JP2011046935A - Method of manufacturing allyl alcohol copolymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing an allyl alcohol copolymer excellent in compatibility with various resins, adhesiveness, an electric insulating property, low water absorbability, thermal stability and surface-active effect, and useful, for example, as a resin improver, a paint component, an ink component, an adhesive component, a primer component, a high-performance wax, a compatibilizer, a surfactant, a lubricating oil additive, a polyurethane raw material and a polyester raw material. <P>SOLUTION: The method for manufacturing the allyl alcohol copolymer is characterized by subjecting a copolymer containing structure indicated by an ester of a 3C or more C alcohol, for example, 1-decene, as a monomer unit, to a transesterification reaction in the presence of the alcohol and a catalyst. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing an allyl alcohol copolymer.

  Olefin polymers having a polar group in the structure are widely used industrially because they are excellent in compatibility with various polar resins and adhesiveness, and are easily colored. Various methods for producing such an olefin polymer having a polar group have been reported, but the introduction of the polar group-containing monomer by graft polymerization accounts for the majority.

  For example, JP 2005-113038 A (Patent Document 1) discloses a polar group-containing higher olefin polymer in which a higher group α-olefin polymer is introduced with a polar group by acting a decomposer and a polar compound. However, in the method using graft polymerization, deterioration due to oxidation of the produced polymer and dispersibility of polar groups are concerned, and it is difficult to say that the method is satisfactory in terms of product quality.

  Therefore, in order to solve this problem, an example of production by copolymerization of a polar group-containing monomer and another olefin monomer has been reported. However, there are few examples of this method, and for example, Japanese Patent Application Laid-Open No. 64-54009 (Patent Document 2) and Japanese Patent Application Laid-Open No. 2003-165809 (Patent Document 3) are known. These are systems utilizing anionic polymerization, and there are disadvantages in terms of production cost, for example, it is necessary to treat the polar group-containing monomer with an equimolar amount or more of an organometallic compound in advance for the expression of catalytic activity. there were.

  On the other hand, US Pat. No. 5,444,141 (Patent Document 4) discloses an example of producing a copolymer by radical copolymerization of allyl alcohol and an aromatic vinyl monomer. In this method, although the productivity of the polymer is improved and the production cost is reduced, only the copolymerization of allyl alcohol and styrene is disclosed in the examples, and is not performed with other polymerizable monomers. It was.

  Furthermore, radical copolymerization of allyl alcohol with monomers other than aromatic vinyl monomers is rare, and even if a product is obtained, the yield is low and the number average molecular weight is less than 1000. For this reason, the method of manufacturing efficiently the polymer which has a polar group using the polymerizable monomer which has carbon-carbon double bonds other than styrene was desired.

JP 2005-113038 A JP-A 64-54009 Japanese Patent Laid-Open No. 2003-165809 US Pat. No. 5,444,141

  An object of the present invention is to provide a method for efficiently producing a copolymer of allyl alcohol and an α-olefin.

  As a result of intensive studies to solve the above problems, the present inventors copolymerized a fatty acid allyl ester and an aliphatic olefin compound having radical polymerization ability in the presence of a radical polymerization initiator, resulting in the result. The resulting copolymer is transesterified in the presence of an alcohol and a catalyst, or the copolymer of a fatty acid allyl ester and an aromatic radical polymerizable monomer is hydrogenated and then subjected to an ester exchange reaction in the presence of an alcohol and a catalyst. Thus, the inventors have found that a polymer having a polar group can be produced efficiently and inexpensively, and completed the present invention.

及び式（２）

（式中、Ｒ¹は炭素数１〜１０の脂肪族炭化水素基を表わし、分岐していても、環状構造を含んでいてもよく、Ｒ²は炭素数２〜２０の脂肪族炭化水素基を表わし、分岐していても、環状構造を含んでいてもよい。）
で示される構造をモノマーユニットとして含む共重合体を触媒の存在下にアルコールとエステル交換反応することを特徴とする
式（３）

及び式（２）

（式中、Ｒ²は前記と同じ意味を表わす。）
で示される構造をモノマーユニットとして含むアリルアルコール共重合体の製造方法。
［２］エステル交換反応に使用するアルコールが炭素数１〜１０のアルキルアルコールである前記［１］に記載のアリルアルコール共重合体の製造方法。
［３］前記炭素数１〜１０のアルキルアルコールが、エタノールまたは１−プロパノールである前記［２］に記載のアリルアルコール共重合体の製造方法。
［４］エステル交換反応に使用する触媒が水酸化ナトリウム、水酸化リチウム、または水酸化カリウムである前記［１］〜［３］のいずれかに記載のアリルアルコール共重合体の製造方法。
［５］エステル交換反応に使用する触媒が水酸化ナトリウムである前記［４］に記載のアリルアルコール共重合体の製造方法。
［６］式（１）中のＲ¹で表わされる炭素数１〜１０の脂肪族炭化水素基が、炭素数１〜５の直鎖状の脂肪族炭化水素基である前記［１］〜［５］のいずれかに記載のアリルアルコール共重合体の製造方法。
［７］前記炭素数１〜５の直鎖状の脂肪族炭化水素基が、メチル基、エチル基、またはｎ−プロピル基である前記［６］に記載のアリルアルコール共重合体の製造方法。
［８］前記炭素数１〜５の直鎖状の脂肪族炭化水素基が、メチル基である前記［１］〜［７］のいずれかに記載のアリルアルコール共重合体の製造方法。
［９］式（２）中のＲ²が炭素数２〜１０の直鎖状脂肪族炭化水素基、または炭素数６〜１０の脂環式炭化水素基である前記［１］〜［８］のいずれかに記載のアリルアルコール共重合体の製造方法。
［１０］式（２）中のＲ²が、エチル基、ｎ−プロピル基、ｎ−ブチル基、ｎ−ぺンチル基、ｎ−ヘキシル基、ｎ−オクチル基、ｎ−デシル基、ｎ−ドデシル基、またはシクロヘキシル基である前記［９］に記載のアリルアルコール共重合体の製造方法。
［１１］式（１）と式（２）のモノマーユニットのみからなる前記［１］〜［１０］のいずれかに記載のアリルアルコール共重合体の製造方法。
［１２］ラジカル重合性のオレフィン化合物を共重合して得られる構造を第三のモノマーユニットとして含む前記［１］〜［１１］のいずれかに記載のアリルアルコール共重合体の製造方法。
［１３］前記第三のモノマーユニットが、アクリル酸メチル、メタクリル酸メチル、酢酸ビニル、またはスチレンに由来する構造である前記［１２］に記載のアリルアルコール共重合体の製造方法。
［１４］式（１）で示されるモノマーユニットが全モノマーユニットに対して３〜６０ｍｏｌ％である前記［１］〜［１３］のいずれかに記載のアリルアルコール共重合体の製造方法。
［１５］ラジカル重合性のオレフィン化合物ユニットを全モノマーユニットに対して０．１〜２０．０ｍｏｌ％含む前記［１２］に記載のアリルアルコール共重合体の製造方法。 That is, the present invention relates to the following [1] to [15].
[1] Formula (1)

And formula (2)

(In the formula, R ¹ represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms, which may be branched or include a cyclic structure, and R ² represents an aliphatic hydrocarbon group having 2 to 20 carbon atoms. And may be branched or include a cyclic structure.)
A copolymer containing the structure represented by the formula (3) as a monomer unit is transesterified with an alcohol in the presence of a catalyst.

And formula (2)

(Wherein R ² represents the same meaning as described above.)
The manufacturing method of the allyl alcohol copolymer which contains the structure shown by as a monomer unit.
[2] The method for producing an allyl alcohol copolymer according to [1], wherein the alcohol used in the transesterification reaction is an alkyl alcohol having 1 to 10 carbon atoms.
[3] The method for producing an allyl alcohol copolymer according to [2], wherein the alkyl alcohol having 1 to 10 carbon atoms is ethanol or 1-propanol.
[4] The method for producing an allyl alcohol copolymer according to any one of [1] to [3], wherein the catalyst used in the transesterification reaction is sodium hydroxide, lithium hydroxide, or potassium hydroxide.
[5] The method for producing an allyl alcohol copolymer according to the above [4], wherein the catalyst used in the transesterification reaction is sodium hydroxide.
[6] The above [1] to [1], wherein the aliphatic hydrocarbon group having 1 to 10 carbon atoms represented by R ¹ in the formula (1) is a linear aliphatic hydrocarbon group having 1 to 5 carbon atoms. [5] The method for producing an allyl alcohol copolymer according to any one of [5].
[7] The method for producing an allyl alcohol copolymer according to [6], wherein the linear aliphatic hydrocarbon group having 1 to 5 carbon atoms is a methyl group, an ethyl group, or an n-propyl group.
[8] The method for producing an allyl alcohol copolymer according to any one of [1] to [7], wherein the straight-chain aliphatic hydrocarbon group having 1 to 5 carbon atoms is a methyl group.
[9] The above [1] to [8], wherein R ² in the formula (2) is a linear aliphatic hydrocarbon group having 2 to 10 carbon atoms or an alicyclic hydrocarbon group having 6 to 10 carbon atoms. The manufacturing method of the allyl alcohol copolymer in any one of.
[10] R ² in formula (2) is an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-octyl group, an n-decyl group, or an n-dodecyl group. The manufacturing method of the allyl alcohol copolymer as described in said [9] which is a group or a cyclohexyl group.
[11] The method for producing an allyl alcohol copolymer according to any one of [1] to [10], comprising only the monomer units of the formula (1) and the formula (2).
[12] The method for producing an allyl alcohol copolymer according to any one of the above [1] to [11], comprising a structure obtained by copolymerizing a radical polymerizable olefin compound as a third monomer unit.
[13] The method for producing an allyl alcohol copolymer according to [12], wherein the third monomer unit has a structure derived from methyl acrylate, methyl methacrylate, vinyl acetate, or styrene.
[14] The method for producing an allyl alcohol copolymer according to any one of [1] to [13], wherein the monomer unit represented by the formula (1) is 3 to 60 mol% with respect to all monomer units.
[15] The method for producing an allyl alcohol copolymer according to [12], wherein the radically polymerizable olefin compound unit is contained in an amount of 0.1 to 20.0 mol% based on all monomer units.

  According to the present invention, a copolymer of allyl alcohol and olefin can be efficiently produced. The allyl alcohol copolymer obtained by the present invention is excellent in compatibility with various resins and adhesiveness in that it has a polar group. In addition, since it has a hydrophobic group, it is excellent in electrical insulation, low water absorption, thermal stability, and surface active effect. Therefore, it is useful as, for example, a resin modifier, a paint component, an ink component, an adhesive component, a primer component, a high-performance wax, a compatibilizer, a surfactant, a lubricant additive, a polyurethane raw material, and a polyester raw material.

2 is a ¹ H-NMR spectrum of an allyl acetate / 1-decene copolymer obtained in Example 3. 4 is an IR spectrum of the allyl acetate / 1-decene copolymer obtained in Example 3. 2 is a ¹ H-NMR spectrum of an allyl alcohol / 1-decene copolymer obtained in Example 3. 3 is an IR spectrum of an allyl alcohol / 1-decene copolymer obtained in Example 3. 2 is a ¹ H-NMR spectrum of a product obtained in Comparative Example 2. 3 is an IR spectrum of the product obtained in Comparative Example 2.

及び式（２）

（式中、Ｒ¹は炭素数１〜１０の脂肪族炭化水素基を表わし、分岐していても、環状構造を含んでいてもよく、Ｒ²は炭素数２〜２０の脂肪族炭化水素基を表わし、分岐していても、環状構造を含んでいてもよい。）
で示される、脂肪酸アリルエステルに由来するモノマーユニット（式（１））とα−オレフィンに由来するモノマーユニット（式（２））を含む共重合体である。この共重合体を本明細書では「アリルエステル共重合体」という。 Hereinafter, the present invention will be described in more detail.
[Allyl ester copolymer]
The copolymer which is a precursor of the allyl alcohol copolymer of the present invention has the formula (1)

And formula (2)

(In the formula, R ¹ represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms, which may be branched or include a cyclic structure, and R ² represents an aliphatic hydrocarbon group having 2 to 20 carbon atoms. And may be branched or include a cyclic structure.)
It is a copolymer containing the monomer unit (Formula (1)) derived from fatty acid allyl ester and the monomer unit (Formula (2)) derived from an α-olefin. This copolymer is referred to herein as an “allyl ester copolymer”.

R ¹ in the formula (1) represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms, which may be linear or branched or may contain a cyclic structure.

Examples of linear aliphatic hydrocarbon groups include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl and n-decyl groups. Etc.
Examples of the branched aliphatic hydrocarbon group include isopropyl group, isobutyl group, sec-butyl group, neopentyl group, isohexyl group, and isooctyl group.
Examples of the alicyclic hydrocarbon group containing a cyclic structure include a cyclohexyl group, a cyclohexylmethyl group, and a cyclohexylethyl group.

The R ¹ Among these, a linear aliphatic hydrocarbon group having 1 to 5 carbon atoms preferred in terms of cost reduction during the polymer production. From the viewpoint of cost reduction during production of the polymer, a methyl group, an ethyl group, and an n-propyl group are particularly preferable.

R ² in Formula (2) represents an aliphatic hydrocarbon group having 2 to 20 carbon atoms, which may be linear or branched or may contain a cyclic structure.

Examples of linear aliphatic hydrocarbon groups include ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n-decyl, n- A dodecyl group, n-tetradecyl group, n-hexadecyl group, n-octadecyl group, n-eicosyl group, etc. are mentioned.
Examples of the branched aliphatic hydrocarbon group include isopropyl group, isobutyl group, sec-butyl group, neopentyl group, isohexyl group, isooctyl group, and isodecyl group.
Examples of the alicyclic hydrocarbon group containing a cyclic structure include a cyclohexyl group, a cyclohexylmethyl group, a cyclohexylethyl group, a decahydronaphthalenyl group, and a cyclohexenyl group.

Among these, R ² is preferably a linear aliphatic hydrocarbon group having 2 to 10 carbon atoms or an alicyclic hydrocarbon group having 6 to 10 carbon atoms from the viewpoint of improving compatibility with various resins. From the viewpoint of improving compatibility with various resins, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group A cyclohexyl group is particularly preferred.

  The allyl ester copolymer of the present invention may consist of only the monomer units of the formulas (1) and (2), and may contain a third monomer unit as necessary. The third monomer unit is the same as that described in the section of the allyl alcohol copolymer described later. Further, when the conversion rate of the transesterification reaction of the allyl ester copolymer of the formula (1) is not 100%, the allyl ester copolymer obtained has a monomer unit derived from the formula (2). However, this can also be counted as a kind of third monomer unit. Two or more types of third monomer units may be used.

で示される構造と式（２）

（式中、Ｒ²は炭素数２〜２０の脂肪族炭化水素基を表わし、分岐していても、環状構造を含んでいてもよい。）
で示される構造をモノマーユニットとして含む共重合体である。必要に応じて第三のモノマーユニットを含んでいてもよい。 [Allyl alcohol copolymer]
The allyl alcohol copolymer of the present invention has the formula (3)

Structure and formula (2)

(Wherein R ² represents an aliphatic hydrocarbon group having 2 to 20 carbon atoms and may be branched or include a cyclic structure.)
It is a copolymer containing the structure shown by as a monomer unit. A third monomer unit may be included as required.

The monomer unit having the structure represented by the formula (2) is the same as that described in the description of the allyl ester copolymer, and the same can be exemplified for R ² . The same applies to preferred examples.

  The allyl alcohol copolymer of the present invention is a copolymer containing only the structure represented by the formula (3) and the structure represented by the formula (2) or, if necessary, radical polymerization as a third monomer unit. A structure obtained by copolymerizing a functional olefin compound may be introduced. Two or more types of third monomer units may be used.

  Examples of radically polymerizable olefin compounds include acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, acrylic acid (n-propyl), acrylic acid (n-butyl), methyl methacrylate, ethyl methacrylate, methacrylic acid. Examples include acid (n-propyl), methacrylic acid (n-butyl), 2-norbornene, vinyl acetate, ethylene, and styrene.

  Among these, methyl acrylate, methyl methacrylate, vinyl acetate, and styrene are preferable from the viewpoint of improving productivity during the production of the copolymer.

  In the allyl alcohol copolymer of the present invention, the copolymerization mode of the monomer unit represented by the formula (3) and the monomer unit represented by the formula (2) can be random, block, or alternating depending on the polymerization conditions. Randomness is desirable from the viewpoint of improving compatibility with each resin. The same applies when the third monomer unit is included.

  In the allyl alcohol copolymer of the present invention, the composition of each monomer unit corresponds to the allyl ester corresponding to the monomer unit represented by the formula (1) and the monomer unit represented by the formula (2) at the time of producing the allyl ester copolymer. It can control by the preparation ratio and polymerization conditions of the olefin compound and radically polymerizable olefin compound.

  It is preferable that the monomer unit shown by Formula (1) is 3-60 mol% with respect to all the monomer units from a viewpoint of making compatibility and adhesiveness to the various resin of the allyl alcohol copolymer of this invention compatible. Furthermore, 4 to 40 mol% is more preferable, and 10 to 30 mol% is most preferable. When the monomer unit represented by the formula (1) is less than 3 mol%, the adhesiveness is remarkably lowered, and when it exceeds 60 mol%, the compatibility with a resin having a low polarity is deteriorated.

  Moreover, when a radically polymerizable olefin compound unit is included, it is preferable that those monomer units are 0.1-20.0 mol% with respect to all the monomer units from a viewpoint of the compatibility improvement to various resin. Furthermore, 0.5 to 15.0 mol% is more preferable, and 2.0 to 10.0 mol% is most preferable. When the radically polymerizable olefin compound unit is less than 0.1 mol%, the compatibility with a highly polar resin is deteriorated, and when it exceeds 20.0 mol%, the compatibility with a low polarity resin is deteriorated.

  The hydroxyl value of the allyl alcohol copolymer of the present invention is preferably 10 to 300 mgKOH / g from the viewpoint of achieving compatibility with various resins and adhesiveness. Furthermore, it is more preferable that it is 50-250 mgKOH / g, and 100-200 mgKOH / g is the most preferable. When the hydroxyl value of the copolymer is less than 10 mgKOH / g, the adhesiveness is lowered, and when it exceeds 300 mgKOH / g, the compatibility with a resin having low polarity is deteriorated. The hydroxyl value is a value measured according to the method described in JIS K0070.

  There is no restriction | limiting in particular in the number average molecular weight (Mn) of the copolymer of this invention. The polystyrene-equivalent number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is preferably Mn = 500 to 8000 in consideration of compatibility with various resins. Furthermore, it is more preferable that it is 500-5000, and 650-3000 are the most preferable. When the number average molecular weight (Mn) in terms of polystyrene is less than 500, the compatibility with the solid resin is deteriorated, and when it exceeds 8000, the compatibility with the liquid resin is deteriorated.

[Production method]
Next, the manufacturing method of the allyl alcohol copolymer of this invention is demonstrated. The allyl alcohol copolymer of the present invention can be produced by the following two methods: Method A and Method B.
Method A: radically polymerizable, which is a fatty acid allyl ester corresponding to the monomer unit represented by formula (1), an olefin compound corresponding to the monomer unit represented by formula (2), and, if necessary, a third monomer The olefin compound is copolymerized in the presence of a radical polymerization initiator, and the resulting allyl ester copolymer (precursor A) is transesterified in the presence of an alcohol and a catalyst.
Method B: A copolymer of a fatty acid allyl ester and an aromatic radical polymerizable monomer is hydrogenated, and the resulting allyl ester copolymer (precursor B) is transesterified in the presence of an alcohol and a catalyst.

Method A: Precursor A prepared by radical copolymerization of fatty acid allyl ester with an olefin compound corresponding to the monomer unit represented by formula (2) and a radically polymerizable olefin compound is transesterified in the presence of an alcohol and a catalyst. Method <Preparation of Precursor A>
In the method for producing a copolymer of the present invention, the olefin compound corresponding to the monomer unit represented by the formula (2) used for the production of the precursor A is not particularly limited as long as it can be radically polymerized. When the structure described in the detailed description part of the allyl ester copolymer is expressed in the form of an olefin compound, for example, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1 -Linear terminal olefins such as dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, 1-tricosene, 3-methyl-1-butene, 4-methyl-1-pentene, 3-methyl- Branched olefins such as 1-pentene, 4,4-dimethyl-1-pentene, 3-methyl-1-heptene, 3-methyl-1-nonene, 3-methyl-1-undecene, cyclohexylethylene, 3- Cyclohexyl-1-propene, 4-cyclohexyl-1-butene, decahydronaphthalenylethylene, 4-vinyl-1-cyclohex Such a terminal olefin containing a cyclic structure and the like. Olefin having an unsaturated bond at the 2-position, such as 2-decene, is difficult to polymerize because the growth radical is resonance-stabilized.

  Among these, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, and cyclohexylethylene are particularly preferable from the viewpoint of improving compatibility with various resins. .

  In the production of the copolymer of the present invention, the amount of the fatty acid allyl ester used in the production of the precursor A and the radical polymerizable olefin compound corresponding to the monomer unit represented by the formula (2) is usually represented by the formula (2 The fatty acid allyl ester is preferably used in an amount of 0.05 to 2.0 mol, particularly preferably 0.10 to 1.0 mol, relative to 1 mol of the olefin compound corresponding to the monomer unit represented by If the fatty acid allyl ester is less than 0.05 mol, the resulting precursor A is transesterified, the hydroxyl value becomes too low and the compatibility deteriorates, and if it exceeds 2.0 mol, the molecular weight of the precursor A is increased. It tends to decrease.

  The amount of the radically polymerizable olefin compound used as the third monomer is preferably 0.005 to 0.3 mol based on 1 mol of the olefin compound corresponding to the monomer unit represented by the formula (2). 0.01 to 0.1 mol is particularly preferable. When the radically polymerizable olefin compound as the third monomer is less than 0.005 mol, the yield of the precursor A obtained is lowered, and when it exceeds 0.2 mol, a high molecular weight solid is contained in the precursor A. Products may form and become cloudy. In addition, since the reactivity of each monomer is different, generally the amount ratio of charged monomers and the monomer unit amount ratio in the produced polymer do not coincide.

  The copolymerization reaction in the production of the precursor A may be performed without a solvent, or a solvent that does not react with the substrate and has a small chain transfer constant may be used. Examples of the solvent include hydrocarbon solvents such as toluene, benzene and t-butylbenzene, ketone solvents such as acetone, and halogen solvents such as dichloromethane, chloroform and chlorobenzene. These solvents can be used alone or in combination of two or more.

  The copolymerization reaction in the production of the precursor A can be carried out using a radical polymerization initiator. Any radical polymerization initiator can be used as long as it generates radicals by heat, ultraviolet rays, electron beams, radiation, etc., but those having a half-life of 1 hour or more at the reaction temperature are preferred.

  As thermal radical polymerization initiators, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile) Azo compounds such as dimethyl-2,2′-azobisisobutyrate, 4,4′-azobis (4-cyanopentanoic acid), 2,2′-azobis (2,4,4-trimethylpentane); Ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide; diacyl peroxides such as benzoyl peroxide, decanoyl peroxide, lauroyl peroxide; dicumyl peroxide, t-butylcumyl peroxide , Dialkyl peroxides such as di-t-butyl peroxide; 1,1-di t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-di-t-butylperoxycyclohexane, 2,2-di (t Peroxyketals such as -butylperoxy) butane; t-butylperoxypivalate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, di-t-butylperoxy Hexahydroterephthalate, di-t-butylperoxyazelate, t-butylperoxy-3,5,5-trimethylhexanoate, t-hexylperoxy-2-ethylhexanoate, 1,1,3 3-tetramethylbutylperoxy-2-ethylhexanoate, t-butylperoxyacetate, t-butylperper Alkyl peroxyesters such as xylbenzoate, di-t-butylperoxytrimethyladipate, t-hexylperoxyisopropylmonocarbonate, t-butylperoxylaurate, t-hexylperoxybenzoate; diisopropylperoxydicarbonate, Examples thereof include, but are not limited to, peroxycarbonates such as di-sec-butylperoxydicarbonate and t-butylperoxyisopropyl carbonate; hydrogen peroxide and the like. Two or more of these thermal radical polymerization initiators may be used in combination.

  Examples of radical polymerization initiators by ultraviolet rays, electron beams, and radiation include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, diethoxyacetophenone, 1-hydroxy-cyclohexyl-phenylketone, 2-methyl-1- [ 4- (Methylthio) phenyl] -2-morpholinopropanone-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-hydroxy-2-methyl-1-phenyl Acetophenone derivatives such as propan-1-one; benzophenone derivatives such as benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4-trimethylsilylbenzophenone, 4-benzoyl-4′-methyl-diphenyl sulfide; benzoin, benzoin ethyl ether Examples include, but are not limited to, benzoin derivatives such as benzoin propyl ether, benzoin isobutyl ether, and benzoin isopropyl ether; methylphenylglyoxylate, benzoin dimethyl ketal, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and the like. I don't mean. These ultraviolet rays, electron beams, and radiation radical polymerization initiators may be used in combination of two or more.

  The amount of these polymerization initiators used varies depending on the reaction temperature and the composition ratio of each monomer, and thus cannot be unconditionally limited, but is 0.1 to 15 parts by mass with respect to 100 parts by mass of radical polymerizable monomers. 1.0 to 10 parts by mass is preferable. When the addition amount of the radical polymerization initiator is less than 0.1 parts by mass, the polymerization reaction hardly proceeds, and when the addition amount exceeds 15 parts by mass, the molecular weight of the precursor A may become too low. Moreover, it is not preferable also economically.

  What is necessary is just to select reaction temperature (polymerization temperature) suitably according to the kind of polymerization initiator, and you may make it react (polymerize) by changing temperature in steps. Polymerization with ultraviolet rays or the like is possible even at room temperature. In the case of thermal polymerization, it is desirable to appropriately determine the temperature in accordance with the decomposition temperature of the initiator, and generally the range of 50 to 180 ° C is preferable, and 70 to 170 ° C is particularly preferable. If it is less than 50 ° C., the reaction is extremely slow, and if it exceeds 180 ° C., the radical initiator is too quickly decomposed and the chain transfer is also accelerated, so that the molecular weight of the precursor A tends to decrease.

  After completion of the reaction, the product, allyl ester copolymer (precursor A), is obtained by known operations and processing methods (for example, neutralization, solvent extraction, water washing, liquid separation, solvent distillation, reprecipitation, etc.). Processed and isolated.

<Transesterification reaction of precursor A>
The transesterification reaction can be performed by bringing the precursor A and an alcohol compound into contact with each other in the presence of a catalyst.

  The alcohol compound used in the transesterification reaction is not particularly limited as long as it reacts with an ester, but a primary alcohol is preferable. In view of the affinity with the precursor A, an alkyl alcohol having 1 to 10 carbon atoms is preferable, and ethanol and 1-propanol are particularly preferable.

  Examples of the catalyst that can be used in the transesterification reaction include inorganic acids, inorganic bases, and organic acids. Specific examples of inorganic acids include sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid and the like. Specific examples of the inorganic base include lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide and the like. Specific examples of the organic acid include acetic acid, benzenesulfonic acid, p-toluenesulfonic acid and the like. Among these, as the catalyst, an inorganic base is preferable, and lithium hydroxide, sodium hydroxide, and potassium hydroxide are particularly preferable, and sodium hydroxide is most preferable.

The transesterification reaction can be carried out either in the presence of a solvent or in the absence of a solvent, but for the purpose of removing reaction heat, it is preferable to use a solvent and carry out the reaction in a liquid phase. Any solvent can be used as long as it does not interfere with the reaction. Specifically, halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane; aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane; diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, ethylene Ether solvents such as glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, tetrahydrofuran, 1,4-dioxane; methanol, ethanol, 1-propanol, 2-propanol, 1- Selected from alcohol solvents such as butanol, 2-butanol, isobutyl alcohol and cyclohexanol It can be used alone or in mixture of two or more solvents that.
Among these, an alcohol solvent is preferable from the advantage that it also serves as an alcohol compound used for transesterification, and considering the solubility of the precursor A, ethanol, 1-propanol, and 1-butanol are preferable. In particular, ethanol, 1-propanol Is preferred.

  The transesterification reaction can be carried out at any temperature as long as the reaction efficiency of the catalyst is not lowered, but is usually 0 to 200 ° C, preferably 50 to 150 ° C, more preferably 70 to 120 ° C. The product tends to be colored at high temperatures, and practically no useful reaction rates can be obtained at low temperatures.

  As the reaction form of the transesterification reaction, any reaction form used for a normal transesterification reaction such as a batch reaction or a flow reaction can be taken depending on the process. From the viewpoint of improving the reaction rate, it is desirable to carry out the reaction while distilling the ester compound produced by the reaction out of the reaction system. Moreover, since the usage-amount of a catalyst changes with these reaction forms, there is no restriction | limiting in particular. In a batch process, it is used in the range of usually 0.001 to 10 parts by mass, preferably 0.01 to 5 parts by mass, more preferably 0.05 to 1 part by mass with respect to 100 parts by mass of the precursor A as a substrate. When the amount of catalyst is small, a substantially sufficient reaction rate cannot be obtained, and when the amount of catalyst is large, there is a problem of coloring the product or increasing the catalyst cost.

  After completion of the transesterification reaction, the catalyst residue can be removed by treating the reaction solution with an ion exchange resin. The ion exchange resin used at that time is preferably a strong acid cation exchange resin, and a porous strong acid cation exchange resin (sulfonic acid type) is particularly preferred in view of the removal efficiency of the catalyst residue. The ion exchange resin deteriorated by the catalyst treatment can be reused after being regenerated by a known operation and treatment method (for example, treatment with a hydrochloric acid aqueous solution or the like).

  After removal of the catalyst residue, the product, allyl alcohol copolymer, is isolated by being post-treated by known operations and processing methods (for example, filtration, solvent extraction, water washing, liquid separation, solvent distillation, reprecipitation, etc.). It is.

  The conversion rate of the transesterification reaction can be controlled by the amount of alcohol used, reaction temperature, etc., and there is no particular limitation. Although the required conversion rate varies depending on the use of the product, for example, in the case of use as a polyol, it is preferably 70% or more, and more preferably 90% or more. Considering reactivity, 100% is most preferable. When the conversion rate of the transesterification reaction is less than 100%, the obtained allyl ester copolymer has monomer units derived from the formula (2). By adjusting this conversion rate, the monomer unit derived from the formula (2) can be substituted for the third monomer.

Method B: Method of hydrogenating a copolymer of fatty acid allyl ester and aromatic radical polymerizable monomer, and transesterifying the resulting allyl ester copolymer (precursor B) in the presence of an alcohol and a catalyst. First, a copolymer of a fatty acid allyl ester and an aromatic radical polymerizable monomer is obtained, the aromatic ring of this copolymer is hydrogenated (hydrogenation reaction), and then transesterified. For the copolymer of the fatty acid allyl ester and the aromatic radical polymerizable monomer, refer to the method for producing a copolymer of allyl alcohol and styrene described in US Pat. No. 5,444,141 (Patent Document 4). It can be produced by using a fatty acid allyl ester (preferably allyl acetate).
Examples of the aromatic radical polymerizable monomer include styrene and vinyl toluene.

<Hydrogenation reaction>
The hydrogenation reaction can be performed by contacting a copolymer of a fatty acid allyl ester and an aromatic radical polymerizable monomer with hydrogen gas in the presence of a catalyst.

  Examples of the catalyst that can be used for the hydrogenation reaction include a catalyst containing at least one metal element selected from Groups 6 to 12 of the periodic table as a catalyst component. Specifically, sponge Ni, Ni-diatomaceous earth, Ni-alumina, Ni-silica, Ni-silica alumina, Ni-zeolite, Ni-titania, Ni-magnesia, Ni-chromia, Ni-Cu, Ni-Cu- Co, sponge Co, Co-diatomaceous earth, Co-alumina, Co-silica, Co-silica alumina, Co-zeolite, Co-titania, Co-magnesia, sponge Ru, Ru-carbon, Ru-alumina, Ru-silica, Ru-silica alumina, Ru-zeolite, Rh-carbon, Rh-alumina, Rh-silica, Rh-silica alumina, Rh-zeolite, Pt-carbon, Pt-alumina, Pt-silica, Pt-silica alumina, Pt-zeolite , Pd-carbon, Pd-alumina, Pd-silica, Pd-silica aluminum Include catalysts selected from combinations such as Pd- zeolite. Among these, as the catalyst component, a catalyst containing Rh, Ru or Pd as the metal component is particularly preferable, and Rh-carbon, Ru-carbon, Ru-alumina, Pd-carbon, and Pd-alumina catalyst are particularly preferable.

  The method for preparing the catalyst is not particularly limited, and an ordinary catalyst preparation method can be used. For example, a method of preparing a catalyst by reducing a metal salt solution impregnated as a catalyst with a reducing agent; impregnating a metal salt solution as a catalyst into a simple substance; A method of calcining a metal hydroxide or oxide precipitated on a support by contact with an alkali solution or the like; impregnating a solution of a metal salt serving as a catalyst alone and then contacting the support with an alkali solution or the like A method of preparing a catalyst by calcining a metal hydroxide or oxide precipitated on it and then reducing it with a reducing agent; a method of preparing an alloy of metal and Al, and further eluting Al by alkali treatment However, the present invention is not limited to these.

The hydrogenation reaction is preferably performed in a liquid phase using a solvent for the purpose of removing heat of reaction and lowering the diffusion efficiency of hydrogen due to an increase in viscosity. Any solvent can be used as long as it does not interfere with the reaction. Specifically, halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane; aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane; diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, ethylene Ether solvents such as glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, tetrahydrofuran, 1,4-dioxane; 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol , 2-isopropoxyethanol, 2-butoxyethanol, diethylene glycol monomethyl Ether alcohol solvents such as ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether; methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, cyclohexanol, etc. Alcohol solvent; one or two or more mixed solvents selected from water and the like can be used.
Among these, considering the solubility of hydrogen and the solubility of a copolymer of a fatty acid allyl ester and an aromatic radical polymerizable monomer, ether solvents and halogenated hydrocarbon solvents are preferred, particularly tetrahydrofuran, 1,4-dioxane. And chloroform are preferred.

  The hydrogen pressure in the hydrogenation reaction can be either normal pressure or under pressure, but in order to advance the reaction efficiently, the reaction under pressure is preferred. Usually, the gauge pressure is 0 to 30 MPaG, preferably 1 to 20 MPaG, more preferably 2 to 15 MPaG.

  The hydrogenation reaction can be carried out at any temperature as long as the reaction efficiency of the catalyst is not lowered, but is usually 0 to 300 ° C, preferably 50 to 250 ° C, more preferably 70 to 220 ° C. Side reactions tend to proceed at high temperatures, and practically useful reaction rates cannot be obtained at low temperatures.

The reaction form of the hydrogenation reaction is any reaction form used for normal liquid phase hydrocracking reaction or liquid phase hydrogenation reaction such as suspension bed batch reaction, fixed bed flow reaction, fluidized bed flow reaction, etc. depending on the process. Can also be taken. The amount of the catalyst used varies depending on the reaction form, but is not particularly limited. In the suspension bed batch process, it is usually 0.01 to 100 parts by weight, preferably 0.1 to 50 parts by weight, more preferably 100 parts by weight of the copolymer of fatty acid allyl ester and aromatic radical polymerizable monomer as a substrate. Is used in the range of 0.5 to 20 parts by mass.
When the amount of catalyst is small, a substantially sufficient reaction rate cannot be obtained, and when the amount of catalyst is large, there are problems of an increase in side reactions and an increase in catalyst cost.

  After completion of the hydrogenation reaction, the hydrogenated product of the allyl ester copolymer, which is a product, can be recovered by known operations and processing methods (for example, filtration, solvent extraction, water washing, liquid separation, solvent distillation, reprecipitation, etc.). Processed and isolated.

<Transesterification>
The transesterification reaction can be carried out by bringing a hydrogenated allyl ester copolymer and an alcohol compound into contact with each other in the presence of a catalyst.

  The transesterification reaction can be carried out under the same conditions as described in the description of the method A except that a hydrogenated allyl ester copolymer is used instead of the precursor A.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further in detail, this invention does not receive any limitation by these description.

Various physical properties of the materials synthesized in Examples and Comparative Examples were measured as follows.
1. FT-IR
Model used: Spectrum GX (manufactured by PerkinElmer),
Measurement method: Measured by a liquid film method using a KBr plate.

2. ¹ H-NMR, ¹³ C-NMR
Model used: JEOL EX-400 (400 MHz, manufactured by JEOL Ltd.)
Measurement method: A sample was dissolved in deuterated chloroform or deuterated methanol, and measurement was performed using tetramethylsilane as an internal standard substance.

3. Gel permeation chromatography (GPC)
Equipment used Column: Shodex GPC KG + K-802 + K-802.5 + K-801 (Showa Denko)
Detector: Shodex SE-61 (manufactured by Showa Denko)
Measurement conditions Solvent: Chloroform or tetrahydrofuran,
Measurement temperature: 40 ° C.
Flow rate: 1.0 ml / min,
Sample concentration: 1.0 mg / ml,
Injection volume: 1.0 μl,
Calibration curve: Universal Calibration curve,
Analysis program: SIC 480II (manufactured by System Instruments).

4). Hydroxyl value was measured according to the method described in JIS K0070.
5). Allyl alcohol monomer unit mol%
It calculated from the number average molecular weight and the hydroxyl value.

Example 1: Production of allyl alcohol / 1-decene copolymer Allyl acetate (Tokyo Kasei Kogyo Co., Ltd., 12.00 g, 0.120 mol) and 1-decene (300 ml stainless steel autoclave) Wako Pure Chemical Industries, Ltd., 84.16 g, 0.600 mol), di-t-butyl peroxide (Kishida Chemical Co., Ltd., 4.81 g, 0.0329 mol) were added, and after attaching the flange portion, the system was filled with nitrogen. With 3 replacements. Next, the temperature was raised while stirring the content at 400 rpm, and the reaction was carried out at 145 ° C. for 6 hours.
After the contents were cooled to room temperature and depressurized, the reactor was opened to take out the contents, and unreacted allyl acetate, 1-decene and initiator residue were removed under reduced pressure at 100 ° C. 42.11 g of oil was obtained.
20.00 g of this oily substance, 250 ml of ethanol and sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd., 0.04 g, 0.001 mol) were added to a 500 ml two-necked flask, and the inside of the system was replaced with nitrogen. The reaction was carried out at 4 ° C. for 4 hours. After the contents were cooled to room temperature, the sodium residue was removed through a column packed with 30 g of ion exchange resin (manufactured by Mitsubishi Chemical, DAIAION PK208H), and then ethanol was removed under reduced pressure to obtain 17.87 g of a slightly yellow oily substance. It was. The recovery rate from the raw material was 41.7%.
¹ H-NMR, ¹³ C-NMR and IR spectrum of the obtained oily substance were measured and confirmed to be the desired copolymer. Most of the peaks derived from allyl acetate disappeared. The number average molecular weight of this copolymer was Mn = 1640, the hydroxyl value was 88 mgKOH / g, and the allyl alcohol monomer unit was 19.5 mol%. Furthermore, Table 2 shows the evaluation results of the solubility in hexane, heptane, chloroform, methanol, ethanol and acetone.

Example 2: Production of allyl alcohol / 1-decene copolymer Allyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd., 18.02 g, 0.180 mol) and 1-decene (manufactured by Wako Pure Chemical Industries, Ltd., 84.16 g, 0.600 mol) ), Di-t-butyl peroxide (Kishida Chemical Co., Ltd., 5.10 g, 0.0349 mol) was added, and the reaction and post-treatment were performed in the same manner as in Example 1 to obtain 18.16 g of a slightly yellow oily substance. It was. The recovery rate from the raw material was 44.0%.
¹ H-NMR, ¹³ C-NMR and IR spectrum of the obtained oily substance were measured and confirmed to be the desired copolymer. Most of the peaks derived from allyl acetate disappeared. Moreover, the number average molecular weight of this copolymer was Mn = 1630, the hydroxyl value was 129 mgKOH / g, and the allyl alcohol monomer unit was 27.5 mol%. Furthermore, the evaluation results of the solubility in various solvents are shown in Table 2.

Example 3 Production of Allyl Alcohol / 1-Decene Copolymer A 1 L glass autoclave (manufactured by Pressure Glass Industrial Co., Ltd.) was mixed with allyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd., 100.10 g, 1.000 mol) and 1-decene ( Wako Pure Chemical Industries, 280.60 g, 2.000 mol), di-t-butyl peroxide (Kishida Chemical Co., Ltd., 19.00 g, 0.1299 mol) were added and the flange was attached. With 3 replacements. Next, the temperature was raised while stirring the content at 400 rpm, and the reaction was carried out at 145 ° C. for 6 hours.
After the contents were cooled to room temperature and depressurized, the reactor was opened to take out the contents, and unreacted allyl acetate, 1-decene and initiator residue were removed under reduced pressure at 100 ° C. 180.50 g of oil was obtained. 1H-NMR, 13C-NMR and IR spectrum of the obtained oily substance were measured and confirmed to be the desired copolymer. Most of the peaks derived from allyl acetate disappeared. The results of ¹ H-NMR and IR spectrum measurements are shown in FIGS.
50.00 g of this oily substance, 600 ml of ethanol, and sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd., 0.10 g, 0.0025 mol) were added to a 1 L two-necked flask, and the system was replaced with nitrogen. The reaction was carried out at 5 ° C. for 5 hours. After the contents were cooled to room temperature, the sodium residue was removed through a column packed with 100 g of ion exchange resin (manufactured by Mitsubishi Chemical Corporation, DAIAION PK208H), and then ethanol was removed under reduced pressure to obtain 39.99 g of a slightly yellow oily substance. It was. The recovery rate from the raw material was 45.2%.
¹ H-NMR, ¹³ C-NMR and IR spectrum of the obtained oily substance were measured and confirmed to be the desired copolymer. The results of ¹ H-NMR and IR spectrum measurements are shown in FIGS. The number average molecular weight of this copolymer was Mn = 1880, the hydroxyl value was 207 mgKOH / g, and the allyl alcohol monomer unit was 39.7 mol%. Furthermore, the evaluation results of the solubility in various solvents are shown in Table 2.

Example 4: Production of allyl alcohol / 1-decene copolymer Allyl acetate (Tokyo Chemical Industry, 140.14 g, 1.400 mol) and 1-decene (Wako Pure Chemical Industries, 280.60 g, 2.000 mol) ), Di-t-butyl peroxide (Kishida Chemical Co., Ltd., 21.00 g, 0.144 mol) was added, and the same reaction and post-treatment as in Example 3 were performed to obtain 41.39 g of a slightly yellow oily substance. It was. The recovery rate from the raw material was 52.3%.
¹ H-NMR, ¹³ C-NMR and IR spectrum of the obtained oily substance were measured and confirmed to be the desired copolymer. Most of the peaks derived from allyl acetate disappeared. The copolymer had a number average molecular weight of Mn = 1770, a hydroxyl value of 256 mgKOH / g, and an allyl alcohol monomer unit of 46.6 mol%. Furthermore, the evaluation results of the solubility in various solvents are shown in Table 2.

Example 5: Production of allyl alcohol / 1-decene copolymer Allyl acetate (Tokyo Chemical Industry, 200.20 g, 2.000 mol) and 1-decene (Wako Pure Chemical Industries, 280.60 g, 2.000 mol) ), Di-t-butyl peroxide (Kishida Chemical Co., Ltd., 24.00 g, 0.164 mol) was added, and the same reaction and post-treatment as in Example 3 were performed to obtain 35.50 g of a slightly yellow oily substance. It was. The recovery rate from the raw materials was 53.4%.
¹ H-NMR, ¹³ C-NMR and IR spectrum of the obtained oily substance were measured and confirmed to be the desired copolymer. Most of the peaks derived from allyl acetate disappeared. The number average molecular weight of this copolymer was Mn = 1650, the hydroxyl value was 350 mgKOH / g, and the allyl alcohol monomer unit was 57.8 mol%. Furthermore, the evaluation results of the solubility in various solvents are shown in Table 2.

Example 6: Production of allyl alcohol / vinylcyclohexane copolymer 300 ml of stainless steel autoclave (manufactured by pressure-resistant glass industry), allyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd., 50.06 g, 0.500 mol) and styrene (Wako Pure Chemical Industries, Ltd.) (Comparative, 52.08 g, 0.500 mol), di-t-butyl peroxide (Kishida Chemical Co., Ltd., 5.11 g, 0.0349 mol) were added, the flange was attached, and the system was filled with nitrogen three times. Replaced. Next, the temperature was raised while stirring the content at 400 rpm, and the reaction was carried out at 155 ° C. for 5 hours.
After the contents are cooled to room temperature and depressurized, the reactor is opened to take out the contents, and unreacted allyl acetate, styrene and initiator residue are removed under reduced pressure at 100 ° C. 75.08 g was obtained.
120 ml of stainless steel autoclave containing 6.0 g of the obtained oily substance, 1,4-dioxane (Wako Pure Chemical Industries, 55.0 ml) and powdered 5% Rh-carbon (Wako Pure Chemical Industries, 0.7 g) In addition to (made by pressure-resistant glass industry), after attaching the flange part, the inside of the system is replaced with nitrogen three times, further replaced with hydrogen gas, and finally a hydrogen pressure of 4.5 MPaG (gauge pressure) is applied. It was. Next, the temperature was raised while stirring the content at 400 rpm, and the reaction was carried out at 200 ° C. for 7 hours. During this time, hydrogen was introduced so that the reaction pressure was constant.
The contents were cooled to room temperature, depressurized, and purged with nitrogen. Then, the reactor was opened, the contents were taken out, and the catalyst was removed by filtration. From the resulting filtrate, 1,4-dioxane was distilled off under reduced pressure to obtain 6.0 g of a highly viscous oil.
5.00 g of this oil, 60 ml of ethanol and sodium hydroxide (manufactured by Wako Pure Chemical Industries, 0.01 g, 0.00025 mol) were added to a 100 ml two-necked flask, and the system was replaced with nitrogen. The reaction was carried out at 4 ° C. for 4 hours. After the contents were cooled to room temperature, sodium residue was removed through a column packed with 10 g of ion exchange resin (manufactured by Mitsubishi Chemical Co., Ltd., DAIAION PK208H), and then ethanol was removed under reduced pressure to obtain 4.36 g of a slightly yellow oily substance. It was. The recovery rate from the raw material was 65.5%.
¹ H-NMR, ¹³ C-NMR and IR spectrum of the obtained oily substance were measured and confirmed to be the desired copolymer. Most of the peaks derived from allyl acetate disappeared. The number average molecular weight of this copolymer was Mn = 2560, the hydroxyl value was 82 mgKOH / g, and the allyl alcohol monomer unit was 15 mol%. Furthermore, the evaluation results of the solubility in various solvents are shown in Table 2.

Example 7: Production of allyl alcohol / 1-octene copolymer 120 ml of stainless steel autoclave (manufactured by pressure-resistant glass industry), allyl acetate (Tokyo Chemical Industry Co., Ltd., 20.00 g, 0.200 mol) and 1-octene ( Wako Pure Chemical Industries, 44.83 g, 0.400 mol), di-t-butyl peroxide (Kishida Chemical Co., Ltd., 3.24 g, 0.022 mol) were added, and after the flange was attached, the system was filled with nitrogen. With 3 replacements. Next, the temperature was raised while stirring the content at 400 rpm, and the reaction was carried out at 155 ° C. for 5 hours.
After the contents were cooled to room temperature and depressurized, the reactor was opened to take out the contents, and unreacted allyl acetate, 1-octene and initiator residue were removed under reduced pressure at 100 ° C. 28.92 g of oil was obtained.
10.00 g of this oily substance, 120 ml of ethanol and sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd., 0.02 g, 0.0005 mol) were added to a 300 ml two-necked flask, and the inside of the system was replaced with nitrogen. The reaction was carried out at 4 ° C. for 4 hours. After the contents were cooled to room temperature, sodium residue was removed through a column packed with 15 g of ion exchange resin (manufactured by Mitsubishi Chemical Corporation, DAIAION PK208H), and then ethanol was removed under reduced pressure to obtain 8.49 g of a slightly yellow oily substance. It was. The recovery rate from the raw material was 42.5%.
¹ H-NMR, ¹³ C-NMR and IR spectrum of the obtained oily substance were measured and confirmed to be the desired copolymer. Most of the peaks derived from allyl acetate disappeared. The copolymer had a number average molecular weight of Mn = 1180, a hydroxyl value of 248 mgKOH / g, and an allyl alcohol monomer unit of 46.7 mol%. Furthermore, the evaluation results of the solubility in various solvents are shown in Table 2.

Example 8: Production of allyl alcohol / 1-hexene copolymer A 120 ml stainless steel autoclave (made by pressure-resistant glass industry) was charged with allyl acetate (Tokyo Chemical Industry Co., Ltd., 14.00 g, 0.140 mol) and 1-hexene ( Wako Pure Chemical Industries, 39.23 g, 0.466 mol), di-t-butyl peroxide (Kishida Chemical Co., Ltd., 2.66 g, 0.018 mol) were added, and after attaching the flange portion, the system was filled with nitrogen. With 3 replacements. Next, the temperature was raised while stirring the content at 400 rpm, and the reaction was carried out at 155 ° C. for 5 hours.
After the contents were cooled to room temperature and depressurized, the reactor was opened to take out the contents, and unreacted allyl acetate, 1-hexene and initiator residue were removed under reduced pressure at 100 ° C. 16.56 g of oil was obtained.
10.00 g of this oily substance, 120 ml of ethanol and sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd., 0.02 g, 0.0005 mol) were added to a 300 ml two-necked flask, and the inside of the system was replaced with nitrogen. The reaction was carried out at 4 ° C. for 4 hours. After the contents were cooled to room temperature, the sodium residue was removed through a column packed with 15 g of ion exchange resin (manufactured by Mitsubishi Chemical Corporation, DAIAION PK208H), and then ethanol was removed under reduced pressure to obtain 7.69 g of a slightly yellow oily substance. It was. The recovery rate from the raw material was 29.6%.
¹ H-NMR, ¹³ C-NMR and IR spectrum of the obtained oily substance were measured and confirmed to be the desired copolymer. Most of the peaks derived from allyl acetate disappeared. Further, the number average molecular weight of this copolymer was Mn = 1120, the hydroxyl value was 222 mgKOH / g, and the allyl alcohol monomer unit was 37.2 mol%. Furthermore, the evaluation results of the solubility in various solvents are shown in Table 2.

Example 9: Production of allyl alcohol / 1-tetradecene copolymer Allyl acetate (Tokyo Chemical Industry Co., Ltd., 35.00 g, 0.350 mol) and 1-tetradecene (manufactured by Tokyo Kasei Kogyo Co., Ltd.) were added to a 300 ml stainless steel autoclave (made by pressure-resistant glass industry). Tokyo Chemical Industry Co., Ltd., 114.43 g, 0.583 mol), di-t-butyl peroxide (Kishida Chemical Co., Ltd., 7.47 g, 0.051 mol) were added, the flange part was attached, and the system was filled with nitrogen. With 3 replacements. Next, the temperature was raised while stirring the content at 400 rpm, and the reaction was carried out at 145 ° C. for 6 hours.
After the contents were cooled to room temperature and depressurized, the reactor was opened to take out the contents, and unreacted allyl acetate, 1-tetradecene and initiator residue were removed under reduced pressure at 160 ° C. 94.27 g of oil was obtained.
93.00 g of this oily substance, 280 ml of ethanol, and sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd., 0.19 g, 0.0048 mol) were added to a 300 ml two-necked flask, and the inside of the system was replaced with nitrogen. The reaction was carried out at 4 ° C. for 4 hours. After the contents were cooled to room temperature, the sodium residue was removed through a column packed with 100 g of an ion exchange resin (manufactured by Mitsubishi Chemical, DAIAION PK208H), and then ethanol was removed under reduced pressure to obtain 83.11 g of a slightly yellow oily substance. It was. The recovery rate from the raw material was 60.1%.
¹ H-NMR, ¹³ C-NMR and IR spectrum of the obtained oily substance were measured and confirmed to be the desired copolymer. Most of the peaks derived from allyl acetate disappeared. The copolymer had a number average molecular weight of Mn = 2350, a hydroxyl value of 150 mgKOH / g, and an allyl alcohol monomer unit of 38.4 mol%. Furthermore, the evaluation results of the solubility in various solvents are shown in Table 2.

Example 10: Production of allyl alcohol / 1-decene / 2-norbornene copolymer 120 ml of stainless steel autoclave (made by pressure-resistant glass industry) and allyl acetate (Tokyo Chemical Industry Co., Ltd., 19.49 g, 0.195 mol) 1-decene (manufactured by Wako Pure Chemical Industries, 30.00 g, 0.214 mol), 2-norbornene (manufactured by Tokyo Chemical Industry Co., Ltd., 6.04 g, 0.064 mol), di-t-butyl peroxide (manufactured by Kishida Chemical Co., Ltd.) , 2.78 g, 0.019 mol) was added, the flange portion was attached, and the inside of the system was replaced with nitrogen three times. Next, the temperature was raised while stirring the content at 400 rpm, and the reaction was carried out at 145 ° C. for 5 hours.
After the contents are cooled to room temperature and depressurized, the reactor is opened to take out the contents, and unreacted allyl acetate, 1-decene, 2-norbornene and initiator residue are removed at 100 ° C. under reduced pressure. As a result, 30.34 g of a highly viscous oily substance was obtained.
5.00 g of this oily substance, 30 ml of ethanol and sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd., 0.02 g, 0.0005 mol) were added to a 100 ml two-necked flask, and the system was replaced with nitrogen. The reaction was carried out at 4 ° C. for 4 hours. After the contents were cooled to room temperature, the sodium residue was removed through a column packed with 10 g of an ion exchange resin (manufactured by Mitsubishi Chemical Corporation, DAIAION PK208H), and then ethanol was removed under reduced pressure to obtain 4.00 g of a slightly yellow oily substance. It was. The recovery rate from the raw material was 52.0%.
¹ H-NMR, ¹³ C-NMR and IR spectrum of the obtained oily substance were measured and confirmed to be the desired copolymer. Most of the peaks derived from allyl acetate disappeared. Moreover, the number average molecular weight of this copolymer was Mn = 1650, and the hydroxyl value was 220 mgKOH / g. Furthermore, the evaluation results of the solubility in various solvents are shown in Table 2.

Example 11: Production of allyl alcohol / 1-decene copolymer 50.00 g of allyl acetate / 1-decene copolymer prepared in Example 3, 600 ml of ethanol, sulfuric acid (manufactured by Wako Pure Chemical Industries, 0.20 g). In addition to the 1 L 2-neck flask, the inside of the system was replaced with nitrogen, and then reacted at 80 ° C. for 5 hours with stirring. The content was cooled to room temperature, sodium hydroxide was added to neutralize the sulfuric acid residue, the resulting salt was filtered, and ethanol was removed under reduced pressure to obtain 44.75 g of a slightly yellow oil.
As a result of measuring ¹ H-NMR, ¹³ C-NMR and IR spectrum of the obtained oily substance, the conversion rate of the transesterification reaction was 52%, and the ester structure remained in the product. The copolymer had a number average molecular weight of Mn = 2050, a hydroxyl value of 95 mgKOH / g, and an allyl alcohol monomer unit of 20.0 mol%. Furthermore, the evaluation results of the solubility in various solvents are shown in Table 2.

Example 12: Production of allyl alcohol / 1-decene copolymer (reduction in the amount of ethanol during the transesterification reaction)
1 L glass autoclave (made by pressure-resistant glass industry), allyl acetate (Tokyo Chemical Industry, 16.00 g, 0.360 mol) and 1-decene (Wako Pure Chemical Industries, 360.00 g, 2.567 mol), Di-t-butyl peroxide (Kishida Chemical Co., Ltd., 19.80 g, 0.1354 mol) was added, the flange was attached, and the system was replaced with nitrogen three times. Next, the temperature was raised while stirring the content at 600 rpm, and the reaction was carried out at 155 ° C. for 5 hours.
After the contents were cooled to room temperature and depressurized, the reactor was opened to take out the contents, and unreacted allyl acetate, 1-decene and initiator residue were removed under reduced pressure at 160 ° C. 174.52 g of oil was obtained.
After adding 150.00 g of this oily substance, 450 ml of ethanol, and sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd., 0.30 g, 7.50 mmol) to a 1 L three-necked flask, the inside of the system was replaced with nitrogen, The reaction was carried out at a bath temperature of 85 ° C. for 5 hours. After the contents were cooled to room temperature, the sodium residue was removed through a column packed with 300 g of ion exchange resin (manufactured by Mitsubishi Chemical Corporation, DAIAION PK216LH), and then ethanol was removed under reduced pressure to obtain 137.22 g of a slightly yellow oily substance. It was. The recovery rate from the raw material was 44.1%.
¹ H-NMR, ¹³ C-NMR and IR spectrum of the obtained oily substance were measured and confirmed to be the desired copolymer. Most of the peaks derived from allyl acetate disappeared. The copolymer had a number average molecular weight of Mn = 1720, a hydroxyl value of 74 mgKOH / g, and an allyl alcohol monomer unit of 16.7 mol%. Furthermore, the evaluation results of the solubility in various solvents are shown in Table 2.

Example 13: Production of allyl alcohol / 1-decene copolymer (reduction of the amount of ethanol during the transesterification reaction and distillation of the produced ester during the reaction)
In the same manner as in Example 12, 175.47 g of a highly viscous oily substance was obtained as a copolymer of allyl acetate and 1-decene.
After adding 150.00 g of this oily substance, 450 ml of ethanol, and sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd., 0.30 g, 7.50 mmol) to a 1 L three-necked flask, the inside of the system was replaced with nitrogen, The reaction was carried out at a bath temperature of 88 ° C. for 2 hours. During this time, ethyl acetate produced by the reaction was distilled out of the system together with a small amount of methanol. After the contents were cooled to room temperature, the sodium residue was removed through a column packed with 300 g of an ion exchange resin (manufactured by Mitsubishi Chemical, DAIAION PK216LH), and then ethanol was removed under reduced pressure to obtain 138.65 g of a slightly yellow oil. It was. The recovery rate from the raw material was 44.3%.
¹ H-NMR, ¹³ C-NMR and IR spectrum of the obtained oily substance were measured and confirmed to be the desired copolymer. Most of the peaks derived from allyl acetate disappeared. The copolymer had a number average molecular weight of Mn = 1760, a hydroxyl value of 72 mgKOH / g, and an allyl alcohol monomer unit of 16.3 mol%. Furthermore, the evaluation results of the solubility in various solvents are shown in Table 2.

Comparative Example 1: Production of allyl alcohol / 1-decene copolymer Allyl alcohol (Showa Denko KK, 8.00 g, 0.138 mol) and 1-decene (sum) were added to a 120 ml stainless steel autoclave (made by pressure-resistant glass industry). Mitsui Pure Chemicals, 38.64 g, 0.275 mol) and di-t-butyl peroxide (Kanto Chemical Co., 2.33 g, 0.0159 mol) were added and the flange part was attached. Replaced 3 times. Next, the temperature was raised while stirring the content at 400 rpm, and the mixture was reacted at 140 ° C. for 5 hours.
After the contents were cooled to room temperature and depressurized, the reactor was opened to take out the contents, and unreacted allyl alcohol, 1-decene and initiator residue were removed under reduced pressure at 100 ° C. 9.08 g of oil was obtained. The recovery rate from the raw material was 18.5%.
¹ H-NMR, ¹³ C-NMR and IR spectrum of the obtained oily substance were measured and confirmed to be the desired copolymer. Moreover, the number average molecular weight of this copolymer was as low as Mn = 830. The hydroxyl value was 217 mgKOH / g, and the allyl alcohol monomer unit was 41.2 mol%. Furthermore, the evaluation results of the solubility in various solvents are shown in Table 2.

Comparative Example 2: Production of allyl alcohol / 1-decene copolymer 50.00 g of allyl acetate / 1-decene copolymer prepared in Example 3, 600 ml of pure water, sodium hydroxide (Wako Pure Chemical Industries, Ltd. 10 g, 0.0025 mol) was added to a 1 L two-necked flask and stirred at 80 ° C. for 5 hours while stirring. The contents were cooled to room temperature and allowed to stand to separate into two phases. The aqueous phase was separated using a separatory funnel, and 500 ml of pure water was added to wash the organic phase. This operation was repeated three times until the organic phase became neutral. Thereafter, the mixture was treated under reduced pressure at 100 ° C. for 2 hours to obtain 49.15 g of a slightly yellow oily substance.
As a result of measuring ¹ H-NMR, ¹³ C-NMR and IR spectrum, the obtained oil was an allyl acetate / 1-decene copolymer, and the hydrolysis reaction did not proceed at all. The results of ¹ H-NMR and IR spectrum measurements are shown in FIGS.

Claims (15)

Formula (1)

And formula (2)

(In the formula, R ¹ represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms, which may be branched or include a cyclic structure, and R ² represents an aliphatic hydrocarbon group having 2 to 20 carbon atoms. And may be branched or include a cyclic structure.)
A copolymer containing the structure represented by the formula (3) as a monomer unit is transesterified with an alcohol in the presence of a catalyst.

And formula (2)

(Wherein R ² represents the same meaning as described above.)
The manufacturing method of the allyl alcohol copolymer which contains the structure shown by as a monomer unit.   The method for producing an allyl alcohol copolymer according to claim 1, wherein the alcohol used in the transesterification reaction is an alkyl alcohol having 1 to 10 carbon atoms.   The method for producing an allyl alcohol copolymer according to claim 2, wherein the alkyl alcohol having 1 to 10 carbon atoms is ethanol or 1-propanol.   The method for producing an allyl alcohol copolymer according to any one of claims 1 to 3, wherein the catalyst used in the transesterification reaction is sodium hydroxide, lithium hydroxide, or potassium hydroxide.   The method for producing an allyl alcohol copolymer according to claim 4, wherein the catalyst used in the transesterification reaction is sodium hydroxide. Aliphatic hydrocarbon group having 1 to 10 carbon atoms represented by R ¹ in the formula (1) is, in any one of claims 1 to 5, a straight-chain aliphatic hydrocarbon group having 1 to 5 carbon atoms The manufacturing method of allyl alcohol copolymer of description.   The method for producing an allyl alcohol copolymer according to claim 6, wherein the linear aliphatic hydrocarbon group having 1 to 5 carbon atoms is a methyl group, an ethyl group, or an n-propyl group. The method for producing an allyl alcohol copolymer according to claim 7, wherein the linear aliphatic hydrocarbon group having 1 to 5 carbon atoms is a methyl group. The R ² in the formula (2) is a linear aliphatic hydrocarbon group having 2 to 10 carbon atoms or an alicyclic hydrocarbon group having 6 to 10 carbon atoms. A method for producing an allyl alcohol copolymer. R ² in the formula (2) is an ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, or The method for producing an allyl alcohol copolymer according to claim 9, which is a cyclohexyl group.   The manufacturing method of the allyl alcohol copolymer in any one of Claims 1-10 which consists only of a monomer unit of Formula (1) and Formula (2).   The manufacturing method of the allyl alcohol copolymer in any one of Claims 1-11 containing the structure obtained by copolymerizing a radically polymerizable olefin compound as a 3rd monomer unit.   The method for producing an allyl alcohol copolymer according to claim 12, wherein the third monomer unit has a structure derived from methyl acrylate, methyl methacrylate, vinyl acetate, or styrene.   The monomer unit shown by Formula (1) is 3-60 mol% with respect to all the monomer units, The manufacturing method of the allyl alcohol copolymer in any one of Claims 1-13.   The manufacturing method of the allyl alcohol copolymer of Claim 12 which contains 0.1-20.0 mol% of radically polymerizable olefin compound units with respect to all the monomer units.

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