TW201116543A - Production method of allyl alcohol copolymer - Google Patents

Abstract

The present invention relates to a method for producing an allyl alcohol copolymer comprising structures represented by formulae (3) and (2) as monomer units (in the formulae, R2 represents an aliphatic hydrocarbon group having 2 to 20 carbon atoms), comprising subjecting a copolymer comprising structures represented by formulae (1) and (2) as monomer units (in the formulae, R1 represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms, which may be branched or include a cyclic structure; and R2 has the same meaning as mentioned above) to transesterification reaction with alcohol in the presence of a catalyst. The allyl alcohol copolymer obtained by the present invention is excellent in compatibility with various resins, electric insulating property, low water absorption, thermal stability and surface activity effect; and therefore is useful as a resin improver, components in coating agent, ink, adhesive agent and primer, high-performance wax, compatibilizer, surfactant, additive for grease, polyurethane material and polyester material.

Description

201116543 6. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a process for producing an allyl alcohol copolymer. [Prior Art] The olefin polymer having a polar group in the structure is industrially widely used because of its compatibility with various polar resins, excellent adhesion, and easy coloring. Although various reports have been proposed for the production of such polar olefin polymers, most of them have been introduced by introducing a polar group-containing monomer via graft polymerization. For example, in JP-A No. 20-5-13-1038 (Patent Document 1), a decomposing agent and a polar compound are caused to act in a high-grade α-olefin polymer, and it is revealed that a polar group-containing group having a polar group is introduced. Olefin polymer. However, by the method of graft polymerization, the deterioration of the polymer due to oxidation and the dispersibility of the polar group are disturbing, and it is difficult to say that the quality of the product is a satisfactory method. Therefore, in order to solve this problem, there has been reported a production example in which a copolymerization between a polar group-based monomer and another olefin-based monomer is carried out. However, there are few examples of such methods, for example, Japanese Laid-Open Patent Publication No. SHO 64-54009 (Patent Document 2) and JP-A-2002-166-096 Document 3). These are reaction systems utilizing anionic polymerization, and in order to exhibit the activity of the catalyst, it is necessary to treat the polar group-containing monomer in advance with an organometallic compound having a molar amount or more, which is disadvantageous in terms of production cost. On the other hand, an example of producing a copolymer by radical copolymerization of allyl alcohol and an aromatic vinyl monomer is disclosed in U.S. Patent No. 5,410,141 (Patent Document No. 5-201116543). Although this method can improve the productivity of the polymer and reduce the manufacturing cost, in the examples, only the copolymerization of allyl alcohol and styrene is carried out, and no other polymerizable monomer is used. Further, there are few examples of radical copolymerization of monomers other than allyl alcohol and an aromatic vinyl monomer, and the yield is low and the number average molecular weight is less than 1,000 even if the product is obtained. Therefore, a polar group polymer containing a carbon-carbon double bond other than styrene is used as a polymerizable monomer, and an efficient production method thereof is expected. [PRIOR ART DOCUMENT] [Patent Document 1] JP-A-2002-165809 (Patent Document 2) JP-A-63-54009 (Patent Document 3) JP-A-2003-165809 [Problem to be Solved by the Invention] The present invention has an object of providing a method for producing a copolymer of allyl alcohol and an α-olefin with high efficiency. [Means for Solving the Problems] In order to solve the above problems, the present inventors have continuously focused on the results of research and found that fatty acid allyl esters and aliphatic-6-201116543 aliphatic aliphatic compounds having a radical polymerization energy are found in Copolymerization occurs in the presence of a radical poly-α initiator, and as a result, the resulting copolymer is subjected to vinegar exchange in the presence of an alcohol and a catalyst, or a fatty acid allyl ester and an aromatic radical polymerizable monomer are used. After the copolymer is hydrogenated, the copolymer is subjected to a transesterification reaction in the presence of an alcohol and a catalyst, whereby a polymer having a polar group can be produced efficiently and inexpensively, and the present invention has been completed. That is, the present invention relates to the following [1] to [1 5 ]. A method for producing an allyl alcohol copolymer, which comprises a structure represented by formula (3) and formula (2) as a monomer unit; characterized in that it is contained in a formula

/π2H—c'lc—o 1 H—c—H

\1/ 11 /IV R1 -c=o and formula (2) TJ 2

HICIH

I 2 HICIR (2) (wherein R1 is represented by an aliphatic hydrocarbon group having 1 to 10 carbon atoms, which may be a branched or cyclic structure; and r2 is an aliphatic hydrocarbon group having 2 to 20 carbon atoms, which may be branched or Contains a ring structure). The copolymer shown as a monomer unit, in the presence of a catalyst, and the compound of the method of 201116543, which is a compound of a propylene propylene, is converted into an alcohol.

"T^H2H HICICIO - HICIH (3) Γ- 1 4

(2) (wherein the R2 table is as described above). [2] The method for producing an allyl alcohol copolymer according to the above [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 the above [2], wherein the above-mentioned 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 the above [1] to [3] wherein the catalyst used in the transesterification reaction is sodium hydroxide, lithium hydroxide or potassium hydroxide. [5] A 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 method for producing an allyl alcohol copolymer according to any one of the above [1], wherein the aliphatic hydrocarbon group having a carbon number of 1 to 10 represented by R1 in the formula (1) is a carbon number of 1 ~5 linear aliphatic hydrocarbon groups. [7] The method for producing an allyl alcohol copolymer according to the above [6], wherein the above aliphatic hydrocarbon group having 1 to 5 carbon atoms is a methyl 'ethyl group or an n-propyl group. [8] The method for producing an allyl alcohol copolymer according to any one of the above [1] to [7] wherein the linear aliphatic hydrocarbon group having 1 to 5 carbon atoms is a methyl group. [9] The method for producing an allyl alcohol copolymer according to any one of the above [1] to [8] wherein R2 in the formula (2) is a linear aliphatic hydrocarbon group having 2 to 10 carbon atoms, or carbon A number of 6 to 10 alicyclic hydrocarbon groups. [1] The method for producing an allyl alcohol copolymer according to the above [9], wherein R in the formula (2) is ethyl, η-propyl, η-butyl, η-pentyl, η-hexyl , η_octyl, η-fluorenyl, η-dodecyl, or cyclohexyl. [11] The method for producing an allyl alcohol copolymer according to any one of the above [1] to [10], which is composed of only the monomer units of the formula (1) and the formula (2).制造2] The method for producing an allyl alcohol copolymer according to any one of the above [1] to [11] wherein 'the structure obtained by copolymerizing the radically polymerizable olefin compound is a third monomer unit. [13] The method for producing an allyl alcohol copolymer according to the above [12], wherein the third monomer unit is a structure derived from methyl acrylate 'methyl methacrylate, vinyl acetate, or styrene. Π 4] The method for producing an allyl alcohol copolymer according to any one of the above [1] to [1 3], wherein the monomer unit represented by the formula (1) is 3 〜 with respect to the all monomer unit. The method for producing an allyl alcohol copolymer according to the above [12], wherein the radical polymerizable olefin compound unit is contained in an amount of from 0.1 to 20.0 mol% based on the all monomer unit ' 9_201116543 [Effect of the Invention] According to the present invention, a copolymer of allyl alcohol and an olefin can be efficiently produced. Since the allyl alcohol copolymer obtained by the present invention has a polar group, it is excellent in compatibility with various resins and adhesion. Further, since it has a hydrophobic group, this point is excellent in electrical insulating properties, low water absorbability, thermal stability, and interface activity. Therefore, for example, it is useful as a resin modifier, a coating component, an ink component, an adhesive component, a primer component, a high performance wax, a compatibilizing agent, a surfactant, a lubricating oil additive, a polyurethane raw material, and a polyester raw material. Mingfa Shishi under the Ming said that the marching Mingfa ___. κ 泠 封 ^ 0 J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J 5

/π2 HICICIOI HICIH N-^ /|\

R1I CHO and formula (2) T J 6

I 2 HICIRI HICIH (2) ο 201116543 (wherein R1 is an aliphatic hydrocarbon group having a carbon number of 1 to 10, which may be a branched or a cyclic structure: R2 is an aliphatic hydrocarbon group having a carbon number of 2 to 20, For branches or those with a ring structure). Shown is a copolymer containing a monomer unit derived from a fatty acid allyl ester (formula) and a monomer unit derived from an α-olefin (formula (2)). This copolymer is referred to as "allyl ester copolymer" in this specification. R1 in the formula (1) is a linear chain having a carbon number of 1 to 10, or may be a branched or aliphatic hydrocarbon group having a cyclic structure. Examples of the linear aliphatic hydrocarbon group include methyl group, ethyl g, η-propyl ' η butyl group, η-pentyl group, η-hexyl group, η-octyl group, and η-fluorenyl group. Examples of the branched aliphatic hydrocarbon group include iso-g, isobutyl, sec-butyl, neopentyl, isohexyl, isooctyl and the like. Examples of the alicyclic hydrocarbon group having a cyclic structure include a mercapto group, a cyclohexylmethyl group, and a cyclohexylethyl group. Among these, when a linear aliphatic hydrocarbon group having 1 to 5 carbon atoms is produced as a polymer of the stomach R, it is preferable to reduce the cost. From the viewpoint of reducing the cost at the time of production, it is particularly preferably a methyl group or an ethyl 'η-propyl group. R2 in the formula (2) is a linear chain having a carbon number of 2 to 20, or may be a branched or an aliphatic hydrocarbon group having a cyclic structure. Examples of the linear aliphatic hydrocarbon group include an ethyl group, an η_@ group, an η-butyl group, an η-pentyl group, an η-hexyl group, an η-octyl group, an η-fluorenyl group, and a η•12-yl group. η -tetradecyl, η -hexadecyl, η-octadecyl, η-tetradecyl, and the like. Examples of the branched aliphatic hydrocarbon group include isopropyl s, -11 - 201116543 isobutyl, sec-butyl, neopentyl, isohexyl, isooctyl, isodecyl and the like. Examples of the alicyclic hydrocarbon group having a cyclic structure include, for example, a cyclohexyl group, a cyclohexylmethyl group, a cyclohexylethyl group, a decahydronaphthyl group, a cyclohexenyl group, and the like, and a carbon number of 2 to 1 Å. When the linear aliphatic hydrocarbon group or the alicyclic hydrocarbon group having 6 to 10 carbon atoms is used as R2, it is preferable because it can improve the compatibility with various trees. From the viewpoint of improving the compatibility with various resins, ethyl, η-propyl ' n -butyl, n -pentyl, n-hexyl, η-octyl, η-fluorenyl, η- are particularly preferred. Twelve bases, cyclohexyl. The allyl ester copolymer of the present invention may be composed only of the monomer units of the formula (1) and the formula (2), and may optionally contain a third monomer unit. The third monomer unit is the same as that described in the item of allyl alcohol copolymer described later. Further, when the conversion ratio of the transesterification reaction of the allyl ester copolymer of the formula (1) is less than 100%, the obtained allyl ester copolymer may have the presence of the monomer unit derived from the formula (2). However, this can also be regarded as one of the third monomer units. The third monomer unit may be two or more types. [Allyl alcohol copolymer] The allyl alcohol copolymer of the present invention is contained in the formula (3)

/Η2Η HICICIO 1 HICIH (3) -12- 201116543 The structure and formula (2) TJ 8

I 2 HICIR I HICIH (wherein R2 is shown as an aliphatic hydrocarbon group having 2 to 20 carbon atoms' may be branched or have a cyclic structure). The copolymer shown is a copolymer of monomer units. The third monomer unit may also be included as needed. The monomer unit having the structure represented by the formula (2) is the same as that described in the description of the allyl vinegar copolymer; the example of R2 can be exemplified as the same. Moreover, the preferred embodiments are also the same. The allyl alcohol copolymer of the present invention may be a copolymer containing only the structure represented by the formula (3) and the structure represented by the formula (2), or may be optionally used, or may be a copolymerized radical polymerization. The structure obtained by the olefin compound is introduced as a third monomer unit. The third monomer unit may be two or more types. Examples of the radical polymerizable olefin compound include propionic acid, methacrylic acid, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, methyl methacrylate, and methacrylic acid B. Vinegar, n-propyl methacrylate, n-butyl methacrylate '2-northene, vinyl acetate, ethylene, styrene, etc. Among these, in view of improving the productivity in the production of the copolymer, methyl acrylate, methyl methacrylate, vinyl acetate, and benzene-13-201116543 olefin are preferable. In the acryl alcohol copolymer of the present invention, the monomer unit represented by the formula (3) is saturated with the copolymerization pattern of the monomer unit represented by the formula (2), and the polymerization condition may be random, grafted or alternated. Any one of them 'is improved from the viewpoint of compatibility with each resin, and is preferably irregular. The same applies to the case where the third monomer unit is contained. In the allyl alcohol copolymer of the present invention, the composition of each monomer unit can be equivalent to the allyl ester of the monomer unit represented by the formula (1) at the time of production of the propyl ester copolymer. The ratio of the olefin compound and the radically polymerizable olefin compound of the monomer unit represented by the formula (2) and the polymerization conditions are controlled. The monomer unit represented by the formula (1) is preferably from 3 to 60 mol% from the viewpoint of the compatibility of the allyl alcohol copolymer of the present invention and the compatibility of the various resins. Further, it is more preferably 4 to 40 mol%, most preferably -30 mol%. When the monomer unit represented by the formula (1) is less than 3 mol / 〇, the subsequent property is remarkably lowered: when it exceeds 60 m ο 1 %, the compatibility with the low-polarity resin is deteriorated. Further, in the case of the case where the radical polymerizable olefin compound unit is contained, from the viewpoint of improving the compatibility with various resins, the monomer units are preferably from 0.1 to 20.0 mol% with respect to the all monomer unit. . Further, it is more preferably 〇·5 to 15. 〇mol%, and most preferably 2.0 to l〇_〇m〇l%. When the radical polymerizable olefin compound unit is less than 0.1 mol%, the compatibility with the highly polar resin is deteriorated: when it exceeds 2.0 mol%, the compatibility with the low polarity resin deteriorates. The hydroxyl group valence of the allyl alcohol copolymer of the present invention is preferably from 10 to 300 mgKOH/g from the viewpoint of coexistence with various resins -14 to 201116543. More preferably, it is 50 to 250 mgKOH/g, and most preferably 100 to 200 mgKOH/g. When the base price of the copolymer is less than 10 mgKOH/g, the adhesion is lowered. When it exceeds 300 mgKOH/g, the compatibility with the low-polar resin is deteriorated. Further, the hydroxyl value is determined by the method described in J I S K 0 0 7 0. The number average molecular weight (??) of the copolymer of the present invention is not particularly limited. The polystyrene-equivalent number average molecular weight (? η ) measured by a gel chromatography (GPC) method is preferably Μ η = 5 0 0 to 8000 in consideration of compatibility with various resins. More preferably, it is 500 to 5,000, and most preferably 650 to 3,000. When the number average molecular weight (?n) of the polystyrene conversion 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, a method for producing the allyl alcohol copolymer of the present invention will be described. The allyl alcohol copolymer of the present invention can be produced by two methods of the oxime method and the oxime method shown below. Method A: A fatty acid allyl ester corresponding to the monomer unit represented by the formula (1) is equivalent The olefin compound of the monomer unit represented by the formula (2) and the optionally polymerizable olefin compound of the third monomer are copolymerized in the presence of a radical polymerization initiator, and the result is copolymerization. The resulting allyl ester copolymer (precursor A) was transesterified in the presence of an alcohol and a catalyst. -15-201116543 Method B: hydrogenation of a copolymer of a fatty acid allyl ester and an aromatic radical polymerizable monomer, and as a result, an allyl ester copolymer (precursor B) is formed in the presence of an alcohol and a catalyst. Transesterification is carried out. Method A: a fatty acid allyl ester and an olefin compound corresponding to a monomer unit represented by the formula (2), and a precursor A prepared by radical copolymerization with a radically polymerizable olefin compound, in an alcohol Method for transesterification in the presence of a catalyst <Production of Precursor A> In the method for producing a copolymer of the present invention, the precursor for producing the precursor A corresponds to the monomer unit represented by the formula (2) The olefin compound is not particularly limited as long as it is a radically polymerizable polymer. When the structure described in the detailed description of the allyl ester copolymer is expressed as an olefin compound, for example, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, a linear terminal olefin of 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 1-tetracosene, etc.; -methyl-1-butene, 4-methyl-1-pentene, 3-methyl-1-pentene, 4,4-dimethyl-1.pentene' 3-methyl-1-glycol a branched terminal olefin such as alkene, 3-methyl-1-nonene or 3-methyl-1-undecene; cyclohexylethylene, 3-cyclohexyl-1-propane, 4-cyclohexyl-1-butene A terminal olefin having a cyclic structure, such as an alkene, a decalin, or a 4-vinyl-1-cyclohexene. For example, an olefin having two unsaturated bonds such as 2-decene has a resonance stabilization due to a chain-linked radical, so polymerization is difficult. Among these, in order to improve compatibility with various resins, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-癸- 16- 201116543 Alkene, 1-dodecene, and cyclohexylethylene. In the method for producing a copolymer of the present invention, the amount of the allylic fatty acid ester used in the production of the precursor A and the radically polymerizable olefin compound corresponding to the monomer unit represented by the formula (2) are usually When the molar ratio of the olefin compound of the monomer unit represented by the formula (2) is 1 mol, the fatty acid allyl ester is preferably used in an amount of 0.05 to 2.0 mol, and particularly preferably 〇.1〇~1. . When the fatty acid allylate does not reach 0 · 〇 5 moles, the obtained precursor A will become too low in the hydroxyl group after transesterification to deteriorate the compatibility; and, in excess of 2.0 moles, the molecular weight of the precursor A There will be a tendency to decrease. The amount of the radically polymerizable olefin compound to be used in the third monomer is usually from 0.005 to 0.3 mol per gram of the monomer unit olefin compound represented by the formula (2). For 〇.〇1~〇.1 Moer. When the radically polymerizable olefin compound of the third monomer is less than 0.005 mol, the recovered amount of the precursor A obtained is decreased; and, when it exceeds 0.2 mol, there is a high molecular weight in the precursor A. When solids are formed, there will be white turbidity. Further, the ratio of the amount of the monomer generally placed to the ratio of the amount of the monomer unit in the resulting polymer may be inconsistent due to the difference in the reactivity of each monomer. The copolymerization reaction in the production of the precursor A can be carried out without a solvent, or a solvent which does not react with the substrate and has a small linkage shift can be used. The solvent may, for example, be a hydrocarbon solvent such as toluene 'benzene or t-butylbenzene; a ketone solvent such as acetone; or a halogen solvent such as dichloromethane, chloroform or chlorobenzene. These solvents may 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 may be used as long as it can generate radicals by heat, ultraviolet rays, electron beams, radiation from -17 to 201116543, etc., but it is preferred that the half-life of the reaction temperature is 1 hour or longer. Examples of the thermal radical polymerization initiator include, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2·-azo Bis(2-methylbutyronitrile), dimethyl-2,2'-azobisisobutyrate, 4,4'-azobis(4-cyanovaleric acid), 2,2'-even An azo compound such as nitrogen bis(2,4,4-trimethylpentane); a ketone peroxide such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide or cyclohexanone peroxide ; bismuth peroxides; bismuth peroxide; Dialkyl peroxides; 1,1_di(tert-hexyl peroxide)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-hexylperoxy)cyclohexane Peroxyketal of 1,1-di-t-butylcyclohexane peroxide, 2,2-di(t-butylperoxy)pentane, etc.; tert-butyl trimethyl bromide Acid ester, tert-butyl-2-ethylhexanoate peroxide, t-butyl isobutyrate, di-tert-butyl hexahydroperoxide Di-t-butylperoxy hexahydroterephthalate, di-t-butylperoxy azelate, t-butyl peroxy-3,5,5-trimethylhexanoate, Tert-butyl-2-ethylhexanoate peroxide, 1,1,3,3-tetramethylbutyl-2-ethylhexanoate peroxide, tert-butylperoxy peroxide, tert-butyl peroxide Benzoyl benzoate, di-tert-butyl trimethyl adipate, t-hexyl isopropyl monocarbonate, t-butyl laurate peroxide, tert-hexyl benzoate, etc. Alkyl peroxyesters: peroxycarbonates such as diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, t-butyl isopropyl peroxide; -18 - 201116543 Hydrogen peroxide, etc. 'But it is not limited to this. Further, these thermal radical polymerization initiators may be used in combination of two or more kinds. The radical polymerization initiator using ultraviolet rays, electron beams, and radiation is exemplified by, for example, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, diethoxyacetophenone, and 1 -hydroxy-cyclohexyl-phenyl ketone, 2-methyl-b[4-(methylthio)phenyl]_2_ misoacetone 丨, 2-benzyl-2.dimethylamino (4- Amorphine phenyl)-butanone ^, 2 - hydroxy 2 - methyl - phenyl propyl - propanyl - ketone derivatives such as ketone; diphenyl ketone, 4, 4 ' bis (dimethyl a diphenyl ketone derivative such as an amino)diphenyl ketone, a trimethyl decyl diphenyl ketone or a 4-benzylformamidine-4'-methyl-diphenyl sulfide; a benzoin, a benzoin ethyl ether , benzoin derivatives such as benzoin propyl ether, benzoin isobutyl ether, benzoin isopropyl ether; tolyl glyoxylate, benzoin dimethyl ketal, 2, 4, 6- Trimethylbenzhydryl diphenylphosphine oxide or the like, but is not limited thereto. Further, the "such ultraviolet rays" electron beam and the radiation radical polymerization initiator may be used in combination of two or more kinds. The amount of the polymerization initiator to be used varies depending on the reaction temperature and the monomer composition ratio, and therefore cannot be uniformly defined, but when it is 1 part by mass based on the total amount of the radical polymerizable monomer' Preferably, it is 〇. 1 to 1 5 parts by mass, particularly preferably 1. 〇~1 〇 by mass. When the amount of the radical polymerization initiator to be added is less than 0.1 part by mass, the polymerization reaction is difficult to proceed: when the amount is more than 15 parts by mass, the molecular weight of the precursor A may become too low. In addition, it is not economically appropriate. The reaction temperature (polymerization temperature) may be appropriately selected depending on the type of the polymerization initiator, and the temperature may be changed stepwise to cause polymerization (polymerization). If -19 - 201116543 is a polymerization using ultraviolet light or the like, it can be used at room temperature. In the case of thermal polymerization, it is preferred to appropriately determine the decomposition temperature of the starter, and it is preferably in the range of from 50 to 180 °C, particularly preferably from 70 to 170 °C. If it is lower than 50 °C, the reaction will become extremely slow; if it exceeds 180 °C, the decomposition of the radical initiator will become too fast, and because the linkage movement will also become faster, the molecular weight of the precursor A will be There will be a tendency to decrease. After the reaction is completed, the product allyl ester copolymer (precursor A) can be post-treated according to well-known operations and treatment methods (for example, neutralization, solvent extraction, water washing, liquid separation, solvent distillation, reprecipitation, etc.). Then it is isolated. <Transesterification reaction of precursor A> The transesterification reaction can be carried out by bringing the precursor A and the alcohol compound into contact with each other in the presence of a catalyst. The alcohol compound to be used in the transesterification reaction is not particularly limited as long as it can react with the ester, but a monohydric alcohol is preferred. When considering the affinity with the precursor A, an alkyl alcohol having a carbon number of 1 to 1 Torr, and a specific amount of ethanol and 1-propanol are preferable. Examples of the catalyst which can be used in the transesterification reaction include inorganic acids, inorganic salt groups, and organic acids. Specific examples of the inorganic acid 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, and hydroxide®. Specific examples of the organic acid include acetic acid, benzenesulfonic acid, and P-toluenesulfonic acid. Among them, inorganic base is preferred as the catalyst, and it is particularly preferred to be lithium hydroxide, sodium hydroxide or potassium hydroxide, and most preferably hydrogen hydroxide -20 - 201116543 sodium. Although the transesterification reaction can be carried out in the presence or absence of a solvent, it is preferred to use a solvent for the liquid phase for the purpose of removing the heat of reaction. The solvent to be used in the reaction may be any solvent as long as it does not interfere with the range of the reaction. Specifically, a halogenated hydrocarbon selected from, for example, dichloromethane, chloroform, 1,2, dichloroethane or the like; an aliphatic hydrocarbon solvent such as pentane, hexane, pentane or octane; diethyl ether, dipropyl ether, or the like can be used. Diisopropyl ether, dibutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl An ether solvent such as ether, tetrahydrofuran or 1,4-dioxane; methanol, ethanol, hydrazine-propanol, 2-propanol' 1-butanol, 2-butanol, isobutyl alcohol, cyclohexanol, etc. One or a mixture of two or more kinds of alcohol solvents. Among these, the advantage of the alcohol compound used in the transesterification is preferably an alcohol solvent; if the solubility of the precursor A is considered, it is preferably ethanol, 1-propanol, 1 - Butanol, particularly preferably ethanol, 丨-propanol 0 vinegar exchange reaction, as long as it does not reduce the efficiency of the catalyst reaction, can be carried out using any temperature, but usually 〇~2 〇〇t, preferably 50 to 150 ° C, more preferably between 70 to 12 ° t. The high temperature makes the product easy to color; at low temperatures, a substantially useful reaction rate cannot be obtained. The reaction type of the transesterification reaction may be any reaction type used for the general transesterification reaction by batch reaction, flow reaction or the like according to the process. From the viewpoint of increasing the reaction rate, it is preferred to carry out the reaction while distilling the ester compound of fx--21 to 201116543 formed in the reaction out of the reaction system. Further, the amount of the catalyst to be used varies depending on the reaction type, and is not particularly limited. In the batch process, the amount of the precursor A1 00 parts by mass is 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. When the amount of the catalyst is too small, a substantially sufficient reaction speed cannot be obtained; and when the amount of the catalyst is too large, there is a problem that the product is colored or the catalyst cost is increased. 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 strongly acidic cation exchange resin; and when considering the removal efficiency of the catalyst residue, a porous strong acid cation exchange resin (sulfonic acid type) is particularly preferred. The ion exchange resin which is deteriorated by the treatment of the catalyst can be reused by a known operation or treatment method (for example, treatment with an aqueous hydrochloric acid solution or the like) and then reused. After the catalyst residue is removed, the allyl alcohol copolymer of the product can be post-treated by well-known operations and treatment methods (for example, filtration, solvent extraction, water washing, liquid separation, solvent distillation, reprecipitation, etc.). Segregation. The conversion ratio of the transesterification reaction can be controlled by the amount of the alcohol to be used or the reaction temperature, and the like, and is not particularly limited. The conversion ratio required for the use of the product is also different. For example, in the case of use as a polyalcohol, a conversion ratio of 70% or more, more preferably 90% or more is preferable. If the reactivity is considered, '100% is the best. If the conversion ratio of the transesterification reaction is less than i 〇〇 %, the monomer unit derived from the formula (2) will be present in the obtained allyl ester copolymer. By adjusting this conversion rate, the monomer unit -22-201116543 from the formula (2) can also be replaced with the third monomer. Method B: hydrogenation of a fatty acid allyl ester and an aromatic radical polymerizable monomer copolymer, and as a result, the resulting allyl ester copolymer (precursor B) is transesterified in the presence of an alcohol and a catalyst. In the method B, first, a copolymer of a fatty acid allyl ester and an aromatic radical polymerizable monomer is obtained, and an aromatic ring of the copolymer is subjected to hydrogenation (hydrogenation reaction), followed by transesterification. A copolymer of a fatty acid allyl ester and an aromatic radical polymerizable monomer is a method for producing a copolymer of allyl alcohol and styrene described in U.S. Patent No. 5,444,541 (Patent Document 4). It is produced by using an allyl fatty acid ester (preferably allyl acetate) instead of allyl alcohol. The aromatic radical polymerizable monomer may, for example, be styrene or vinyltoluene. <Hydrogenation reaction> The hydrogenation reaction is carried out by bringing a copolymer of a fatty acid allyl ester and an aromatic radical polymerizable monomer into contact with hydrogen in the presence of a catalyst. As the catalyst which can be used for the hydrogenation reaction, for example, a catalyst containing at least one metal element selected from Groups 6 to 12 of the periodic table as a catalyst component can be exemplified. Specifically, for example, it is selected from the group consisting of sponge Ni, Ni-diatomaceous earth, Ni-oxidized inscription, Ni-cerium oxide, Ni-cerium oxide oxide, Ni-zeolite, Ni-titanium dioxide, Ni-magnesia, Ni-. Chromium oxide, Ni-Cu, Ni-Cu-Co, sponge Co, Co-diatomaceous earth, Co-alumina, Co-ceria, Co-dioxo-23- 201116543 bismuth oxide, Co-zeolite , Co-titanium dioxide, Co-magnesia, sponge Ru, Ru-carbon, Ru-alumina, RU-ceria ruthenium Ru-alumina alumina, Ru-zeolite, Rh-carbon, Rh-alumina, Rh-cerium oxide, Rh-cerium oxide alumina, Rh-zeolite, Pt-carbon, Pt. alumina, Pt-ceria, Pt-ceria alumina, Pt-zeolite, Pd-carbon, Pd a catalyst of a combination of alumina, Pd-ceria, Pd-ceria alumina, Pd-zeolite, or the like. Among these, a catalyst containing Rh, Ru or Pd as a metal component is particularly preferable, and Rh-carbon, Ru-carbon, Ru-alumina, Pd-carbon, and Pd_alumina catalyst are more preferable. good. The modulation method of the catalyst is not particularly limited, and a general catalyst modulation method may be used. For example, a method of immersing a monomer in a metal salt solution as a catalyst and performing a reductive treatment of a catalyst by a reducing agent; after impregnating the monomer with a metal salt solution as a catalyst, by alkaline a method of sintering a metal hydroxide or an oxide precipitated on a carrier by contacting a solution or the like; impregnating the monomer with a metal salt solution as a catalyst, and contacting the metal hydrogen precipitated on the carrier by contact with an alkaline solution or the like A method of modulating a catalyst after sintering an oxide or an oxide and performing a reductive treatment with a reducing agent; a method of preparing an alloy of the metal and A1, and further eluting A1 with an alkaline treatment. However, the present invention is not limited to these. In the hydrogenation reaction, in order to remove the heat of reaction or to reduce the hydrogen diffusion efficiency due to an increase in viscosity, it is preferred to use a solvent to react in the liquid phase. The solvent to be used in the reaction may be any solvent as long as it does not inhibit the reaction. Specifically, for example, one type or two or more types of halogenated hydrocarbons selected from the group consisting of dichloromethane, chloroform, and 1,2-dichloroethane; pentane, ?-24-201116543 alkane, pentane, octane, etc. may be used. Aliphatic hydrocarbon solvent; diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether , an ether solvent such as diethylene glycol diethyl ether, diethylene glycol dibutyl ether, tetrahydrofuran or 1,4-dioxane; 2 · methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol An ether alcohol solvent such as 2-isopropoxyethanol, 2-butoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether or propylene glycol monoethyl ether An alcohol solvent such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol or cyclohexanol; a mixed solvent of water or the like. In the above, when considering the solubility of hydrogen and the solubility of a copolymer of a fatty acid allyl ester and an aromatic radical polymerizable monomer, an ether solvent and a halogenated hydrocarbon solvent, particularly tetrahydrofuran '1,4- Dioxane' and chloroform are preferred. The pressure of hydrogen in the hydrogenation reaction may be under normal pressure or under pressure, but in order to promote the reaction efficiently, it is preferred to carry out the reaction under pressure. It is usually carried out in the range of 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 it does not reduce the efficiency of the catalyst reaction, but is usually 0 to 300 t, preferably 50 to 250 ° C, more preferably 7 to 220 ° C. get on. High temperatures tend to cause side reactions, and at low temperatures, a substantially useful reaction rate cannot be obtained. The reaction type of the hydrogenation reaction can be carried out by a suspension bed batch reaction, a fixed bed flow reaction, a fluidized bed flow reaction, etc. in response to a process, and is any reaction type used in a general liquid phase hydrogenation decomposition reaction or a liquid phase addition hydrogen reaction. -25- 201116543 Status. The amount of catalyst used will vary depending on the type of reaction, and is not particularly limited. In the suspension bed batch process, 100 parts by mass of the copolymer of the fatty acid allyl ester and the aromatic radical polymerizable monomer with respect to the matrix is usually 0.01 to 100 parts by mass, preferably 0.1 to 50 parts by mass, More preferably used in the range of 0.5 to 20 parts by mass. When the amount of the catalyst is too small, a substantially sufficient reaction rate cannot be obtained. Further, when the amount of the catalyst is too large, there is a problem that the side reaction increases or the catalyst cost increases. After completion of the hydrogenation reaction, the hydride of the product's allyl ester copolymer can be post-treated by well-known procedures and treatment methods (for example, filtration, solvent extraction, water washing, liquid separation, solvent distillation, reprecipitation, etc.). Segregation. <Transesterification reaction> The transesterification reaction can be carried out by bringing the hydride of the allyl ester copolymer into contact with an alcohol compound in the presence of a catalyst. The transesterification reaction can be carried out using the same conditions as described in the description of the A method, except that the hydrogenation of the allyl ester copolymer is used instead of the precursor A. [Embodiment] [Examples] Hereinafter, the present invention will be described in more detail by way of Examples of Comparative Examples and Comparative Examples, but the present invention is not limited thereto. -26- 201116543 The physical properties of the materials synthesized in the examples and comparative examples were measured as follows.

1. FT-1R Model: Spectrum GX (manufactured by PerkinElmer Co., Ltd.), measurement method: Measurement was carried out by a liquid membrane method using a KBr plate.

2, 'H-NMR > l3C-NMR Model: JEOL EX-400 (400 MHz, manufactured by JEOL Ltd.), measurement method: The sample was dissolved in deuterochloroform or deuteromethanol. The internal standard material was determined using tetramethyl decane. 3. Gel Chromatography (GPC) Machine column: Shodex GPC KG + K- 802 + K-802.5 + K-801 (made by Showa Denko), Detector: S h 〇 de XSE - 6 1 (Showa Manufactured by an electrician company, solvent: chloroform or tetrahydrofuran, measuring temperature: 40 °C, flow rate: 1.0 m 1 /min, sample concentration: 〗 〖. 〇mg/ml, -27- 201116543 Injection volume: 1 · 〇μ1, calibration curve: Universal Calibration curve, analysis software: SIC 480II (system instrument company). 4. Hydroxyl valence The measurement was carried out in accordance with the method described in JIS K0070. 5. The allyl alcohol monomer unit mole % is calculated from the number average molecular weight and the hydroxyl value. Example 1: Production of allyl alcohol/1-decene copolymer Into a 300 ml stainless steel autoclave (manufactured by a pressure-resistant industrial company), allyl acetate (12.00 g, manufactured by Tokyo Chemical Industry Co., Ltd.) was added. 0.120 mol) with 1-decene (manufactured by Wako Pure Chemical Industries, Ltd., 84.16 g, 0.600 mol), di-t-butyl peroxide (manufactured by Kishida Chemical Co., Ltd., 4.81 g, 0.0329 mol), fitted with a flange joint After (flange), the system was replaced three times with nitrogen. Then, the content was heated while stirring at 400 rpm, and allowed to react at 145 ° C for 6 hours. The content was cooled to room temperature, and after depressurization, the contents were taken out, and the contents were taken out, and unreacted allyl acetate, 1-decene, and a starter residue were removed at 100 ° C under reduced pressure to obtain high. Viscous oil 42.1 1 g. 20 g of this oil, 250 ml of ethanol, and sodium hydroxide (manufactured by Wako Pure Chemical Industries, Inc., 〇. 4 g, 0.001 mol) were placed in a 500 ml two-necked flask and replaced with nitrogen. When stirring, the reaction was carried out at 80 ° C for 4 hours -28 - 201116543 hours. After the content was cooled to room temperature, the sodium residue was removed by a plug of 30 g of an ion exchange resin (DAIAION PK208H, manufactured by Mitsubishi Chemical Corporation), and then ethanol was removed under reduced pressure to obtain a yellowish oil. 17.87g. The recovery rate from the raw materials was 41.7%. The obtained oily substance was measured for 1H-NMR, 13C-NMR and IR spectrum, and the target copolymer was confirmed. The peak from allyl acetate almost disappeared. Further, the copolymer had a number average molecular weight of Mn = 164 Å, a hydroxyl value of 88 mgKOH/g, and an allyl alcohol monomer unit of 19.5 mol%. Further, the evaluation results of the solubility with hexane, pentane, chloroform, methanol, ethanol and acetone are shown in Table 2. Example 2: Production of allyl alcohol/1-decene copolymer In addition to allyl acetate (18.02 g, 0.180 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) and decimene (manufactured by Wako Pure Chemical Industries, Ltd., 84.1 6 g, 0.600) The same reaction as in Example 1 and post-treatment was carried out except that the mixture was added to the same procedure as in Example 1 to obtain 18.6 g of a slightly yellow oil. The recovery rate from the raw material was 44.0%. The obtained oily substance was determined to have a target copolymer of 1 Η - N M R, 13 C - N M R and IR spectrum. The peak from allyl acetate almost disappeared. Further, the copolymer had a number average molecular weight of Mn = 1630, a hydroxyl value of 129 mgKOH/g, and an allyl alcohol monomer unit of 27.5 mol%. Further, the results of evaluation of solubility with various solvents are shown in Table 2. -29 - 201116543 Example 3: Production of allyl alcohol/1-decene copolymer In a 1 L glass retort (manufactured by Pressure-resistant Industrial Co., Ltd.), allyl acetate (100.10 g, manufactured by Tokyo Chemical Industry Co., Ltd.) was added. , l.OOOmol) and 1-decene (made by Wako Pure Chemical Industries, Ltd., 280.60 g, 2.000 mol), di-t-butyl peroxide (manufactured by Kishida Chemical Co., Ltd., I9.00 g, 0.1299 mol), with a convex After the edge joint portion, the inside of the system was replaced with nitrogen three times. Then, the contents were heated while stirring at 400 rpm, and allowed to react at 145 ° C for 6 hours. The content was cooled to room temperature, and after depressurization, the contents were taken out of the reactor, and the unreacted allyl acetate, 1-decene, and the starter residue were removed at 100 ° C under reduced pressure to obtain a high content. Viscous oil 1 8 0.5 0g. The obtained oily substance was measured for 1H-NMR, 13C-NMR and IR spectrum, and the target copolymer was confirmed. The peaks derived from allyl acetate almost disappeared. The results of 1H-NMR and IR spectroscopy are shown in Figures 1 to 2, respectively. 50.00 g of this oil, 600 ml of ethanol, and sodium hydroxide (0.10 g, 0.0025 mol, manufactured by Wako Pure Chemical Industries, Ltd.) were placed in a 1-L two-necked flask, and the mixture was replaced with nitrogen, followed by stirring for 8 ( The TC was allowed to react for 5 hours. After the content was cooled to room temperature, the sodium residue was removed by plugging a 100 g column of ion exchange resin (DAIAION PK208H, manufactured by Mitsubishi Chemical Corporation), and then the ethanol was removed under reduced pressure. 39.99 g of a yellowish oil was obtained. The recovery rate from the raw material was 45.2%. The obtained oily substance was determined to have a target of 1H-NMR, 13C-NMR and IR spectrum. 1H-NMR and The results of IR spectrum measurement are shown in Figures 3 to 4. In addition, the number average molecular weight of the copolymer was Mn = 128, the hydroxyl value was 207 mgKOH/g, and the allyl alcohol monomer unit was -30-201116543 39.7 mol. The results of the evaluation of the solubility with various solvents are shown in Table 2. Example 4: Production of allyl alcohol/1-decene copolymer In addition to allyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd., 140.14 g) , 1.400mol) and 1-decene (made by Wako Pure Chemical Industries, Ltd., 280.60g, 2.000 mol), di-t-butyl The same reaction as in Example 3 and post-treatment was carried out except that the base peroxide (manufactured by Kishida Chemical Co., Ltd., 21.00 g, 0.144 m·l) was added to give a yellowish oil of 4 1 · 3 9 g. Recovery from the raw material. 52.3%. The obtained oily substance was measured for 1 Η-NMR, 13 C-NMR and IR spectrum, and the target copolymer was confirmed. The peak derived from allyl acetate almost disappeared. The number average molecular weight was Μη=1 770, the hydroxyl value was 25 6 mgKOH/g, and the allyl alcohol monomer unit was 46.6 mol%. The solubility evaluation results with various solvents are shown in Table 2. Example 5: Allyl alcohol /1 - The terpene copolymer was produced by the addition of propyl acetate (200.20 g, 2-OOOmol, manufactured by Tokyo Chemical Industry Co., Ltd.) and 1-decene (280.60 g, 2.000 mol, manufactured by Wako Pure Chemical Industries, Ltd.), T-butyl peroxide (manufactured by Kishida Chemical Co., Ltd., 24 〇〇g, 0.164 mol) was added to the same reaction as in Example 3, and post-treatment was carried out to obtain 35.5 Og of a slightly yellow oil. Recovery from the raw material. 5 3.4%. The obtained oil was measured for 1H-NMR, 13c_NMr and IR light -31 - 201116 543 spectrum, confirmed as the target copolymer. The peak derived from allyl acetate almost disappeared. In addition, the number average molecular weight of the copolymer was Mn = 1 650, the hydroxyl value was 550 mg K 〇 H / g, allyl alcohol The monomer unit was 57.8 mol%. Further, the results of evaluation of solubility with various solvents are shown in Table 2. Example 6: Production of allyl alcohol/ethylene cyclohexane copolymer Allyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd., 50.06 g, 0.500 mol) was added to a 300 ml stainless steel retort (manufactured by a pressure-resistant industrial company). With styrene (manufactured by Wako Pure Chemical Industries, Ltd., 5 2.08 g, 0.500 mol), di-t-butyl peroxide (manufactured by Kishida Chemical Co., Ltd., 5.11 g, 0.03 49 mol), after fitting the flange joint portion, nitrogen was used. Replacement within 3 times. Then, the contents were heated while stirring at 400 rpm, and allowed to react at 1,55 ° C for 5 hours. The content was cooled to room temperature, and after depressurization, the contents were taken out of the reactor, and unreacted allyl acetate, styrene, and starter residue were removed at 100 ° C under reduced pressure to obtain high viscosity. Oil 75.08 g. 6.0 g of the obtained oil was added to 120 ml of 1,4-dioxane (55.0 ml manufactured by Wako Pure Chemical Industries, Ltd.) and powdered 5% Rh-carbon (manufactured by Wako Pure Chemical Industries, Ltd., 〇.7 g). In the stainless steel retort (manufactured by Pressure-resistant Nitrogen Industrial Co., Ltd.), after the flange joint portion is attached, the inside of the system is replaced with nitrogen three times, and the hydrogen gas is replaced with hydrogen gas. Finally, a hydrogen pressure of 4.5 MPaG (pressure gauge) is applied. . Then, the content was heated while stirring at 400 rpm, and reacted at 20 (TC for 7 hours). During this time, hydrogen was introduced to keep the reaction pressure constant. The contents were cooled to room temperature, and the reaction was carried out, and then the reactor was opened. The material was taken out, and the catalyst was removed by filtration. The obtained filtrate was subjected to distillation under reduced pressure -32-201116543 to remove 1,4-dioxane to obtain 6.0 g of a highly viscous oil. It was placed in a two-necked flask of 100 〇 11 with ethanol 60 μm and sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.), and replaced with nitrogen in the system, and then stirred with 8 The reaction was allowed to proceed for 4 hours at 0 ° C. After cooling the contents to room temperature, the sodium residue was removed by plugging a 10 g column of ion exchange resin (DAIAION PK: 2 〇 8H, manufactured by Mitsubishi Chemical Corporation), and thereafter The ethanol was removed under reduced pressure to give 4.36 g of a pale yellow oil. The recovery from the starting material was 65.5 %. The obtained oil was measured by 1 Η - NMR, 13 C - NMR and IR spectra. The target copolymer. The peak from allyl acetate almost disappears. In addition, this copolymerization The number average molecular weight of the material was Μη = 2 5 60, the hydroxyl value was 82 mgKOH/g, and the allyl alcohol monomer unit was 15 mol%. The solubility evaluation results with various solvents are shown in Table 2. Example 7: Allyl Manufacture of alcohol/1-octene copolymer In a 120 ml stainless steel retort (manufactured by Pressure Resistant Industrial Co., Ltd.), allyl acetate (20.00 g, 0.200 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) and 1-octene were added. Was prepared by Wako Pure Chemical Co., Ltd., 44.83 g, 0.400 mol), di-t-butyl peroxide (manufactured by Kishida Chemical Co., Ltd., 3.24 g, 0.022 mol), and the inside of the flange joint was replaced by nitrogen three times. Then, the contents were heated while stirring at 40 Or pm, and allowed to react at i 55 ° C for 5 hours. The contents were cooled to room temperature, and after decompression, the reactor was opened and the contents were taken out. Unreacted allyl acetate, 1-octyl and starter residue were removed at 100 ° C to give a highly viscous oil 2 8.9 2 g. -33- 201116543 This oil was 10.〇〇g with 120 ml of ethanol, sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd., 0.02 g, 〇.〇〇〇5 mol) was added to a 300 ml two-necked flask. After replacing the inside with nitrogen, the mixture was reacted at 80 t for 4 hours while stirring. After the content was cooled to room temperature, sodium was removed by a plug of 15 g of ion exchange resin (DAIAION PK208 H, manufactured by Mitsubishi Chemical Corporation). The residue was removed, and then the ethanol was removed under reduced pressure to give a pale-yellow oil (yield: 8 to 49 g). The obtained oily substance was measured for 1H-NMR, 13C-NMR and IR spectrum, and the target copolymer was confirmed. The peak from allyl acetate almost disappeared. Further, the copolymer had a number average molecular weight of Mn = 1,180, a hydroxyl value of 248 mgKOH/g, and an allyl alcohol monomer unit of 46.7 mol%. Further, the results of evaluation of solubility with various solvents are shown in Table 2. Example 8: Production of allyl alcohol/1-hexene copolymer Into a 120 ml stainless steel retort (manufactured by a pressure-resistant industrial company), allyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd., 14.00 g, 0.140 m 〇) was added. 1) After the flange joint was attached to the 1-joint (made by Wako Pure Chemical Co., Ltd., 39.23 g, 0.466 mol) and di-t-butyl peroxide (manufactured by Kishida Chemical Co., Ltd., 2.66 g, 0.018 mol) Replaced with nitrogen three times. Then, the contents were heated while stirring at 400 rpm, and allowed to react at 15 5 ° C for 5 hours. The content was cooled to room temperature, and after depressurization, the contents were taken out of the reactor, and the unreacted allyl acetate, 1-hexene and the starter residue were removed at 100 ° C under reduced pressure to obtain a high viscosity. Sex oil 1 6.5 6g. 10.00 g of this oil, 120 ml of ethanol, and sodium hydroxide (manufactured by Wako Pure-34-201116543, 0.02 g, 0.0005 mol) were placed in a 300-ml two-necked flask, and the mixture was replaced with nitrogen, and then stirred. The reaction was carried out for 4 hours at 8 (TC). After cooling the contents to room temperature, the sodium residue was removed by plugging a column of 15 g of ion exchange resin (DAIAION PK208 H, manufactured by Mitsubishi Chemical Corporation), and thereafter decompressed. After the ethanol was removed, 7.69 g of a yellowish oil was obtained. The recovery from the raw material was 29.6%. The obtained oily substance was determined to have a target of 1H-NMR, 13C-NMR and IR spectrum. The peak derived from allyl acetate almost disappeared. Further, the copolymer had a number average molecular weight of Μ n = l 120 , a hydroxyl group value of 222 mg KOH / g, and an allyl alcohol monomer unit of 37.2 mol %. The results of the evaluation of the solubility are shown in Table 2. Example 9: Production of allyl alcohol/1-tetradecene copolymer In a 300 ml stainless steel retort (manufactured by Pressure Resistant Industrial Co., Ltd.), allyl acetate was added ( Made by Tokyo Chemical Industry Co., Ltd., 3 5.00g, 0.3 5 0m〇l) and 1-tetradecene Manufactured by Tokyo Chemical Industry Co., Ltd., ll4.43g, 0·5 8 3 τη〇1), di-t-butyl peroxide (7.57g, 0.051 mol, manufactured by Kishida Chemical Co., Ltd.), after the flange joint was attached, The contents were replaced with nitrogen three times. Then, the contents were heated while stirring at 400 rpm, and allowed to react at 145 ° C for 6 hours. The contents were cooled to room temperature, and after decompression, the contents were taken out of the reactor. Under the reduced pressure of 16 (TC unreacted allyl acetate, 1-tetradecene and starting agent residue were removed to obtain 94.2 7 g of highly viscous oil. 93.00 g of this oil and 280 ml of ethanol, hydrogen Sodium oxide (manufactured by Wako Pure-35-201116543 Pharmaceutical Co., Ltd., 〇.19g, 〇.〇〇48mol) was placed in a 30 ml two-necked flask, and the mixture was replaced with nitrogen, and then reacted at 80 ° C with stirring. After cooling the contents to room temperature, the sodium residue was removed by a plug of 100 g of an ion exchange resin (DAIAION PK208H, manufactured by Mitsubishi Chemical Corporation), and then the ethanol was removed under reduced pressure to obtain a yellowish color. The oil was 83.11 g. The recovery from the raw material was 6 0.1%. The obtained oil was determined to be 1H-NMR. The 13C-NMR and IR spectra were confirmed as the target copolymers. The peak derived from allyl acetate almost disappeared. In addition, the number average molecular weight of the copolymer was Mn = 23 50, and the hydroxyl value was 150 mgKOH/g. The alcohol monomer unit was 38.4 mol%, and the solubility evaluation results with various solvents are shown in Table 2. Example 10: Production of allyl alcohol/1-decene/2-norbornene copolymer Allyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to a 120 ml stainless steel retort (manufactured by a pressure-resistant industrial company). 19.49 g, 0.195 m〇l) with 1-decene (30.00 g, 0.214 mol, manufactured by Wako Pure Chemical Industries, Ltd.), 2-northene (manufactured by Tokyo Chemical Industry Co., Ltd., 6. 4 g, 0.064 mol), and T-butyl peroxide (2.78 g, 0.019 mol, manufactured by Kishida Chemical Co., Ltd.) was attached to the flange joint portion, and then replaced with nitrogen three times. Then, the content was heated while stirring at 4,000 rpm, and allowed to react at 145 ° C for 5 hours. The content was cooled to room temperature, and after depressurization, the contents were taken out of the reactor, and unreacted allyl acetate, 1-decene, 2-norbornene and unreacted under reduced pressure at 1 ° C. The residue of the starting agent is removed to obtain a highly viscous oil. 3 0.3 4g ° -36- 201116543 This oil is 5 _ 0 0 g and ethanol 3 0 m 1 , sodium hydroxide (made by Wako Pure Chemical Industries, Ltd., 0.02 g' 0-0005 mol) was placed in a two-neck flask of i〇〇ml, and after replacing the inside with nitrogen, it was made to 80 at the time of stirring. (The reaction was carried out for 4 hours. After the content was cooled to room temperature, the sodium residue was removed by plugging a 10 g column of ion exchange resin (DAIAION PK2 〇 8H, manufactured by Mitsubishi Chemical Corporation), and thereafter, under reduced pressure. The ethanol was removed to obtain a slightly yellow oil of 4.00 g. The recovery from the starting material was 52.0%. The obtained oily substance was determined to have a target of 1H-NMR, 13C-NMR and IR spectrum. The peak derived from the acetic acid vinegar was almost eliminated. The number average molecular weight of the copolymer was Mn = 1650 and the hydroxyl value was 22 〇 mg KOH / g. The results of evaluation of 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 and 600 ml of ethanol, sulfuric acid (manufactured by Wako Pure Chemical Industries, Ltd., 0.20 g After adding to a 1 L two-necked flask, the mixture was replaced with nitrogen, and then reacted at 80 ° C for 5 hours while stirring. After cooling the contents to room temperature, sodium hydroxide was added to neutralize the sulfuric acid. After the residue was filtered and the salt formed was filtered off, the ethanol was removed under reduced pressure to give a slightly yellow oil. 44.75 g of the obtained oily substance was measured for 1H-NMR, 13 C-NMR and IR spectrum, and the conversion ratio of the transesterification reaction was 52 %, and the ester structure remained in the product. The number average molecular weight of the material is Mn = 2050, the hydroxyl value is 95 mgKOH/g, and the allyl alcohol monomer unit is 2 〇. 〇mol%. The solubility evaluation results of the other solvents are shown in Table 2 below. Example 12: Production of allyl alcohol/1-decene copolymer (reduction of the amount of ethanol in the transesterification reaction) Allyl acetate (Tokyo) was added to a 1 L glass retort (manufactured by Pressure Resistant Industrial Co., Ltd.) Chemical Industry Co., Ltd., 16.00 g, 0.360 mol) and 1-decene (made by Wako Pure Chemical Industries, Ltd., 3 60.00 g, 2.5 67 mol), di-t-butyl peroxide (KISHIDA Chemical Co., Ltd., 19.80 g, 0.1354) Mol), after the flange joint portion was attached, the inside was replaced with nitrogen three times. Then, the content was heated while stirring at 600 μm, and allowed to react at 155 ° C for 5 hours. The contents were cooled to room temperature. After depressurization, the reactor was opened and the contents were taken out, and unreacted allyl acetate was distilled at 160 ° C under reduced pressure. , 1-decene and the starter residue were removed to obtain a high-viscosity oil of 1 74.5 2 g. 150.00 g of this oil was added with 450 ml of ethanol and sodium hydroxide (0.30 g, 7.50 mmol, manufactured by Wako Pure Chemical Industries, Ltd.). After a 1 L three-necked flask was replaced with nitrogen, the mixture was reacted for 5 hours at an oil bath temperature of 85 ° C while stirring. After cooling the contents to room temperature, the mixture was passed through an ion exchange resin (Mitsubishi Chemical Corporation). , DAIAION PK216LH) 3 00 g of the column removed the sodium residue, and then the ethanol was removed under reduced pressure to give a slightly yellow oil, 1 37.22 g. The recovery rate from the raw material was 44.1%. The obtained oily substance was measured for 1H-NMR, 13C-NMR and IR spectrum, and the target copolymer was confirmed. The peak from allyl acetate almost disappeared. Further, 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%. In addition, the solubility evaluation results of various solvents with -38- 201116543 are shown in Table 2. Example 1 3: Production of allyl alcohol/1-decene copolymer (reducing the amount of ethanol in the transesterification reaction and the ester formation during the distillation reaction) The same operation as in Example 1 2 was carried out to obtain ethyl acetate as the acrylic acid. A highly viscous oil of the copolymer of ester and 1-decene 1 75.47 g. 1 50·00 g of this oil and 45 ml of ethanol and sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd., 〇.30 g, 7.50 mmol) were placed in a 1-L three-necked flask, and the mixture was replaced with nitrogen. The oil bath was reacted at 8 8 t for 2 hours. In the meantime, ethyl acetate formed by the reaction was co-distilled with a small amount of methanol to the outside of the system. After the content was cooled to room temperature, the sodium residue was removed by a plug of 300 g of an ion exchange resin (DAIAION PK216LH, manufactured by Mitsubishi Chemical Corporation), and then the ethanol was removed under reduced pressure to obtain a yellowish oil. 1.3 8.6 5 g. The recovery rate from the raw material was 44.3%. The obtained oily substance was measured for 1H-NMR, l3C-NMR and IR spectrum, and the target copolymer was confirmed. The peak from allyl acetate almost disappeared. Further, 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%. Further, the results of evaluation of solubility with various solvents are shown in Table 2. Comparative Example 1: Production of allyl alcohol oxime-decene copolymer Into a 120 ml stainless steel retort (manufactured by a pressure-resistant industrial company), allyl alcohol (manufactured by Showa Denko Co., Ltd., 8.00 g, 0.138 mol) and 1- After the ferrene (manufactured by Wako Pure Chemical Industries, Ltd., 38.64 g, 0.275 mol), di-t-butyl peroxy-39-201116543 (manufactured by Kanto Chemical Co., Ltd., 2.33 g, 0.0159 mol) was attached to the flange joint portion. Replace the system three times with nitrogen. Next, the content was heated while stirring at 4 rpm, and allowed to react at 40 ° C for 5 hours. The content was cooled to room temperature, and after depressurization, the contents were taken out of the reactor, and unreacted allyl alcohol, 1-decene, and starter residue were removed at 100 ° C under reduced pressure to obtain high viscosity. The oil was 9.08 g. The recovery from the raw material was 18.5%. The obtained oily substance was measured for 1H-NMR, 13C-NMR and IR spectrum, and the target copolymer was confirmed. Further, the number average molecular weight of this copolymer was a low enthalpy of Mn = 83 0 . The hydroxyl group content was 217 mgKOH/g, and the allyl alcohol monomer unit was 41.2 mol%. Further, the results of evaluation of solubility with 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 and 600 ml of pure water, sodium hydroxide (Wako Pure Chemical Industries, Ltd.) The system, 0.10 g, 0.0025 mol) was placed in a 1 L two-necked flask, and allowed to react at 8 Torr for 5 hours while stirring. After cooling the contents to room temperature, they were separated into two phases if left. The aqueous phase was separated by a separating funnel, and another 500 ml of pure water was added to wash the organic phase. This operation was repeated 3 times until the organic phase became neutral. Thereafter, it was treated under reduced pressure at 〇〇 ° C for 2 hrs to yield 49.1 g of pale yellow oil. The obtained oily substance was subjected to 1H-NMR, 13C-NMR and IR spectroscopy, and found to be an allyl acetate/1-decene copolymer, and the hydrolysis reaction was carried out completely without -40-201116543. The results of 1H-NMR and IR spectroscopy are shown in Figures 5 to 6, respectively. i Comparative Example CNJ II Unreacted 〇o - 41.2 58.8 830 Bu 18.5 CO 16.3 83.7 I 1760 ! 44.3 CNJ 16.7 83.3 1 1720 '44.1 20.00.0 80.0 2050 m σ > I 〇Η * a * * 1650 ^2〇52.0 σ> 38.4 61.6 2350 s ! 60.1 CO 37.2 62.8 1120 ! 29.6 r- 46.7 53.3 1180 m CM 42.5 Street CO 15.0 85.0 2560 CM CO ;65.5 ιο 57.8 42.2 1650 350 53.4 Guard 46.6 53.4 1770 256 52.3 CO 39.7 60,3 1880 s 45.2 CM 27.5 72,5 1630 σ> I 44.0 Strict 19.5 80.5 1640 00 00 41.7 Allyl alcohol is divided into 1_decene styrene (hydrogenated) 1_ Octene 1 -hexene 1 - tetradecene 2 - norbornene C mgKOH / g formula (3) monomer (mol%) formula (2) monomer (mol%) other monomer (mol%) If hydrocarbon price Recovery rate -41 - 201116543

[S TT51 赵 X 〇〇〇〇X 〇〇X 〇〇XXO 1 貤K1 〇ο ο 〇ο ο 〇〇〇〇〇〇〇〇1 advise ffi- XX 〇ο ο X 〇〇X 〇〇XX o 1 iS 枫 〇〇〇〇 0 ο 〇〇〇〇〇〇〇〇1 〇ο ο ο XX 〇〇〇X 〇0 〇〇1 〇〇ο 〇XX 〇〇〇X 〇〇Ο o 1 i 堤μ CM 闺CO 莩m κ inch bracelet LO |i( CO 揖 揖 00 〇 〇 0 0 0 0 0 IK CS CS CS CS CS CS CS CS CS CS CS CS CS CS CS CS CS CS CS CS CS CS CS CS CS CS CS CS CS CS CS CS CS CS CS CS CS CS CS CS CS CS CS CS CS CS [1] The 1 H-NMR spectrum of the allyl acetate/i-pinene copolymer obtained in Example 3 [Fig. 2] The allyl acetate π-pinene obtained in Example 3 IR spectrum of the copolymer [Fig. 3] 'H-NMR of the allyl alcohol / 1-decene copolymer obtained in Example 3. -42 - 201116543 [Fig. 4] The olefin obtained in Example 3 IR spectrum of the alcohol/1-decene copolymer [Fig. 5] 1 Η-NMR spectrum of the product obtained in Comparative Example 2. [Fig. 6] IR spectrum of the product obtained in Comparative Example 2. 43-

Claims (1)

201116543 VII. Patent Application Range: 1. A method for the preparation of allyl alcohol copolymers, which comprises the structure represented by formula (3) and formula (2) as the unit of the body; (1) [Chemical 1] HICICIO1 HICIH /V R1I CMMO and formula (2) [Chemical 2] I 2 HIC—Ri HICIH (2) (wherein R1 is represented by an aliphatic hydrocarbon group having a carbon number of 1 to 1 Å, It is branched or contains a cyclic structure; R2 is shown as an aliphatic hydrocarbon group having 2 to 20 carbon atoms, which may be branched or contains a cyclic structure). A method for producing an allyl alcohol copolymer which is a copolymer of a monomer unit and a transesterification reaction with an alcohol in the presence of a catalyst, TIJ 3 /H2H H-OICIO - HICIH (3) -44- 201116543 TJ 4 HICIH 2 HICIR (2) (wherein R2 is the same as the above). 2. The method for producing an allyl alcohol copolymer according to item 1 of the scope of the patent application * The alcohol used in the cfcj 〃 ψ ' transesterification reaction is an alkyl alcohol having a carbon number of 丨 10 10 . 3 'As a method for producing an allyl alcohol copolymer according to item 2 of the patent application, a: The alkyl alcohol having a carbon number of 1 to 10 is hereinafter referred to as ethanol or 1-propanol. \ 4· The manufacturer of the allyl alcohol copolymer in the first application of the patent range I The catalyst used in the vinegar exchange reaction is sodium hydroxide, a hydroxide cone, or a potassium hydride. 5 ‘ % $ Please consult the manufacturer of the allyl alcohol copolymer in item 4 of the patent range. 7 The acid used in the acid exchange reaction is sodium hydroxide. 6 · $α $ Please refer to the manufacturing method of the allyl alcohol copolymer of the first item of the patent range 'wherein the aliphatic hydrocarbon group having the carbon number of 1 to 10 represented by R 1 in the formula (1) is a carbon number of 1 to 5 straight A chain aliphatic hydrocarbon group. 7. 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 η-propyl group. 8. 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. 9. The method for producing an allyl alcohol copolymer according to the first aspect of the patent application-45-201116543, wherein R2 in the formula (2) is a linear aliphatic hydrocarbon group having a carbon number of 2 to 10, or a carbon number of 6 ～10 alicyclic hydrocarbon groups. 10. The process for producing an allyl alcohol copolymer according to claim 9, wherein R2 in the formula (2) is ethyl, n-propyl, η-butyl, η-pentyl or η-hexyl , η·octyl, η•fluorenyl, η_dodedo, or cyclohexyl. 11. The method for producing an allyl alcohol copolymer according to the first aspect of the patent application, which is composed of only the monomer units of the formula (1) and the formula (2). 12. The method for producing an allyl alcohol copolymer according to claim 1 wherein a structure obtained by copolymerizing a radically polymerizable olefin compound is used as a third monomer unit. 13. The method for producing an allyl alcohol copolymer according to claim 12, wherein the third monomer unit is a structure derived from methyl acrylate, methyl methacrylate, vinyl acetate, or styrene. 14. The method for producing an allyl alcohol copolymer according to claim 1, wherein the monomer unit represented by the formula (1) is from 3 to 60 mol% relative to the all monomer unit. The method for producing an allyl alcohol copolymer according to the item 12, wherein the radically polymerizable olefin compound unit is contained in an amount of 0.1 to 20.0 mol% based on the total monomer unit. -46 -