 ° C. for 4 hours.
A time hydrogenation reaction was performed. After completion of the reaction, the mixture was cooled and dropped into 200 ml of methanol to precipitate a solid. Purification was repeated three times by precipitating this solid content in 200 ml of methanol dissolved in 20 ml of toluene. The purified solid was dried under vacuum. It was a slightly viscous transparent viscous solid.

The GPC of this solid was measured, and the Mn in terms of polystyrene was 4,800 and the Mw / Mn was 2.3.

FIG. 1 shows the results of ¹ H-NMR measurement. Hydrogenated portion of the norbornene skeleton and ethylidene group (CH group, CH ₂ group, CH ₃ group: 1-3 ppm) and methylene group of terminal ester portion (CH ₂ O group: 4.0 ppm)
Was confirmed. Only a part of the double bond (5.2 ppm) was detected, but other peaks were not confirmed. From the integration ratio of each peak, the hydrogenation rate was 99%. ¹ H-NM
The molecular weight Mn calculated from the result of R was 3,800.
^From the result of ¹ H-NMR, the following structure was presumed. This compound is designated as A. In the formula, n represents the number of repeating units.

[0075]

Embedded image (A)

The molecular weight Mn measured by VPO is 36.
00, which was in good agreement with the molecular weight measured by ¹ H-NMR.

[0077] have been introduced functional groups ensure both ends are prepared compound by the method of the present invention from the results, ¹
It was confirmed that the molecular weight Mn can be calculated from the H-NMR measurement results. Thereafter, from the ¹ H-NMR measurement results, the molecular weight Mn
Was calculated.

Example 2 A 300 ml three-necked flask equipped with a cooling tube and a dropping funnel was purged with argon, and 20.64 g of 1,4-diacetoxy-2-butene (120 mmol)
l), 70 ml of toluene was added. The catalyst (Cl
₂ [P (C ₆ H ₁₁ ) ₃ ] ₂ Ru = CH-C ₆ H ₅ ) 0.3 g
(0.35 mmol) was dissolved and stirred with a mechanical stirrer. Place the flask in the oil bath and set the bath temperature to 5
Raise to 5 ° C and adjust separately 28.2g of norbornene
(300 mmol) dissolved in 70 ml of toluene was added dropwise from a dropping funnel over 5 hours. After dropping 5
The reaction was performed at 5 ° C. for 2 hours.

After completion of the reaction, 100 ml of the reaction solution was
Then, the mixture was placed in a stainless steel autoclave and subjected to a hydrogenation reaction at a hydrogen pressure of 0.7 MPa and a temperature of 130 ° C. for 7 hours while stirring. After completion of the hydrogenation reaction, the reaction solution was diluted with 300 ml of methanol.
And the solid content was completely precipitated. This solid was filtered, washed with methanol, and dried under vacuum. The solid was a white powder.

FIG. 2 shows the result of ¹ H-NMR measurement of the obtained white powder. Hydrogenated portion of the norbornene skeleton (C
An H group, a CH ₂ group of 1 to 3 ppm) and a methylene group (4 ppm of a CH ₂ O group) in the terminal acetate portion were confirmed. Only a part of the double bond (5.2 ppm) was detected, but other peaks were not confirmed. From the integration ratio of each peak, the hydrogenation ratio was 99% or more. The molecular weight Mn calculated from each peak was 4,700. ¹ H-NM
The following structure was estimated from the result of R. This compound is designated as B. In the formula, n represents the number of repeating units.

[0081]

Embedded image (B)

Example 3 As a cyclic unsaturated compound,
1,5-Cyclooctadiene and norbornene were used.

A 300 ml three-necked flask equipped with a cooling tube and a dropping funnel was replaced with argon, and 1,4-diacetoxy-
4.13 g (24 mmol) of 2-butene, toluene 30
ml and 25.92 g of 1,5-cyclooctadiene (2
40 mmol) was added. A catalyst (Cl ₂ [P
_{(C 6 H 11) 3]} 2 Ru = CH-C 6 H 5) 0.12g
(0.14 mmol) was dissolved and stirred with a magnetic stirrer. The flask was placed in an oil bath, the bath temperature was raised to 55 ° C, and norbornene 11.2 adjusted separately was used.
A solution of 8 g (120 mmol) dissolved in 45 ml of toluene was added dropwise from a dropping funnel over 5 hours. After the completion of the dropwise addition, the reaction was carried out at 55 ° C for 2 hours.

The solution after the reaction was cooled to room temperature. Take 100 ml of this reaction solution, put it in a 150 ml stainless steel autoclave, and stir with a hydrogen pressure of 0.7 MPa.
a, A hydrogenation reaction was performed at a temperature of 130 ° C. for 7 hours. After completion of the hydrogenation reaction, the reaction solution was dropped into 300 ml of methanol to completely precipitate solids. This solid was filtered, washed with methanol, and dried under vacuum. The solid was a white powder.

Next, the ester portion was saponified. Solid content and 100ml in 200ml eggplant type flask with cooling tube
Tetrahydrofuran was added and stirred at 90 ° C. to dissolve. To this solution, 20 ml of an ethanol solution containing 2 g of sodium ethoxide was added and reacted for 5 hours. After the completion of the reaction, the mixture was cooled and dropped into 300 ml of methanol to completely precipitate a solid content. This solid was filtered, washed with methanol, and dried under vacuum. The solid was a white powder.

FIG. 3 shows the result of ¹ H-NMR measurement. Hydrogenated portion of norbornene skeleton and butadiene skeleton (CH group, CH ₂ group 1.3 ppm) and methylene group of terminal alcohol portion (CH ₂ O group 3.5 ppm)
Was confirmed. Only a part of the double bond (5.2 ppm) was detected, but other peaks were not confirmed. From the integration ratio of each peak, the hydrogenation ratio was 99% or more. The copolymerization ratio of norbornene and cyclooctadiene calculated from each peak was 0.67: 0.33, and the molecular weight M
n was 3600. ^From the result of ¹ H-NMR, the following structure was presumed. This compound is designated C.
In the formula, m and n represent the number of repeating units.

[0087]

Embedded image (C)

Example 4 The solubility of compounds A, B and C in a solvent was examined. Table 1 shows the results.

[0089]

[Table 1]

Example 5 DSC thermal analysis of compounds A, B and C was performed. Table 2 shows the results.

[0091]

[Table 2]

From Example 4 and the results, it was found that Compound B had strong crystallinity and had a melting point (Tm). Since compound C has almost the same physical properties as compound B, it is presumed that compound C has strong crystallinity. Since compound A has an ethyl group in the side chain of the norbornene skeleton, it is considered that the oligomer is non-crystalline, has a low melting point, and has high solubility in a solvent.

Test Example 1 A stability test was conducted on a ring-opened polymer and a hydrogenated product of the ring-opened polymer. The ring-opened polymer was prepared in Example 1,
About 1 ml was taken out of the reaction solution immediately after the ring-opening polymerization of 2, 3 and precipitated with methanol. The precipitate was dissolved in tetrahydrofuran, and this solution was added dropwise to methanol to cause reprecipitation. This operation was repeated twice. This precipitate was vacuum-dried at room temperature to obtain a ring-opened polymer (before hydrogenation). The ring-opening polymers of Examples 1, 2, and 3 were A ', B',
C ′ and the hydrogenated product of the ring-opening polymer are A, B and C, respectively.

Table 3 shows the results of observing the color change after each compound was placed in a sample bottle and left at room temperature for one month in an air atmosphere. Any ring-opened polymer not hydrogenated was colored. This is considered to have been oxidized by oxygen. From this, it was confirmed that the hydrogenated product was extremely stable.

[0095]

[Table 3]

(Example 6) A 50-ml three-necked flask equipped with a cooling tube and a dropping funnel was replaced with nitrogen, and 2.64 g (30 mmol) of 1,4-dihydroxy-2-butene and 10 ml of toluene were added. The catalyst (Cl ₂ [P (C ₆ H
₁₁ ) ₃ ] ₂ Ru = CH—C ₆ H ₅ ) 0.06 g (0.07 m)
mol) was dissolved and stirred with a magnetic stirrer. The flask was placed in an oil bath, the bath temperature was raised to 40 ° C., and 6.0 g of separately prepared ethylidene norbornene.
(50 mmol), 2.4 g of norbornene (25 mmol)
A solution of l) dissolved in 10 ml of toluene was added dropwise from a dropping funnel over 1 hour and 30 minutes. After completion of dropping, 2 at 40 ° C
Reacted for hours.

The solution after the reaction was cooled to room temperature. The reaction solution was mixed with 0.5 ml of triethylamine and 5% Pd /
0.1 g of C was placed in a 100 ml stainless steel autoclave and stirred at a hydrogen pressure of 7 MPa at a temperature of 155 ° C. for 2 hours.
A time hydrogenation reaction was performed. After the completion of the reaction, the mixture was cooled and a part thereof was dropped into methanol to precipitate a solid content. Purification was repeated three times by dissolving this solid in cyclohexane and dropping it into methanol to precipitate. The solids separated by filtration were dried under vacuum.

FIG. 4 shows the results of ¹ H-NMR measurement. Hydrogenated portion of the norbornene skeleton and ethylidene group (CH group, CH ₂ group, CH ₃ group 1 to ₃ ppm) and methylene group of terminal ester portion (CH ₂ O group 3.6 ppm)
Was confirmed. Although some double bonds (5.2 ppm) were detected, the hydrogenation rate was 90% based on the integration ratio of each peak. ^The molecular weight Mn calculated from the result of ¹ H-NMR is 38.
00. ^From the result of ¹ H-NMR, the following structure was presumed. This compound is designated as D. In the formula, m and n represent the number of repeating units.

[0099]

Embedded image (D)

[0100]

Industrial Applicability The present invention provides a compound having functional groups at both ends having an alicyclic structure or a heterocyclic structure in the main chain, which is excellent in mechanical strength and thermal stability, and a novel method for producing the same. The both-end functional compound produced by the present invention can be used in a wide range of fields such as resin modifiers, plasticizers and raw materials for polycondensation polymers.

[0101]

[Brief description of the drawings]

¹ in FIG. 1 both end functional type compound prepared in Example 1
H-NMR spectrum

FIG. 2 shows ^{one of the} compounds having functional groups at both ends prepared in Example 2.
H-NMR spectrum

¹ of Figure 3 both terminal functional type compound prepared in Example 3
H-NMR spectrum

FIG. 4 shows ^{one of the} compounds having functional groups at both ends produced in Example 6.
H-NMR spectrum

Continued on the front page F-term (reference) 4J032 BA07 BB01 BB03 BC03 BD05 CA32 CA33 CA34 CA43 CA45 CA68 CB01 CB03 CD02 CE03 CF03

Claims (13)

[Claims] 1. Both ends are each independently of the general formula (I)
And a repeating unit represented by the general formula (II) or a repeating unit represented by the general formula (II) and the general formula (III). X _1- (CH ₂ ) _m -CH _2- , X _2- (CH ₂ ) _n -CH _2- (I) wherein X ₁ and X ₂ are independently OR, COOR or OCO
R (R represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms), and m and n each independently represent an integer of 0 to 5. [Formula 1] (II) (II ') wherein, A represents the general formula (II') or an oxygen atom, R ₁ ~
R ₈ is independently a halogen atom, a hydrogen atom, or an optionally substituted hydrocarbon group having 1 to 20 carbon atoms (two or more of R _{1 to} R ₈ may be linked to form a ring .), A cyano group, a hydroxyl group, an alkoxyl group, an acyloxy group, a formyl group, a carboxyl group (an acid anhydride may be formed from its ester or two carboxyl groups) or a silyl group. -Y- (III) [wherein, Y represents an alkylene group having 4 to 12 carbon atoms. ] 2. Both ends are each independently represented by the general formula (I)
The compound having both ends functionalized according to claim 1, wherein the compound comprises a repeating unit represented by the general formula (II). 3. R _{1 to} R _{8 in} the general formula (II) each independently represent a halogen atom, a hydrogen atom, or an optionally substituted hydrocarbon group having 1 to 20 carbon atoms (R _{1 to} R _8). Two or more of which may be linked to form a ring).
2. A compound having both ends functionalized according to the above. 4. Both ends are each independently of the general formula (I)
V), between which repetition represented by the general formula (V)
Hydrogenation of the carbon-carbon double bond of compound (a) containing
Characterized in that both ends are independent of each other
A main chain structure represented by the general formula (I)
Is a repeating unit containing a repeating unit represented by the general formula (II)
A method for producing a bifunctional compound comprising a repeating unit. X₁− (CH_Two)_m-CH =, X_Two− (CH_Two) N-CH = (IV) wherein X₁, X_TwoAre independently OR, COOR or OCO
R (R represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms
Represent. ), And m and n independently represent an integer of 0 to 5
You. [Chemical formula 3](V)(V ′) wherein A represents the general formula (V ′) or an oxygen atom, R₉~ R
₁₆Has independently a halogen atom, a hydrogen atom and a substituent
And a hydrocarbon group having 1 to 20 carbon atoms (R₁₁And R ₁₂, R
₁₃And R₁₄Is an independent alkylide
R may be a group ₉~ R₁₆Two or more of
It may be formed. ), Cyano group, hydroxyl group, alkoxyl
Group, acyloxy group, formyl group, carboxyl group
An acid anhydride from an ester or two carboxyl groups
It may be formed. ) Or a silyl group. X₁− (CH_Two)_m-CH_Two-, X_Two− (CH_Two)_n-CH_Two-(I) wherein X₁, X_TwoAre independently OR, COOR or OCO
R (R represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms
Represent. ), And m and n independently represent an integer of 0 to 5
You. [Chemical formula 5](II)(II ′) wherein A represents the general formula (II ′) or an oxygen atom;₁~
R₈Independently has a halogen atom, a hydrogen atom and a substituent
A C 1-20 hydrocarbon group (R₁~ R₈Horse
Two or more may be linked to form a ring. ), Cyano
Group, hydroxyl group, alkoxyl group, acyloxy group,
Group, carboxyl group (the ester or two
An acid anhydride may be formed from a boxyl group. ) Or
Represents a ril group. ] 5. The compound of the general formula (V)₉~ R₁₆Independently
Halogen atom, hydrogen atom, and optionally substituted charcoal
A hydrocarbon group having a prime number of 1 to 20 (R₁₁And R₁₂, R ₁₃And R₁₄Is
Each group may be independently an alkylidene group.
K, R₉~ R_{1 6}Even when two or more of
Good. )).
Production method. 6. A catalyst comprising at least a cyclic unsaturated compound (b) containing a compound represented by the general formula (VI) and a chain unsaturated compound (c) having a functional group at both terminals,
The bifunctional compound according to claim 4, which is obtained by hydrogenating a carbon-carbon double bond of a compound (a) having an alicyclic structure or a heterocyclic structure in a main chain produced by ring-opening polymerization. Production method. Embedded image (VI) (VI ') wherein, A represents the general formula (VI') or an oxygen atom, R ₉ ~
R ₁₆ is independently a halogen atom, a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 20 carbon atoms (R ₁₁ and R ₁₂ ,
R ₁₃ and R ₁₄ may be independently an alkylidene group in each group, or two or more of R _{9 to} R ₁₆ may be linked to form a ring. ), A cyano group, a hydroxyl group, an alkoxyl group, an acyloxy group, a formyl group, a carboxyl group (an acid anhydride may be formed from its ester or two carboxyl groups) or a silyl group. ] 7. A chain unsaturated compound (c) having functional groups at both ends is represented by the general formula (VII): (VII) [wherein, m and n are each independently an integer of 0 to 5, X ₁ and X ₂ are each independently OR, COOR or OCOR (R represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms). ). ] The method for producing a compound having functional groups at both ends according to claim 6, which is represented by the formula: 8. The cyclic unsaturated compound (b) represented by the general formula (V)
The method for producing a compound having both ends functionalized according to claim 6 or 7, which is a combination of the compound represented by I) and a monocycloalkene having 4 to 12 carbon atoms. 9. The method according to claim 4, wherein the ring-opening polymerization catalyst is a ruthenium complex. 10. The method for producing a compound having both ends functionalized according to claim 9, wherein hydrogenation is carried out with hydrogen continuously after the ring-opening polymerization. 11. The method for producing a compound having both terminal functional groups according to claim 4, wherein the hydrogenation catalyst includes a ring-opening polymerization catalyst. 12. The double-terminal functional compound according to any one of claims 1 to 3, wherein the double-terminal functional compound has a number average molecular weight of 300 to 30,000. 13. The method for producing a compound having both terminal functional groups according to claim 4, wherein the number average molecular weight of the compound having both terminal functional groups is 300 to 30,000.