WO2011013844A2

WO2011013844A2 - Production method of allyl alcohol copolymer

Info

Publication number: WO2011013844A2
Application number: PCT/JP2010/063133
Authority: WO
Inventors: Nobuyuki Kibino; Yukiharu Hetsugi; Tsuneo Tajima
Original assignee: Showa Denko K.K.
Priority date: 2009-07-29
Filing date: 2010-07-28
Publication date: 2011-02-03
Also published as: JP2011046935A; TW201116543A; WO2011013844A3

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, R²represents 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 R²has 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

DESCRIPTION

PRODUCTION METHOD OF ALLYL ALCOHOL COPOLYMER TECHNICAL FIELD

The present invention relates to a production method of an allyl alcohol copolymer.

BACKGROUND ART

Olefin polymers having polar groups in the structure, having compatibility with various polar resins, excellent adhesiveness and colorability, are being widely used industrially. Although there have been various reports on production methods of olefin polymers having polar groups, most of the methods include introduction of polar-group-containing monomers through graft

polymerization .

For example, Japanese Patent Application Laid- Open No. 2005-113038 (U.S. Patent No. 7,569,642; Patent Document 1) discloses a higher α-olefin polymer containing a polar group in which the polar group has been introduced by allowing a higher α-olefin polymer to react with a decomposition agent and a polar compound. In a method using graft polymerization, however, there is concern about degradation of the produced polymer due to

oxidization and dispersibility of the polar group. Thus, such a method cannot be considered to be satisfactory in securing product quality.

There have been reports on examples of

production method for solving the above problem by using copolymerization of polar-group-containing monomer and other olefin-based monomer, though not many. For example, Japanese Patent Application Laid-Open. No . S64-54009 (U.S. Patent No. 4,987,200; Patent Document 2) and Japanese Patent Application Laid-Open No. 2003-165809 (Patent

Document 3) are known. The methods described in these documents use anion polymerization, in which it is

necessary to treat a polar-group-containing monomer with an equimolar amount or more of an organic metal compound in order for catalyst activity to be expressed. This is disadvantageous in production costs.

On the other hand, U.S. Patent No. 5,444,141 (Patent Document 4) discloses an example of a method for producing a copolymer by radical copolymerization between an allyl alcohol and an aromatic vinyl monomer. In this ■ method, productivity of polymer can be improved and

production costs can be reduced. The document, however, which discloses only copolymerization between allyl alcohol and styrene in its examples, and no example using other polymerizable monomers is included.

Furthermore, radical copolymerization of allyl alcohol and monomers other than aromatic vinyl monomer has had little precedent and even if a product were obtained, the yield was low and the number average molecular weight of the product was less than 1000. Therefore, there have been demands for an efficient production method using a polar-group-containing polymerizable monomer having a carbon-carbon double bond other than styrene. PRIOR ART DOCUMENTS [Patent Documents]

[Patent Document 1] JP-A-2005-113038 (U.S. Patent No. 7, 569, 642)

[Patent Document 2] JP-A-S64-54009 (U.S. Patent- No.

4,987,200

[Patent Document 3] JP-A-2003-165809

[Patent Document 4] U.S. Patent No. 5,444,141

SUMMARY OF THE INVENTION

[Problems to be Solved by the Invention]

The present invention aims to provide a method for efficiently producing a copolymer of allyl alcohol and α-olefin .

[Means to Solve the Problems]

As a result of intensive studies made with a view to solving the above problems, the present inventors have found that by allowing an aliphatic acid allyl ester to react with an radically polymerizable aliphatic olefin compound in the presence of a radical polymerization initiator and subjecting the thus-generated copolymer to transesterification in the presence of alcohol and a catalyst; or by hydrogenating a copolymer of an aliphatic acid allyl ester and an radical polymerizable aromatic monomer and subjecting the thus-generated copolymer to transesterification in the presence of alcohol and a catalyst, a polymer having a polar group can be

efficiently produced, whereby completing the present invention .

That is, the present invention relates to the following [1] to [15]. [1] 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. [2] The method for producing an allyl alcohol copolymer as described in [1] above, wherein the alcohol used in transesterification reaction is alkyl alcohol having 1 to 10 carbon atoms.

[3] The method for producing an allyl alcohol copolymer as described in [2] above, wherein the alkyl alcohol having 1 to 10 carbon atoms is ethanol or 1- propanol .

[4] The method for producing an allyl alcohol copolymer as described in any one of [1] to [3] above, wherein the catalyst used in transesterification reaction is sodium hydroxide, lithium hydroxide or potassium hydroxide .

[5] The method for producing an allyl alcohol copolymer as described in [4] above, wherein the catalyst used in transesterification reaction is sodium hydroxide.

[6] The method for producing an allyl alcohol copolymer as described in any one of [1] to [5] above, wherein the aliphatic hydrocarbon group having 1 to 10 carbon atoms represented by R¹ is a linear aliphatic hydrocarbon group having 1 to 5 carbon atoms.

[7] The method for producing an allyl alcohol copolymer as described in [6] above, wherein the linear aliphatic hydrocarbon group having 1 to 5 carbon atoms is methyl group, ethyl group or n-propyl group.

[8] The method for producing an allyl alcohol copolymer as described in [7] above, wherein the linear aliphatic hydrocarbon group having 1 to 5 carbon atoms is methyl group.

[9] The method for producing an allyl alcohol copolymer as described in any one of [1] to [8] above, wherein R² in formula (2) is a linear aliphatic

hydrocarbon group having 2 to 10 carbon atoms or an alicyclic hydrocarbon group having 6 to 10.

[10] The method for producing an allyl alcohol copolymer as described in [9] above, wherein R² in formula (2) is ethyl group, n-propyl group, n-butyl group, n- pentyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group or cyclohexyl group.

[11] The method for producing allyl alcohol

copolymer according to any one of [1] to [10] above, wherein the copolymer comprises as monomer units the structures represented by formulae (1) and (2) only.

[12] The method for producing allyl alcohol

copolymer according to any one of [1] to [11] above, wherein the copolymer comprises as a third monomer unit the structure obtained by copolymerizing radically

copolymerizable olefin compounds.

[13] The method for producing allyl alcohol

copolymer according to [12] above, wherein the third monomer unit is a structure derived from methyl acrylate, methyl methacrylate, vinyl acetate or styrene.

[14] The method for producing allyl alcohol

copolymer according to any one of [1] to [13] above, wherein the copolymer comprises 3 to 60 mol% of the monomer unit represented by formula (1) to the total monomer units.

[15] The allyl alcohol copolymer according to [12] above, comprising 0.1 to 20.0 moll of the unit of

radically polymerizable olefin compound to the total monomer units.

EFFECTS OF THE INVENTION

According to the present invention, a copolymer of an allyl alcohol and an olefin compound can be

efficiently produced. The allyl alcohol copolymer obtained by the present invention, having a polar group, is excellent in compatibility with various resins and adhesion. Also, since the copolymer has a hydrophobic group, it is excellent in electric insulating property, low water absorption, thermal stability and surface activity effect. Thanks to these properties, the copolymer 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.

BRIEF DESCRIPTION OF DRAWINGS

Fig. 1 is a ¹H-NMR spectrum of the copolymer of allyl acetate and 1-decene obtained in Example 3.

Fig. 2 is an IR spectrum of the copolymer of allyl acetate and 1-decene obtained in Example 3.

Fig. 3 is a ¹H-NMR spectrum of the copolymer of allyl alcohol and 1-decene obtained in Example 3.

Fig. 4 is an IR spectrum of the copolymer of allyl alcohol and 1-decene obtained in Example 3.

Fig. 5 is a ¹H-NMR spectrum of the reaction product obtained in Comparative Example 2.

Fig. 6 is an IR spectrum of the reaction product obtained in Comparative Example 2. BEST MODE FOR CARRYING OUT INVENTION

Hereinafter, the present invention is described in greater detail.

[allyl ester copolymer]

The copolymer which is a precursor of the allyl alcohol copolymer of the present invention is a copolymer comprising monomer units represented by formula (1) and

(2) as monomer units

(In the formula, R¹ represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms, which may be branched or include a cyclic structure and R² represents an

aliphatic hydrocarbon group having 2 to 20 carbon atoms, which may be branched or include a cyclic structure.) :

i.e. a monomer unit derived from aliphatic acid allyl ester (formula (I)) and a monomer unit derived from α- olefin (formula (2) ) . The copolymer is referred to as "allyl ester copolymer" in the present specification.

R¹ in formula (1) represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms, which may be linear or branched or include a cyclic structure. Examples of linear aliphatic hydrocarbon group include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group and n- decyl group.

Examples of branched aliphatic hydrocarbon group include isopropyl group, isobutyl group, sec-butyl group, neo-pentyl group, isohexylgroup and isooctyl group.

Examples of aliphatic hydrocarbon group

containing a cyclic structure include cyclohexyl group, cyclohexylmethyl group and cyclohexylethyl group.

Preferred among them as R¹ are linear aliphatic hydrocarbon group having 1 to 5 carbon atoms from a cost- cutting point of view in the polymer production.

Particularly preferred in consideration for cost-cutting in the polymer production are methyl group, ethyl group and n-propyl group.

R² in formula (2) represents an aliphatic hydrocarbon group having 2 to 20 carbon atoms, which may be linear or branched or include a cyclic structure.

Examples of linear aliphatic hydrocarbon group include ethyl group, n-propyl group, n-butyl group, n- pentyl group, n-hexyl group, n-octyl group and n-decyl group, n-dodecyl group, n-tetradecyl group, n-hexadecyl group, n-octadecyl group and n-eicosyl group.

Examples of branched aliphatic hydrocarbon group include isopropyl group, isobutyl group, sec-butyl group, neo-pentyl group, isohexyl group, isooctyl group and isodecyl group.

Examples of aliphatic hydrocarbon group

containing a cyclic structure include cyclohexyl group, cyclohexylmethyl group, cyclohexylethyl group,

decahydronaphthalenyl group and cyclohexenyl group.

Preferred among them as R² are linear aliphatic hydrocarbon group having 2 to 10 carbon atoms and

alicyclic hydrocarbon group having 6 to 10 carbon atoms in consideration for enhancement in compatibility with various resins. Particularly preferred in consideration for enhancement in compatibility with various resins are ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group, n- dodecyl group and cyclohexyl group.

The copolymer of the present invention may comprise structures represented by formulae (1) and (2) only or may contain a third monomer unit as needed. The third monomer unit is the same one as described below in the section on allyl alcohol copolymer. Also, the allyl alcohol copolymer obtained with transesterification conversion less than 100% shall contain a monomer unit derived from a structure represented by formula (2) , which may be counted as a type of the third monomer unit. Two or more kinds of third monomer units may be introduced.

[Allyl alcohol copolymer]

The allyl alcohol copolymer of the present invention comprises structures represented by formula (3) and (2) as monomer units.

(In the formula, R² represents an aliphatic hydrocarbon group having 2 to 20 carbon atoms, which may be branched or include a cyclic structure) . If necessary, the

copolymer may contain a third monomer unit.

The monomer unit having a structure represented by formula (2) is the same one as those explained in the section on the allyl ester copolymer, and the compounds as an example and preferred example of R² are similar to those in the case of the allyl ester copolymer.

The allyl alcohol copolymer of the present invention may be a copolymer comprising structures

represented by formulae (3) and (2) only; or a structure obtained by copolymerizing a radically-polymerizable olefin compound may be introduced into the copolymer as a third unit as needed. Two or more kinds of such third monomer units may be introduced.

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

Preferred radically polymerizable olefin compounds among them are methyl acrylate, methyl methacrylate, vinyl acetate and styrene in the interest of productivity improvement in the production of the

copolymer.

In the allyl alcohol copolymer of the present invention, the bonding mode of the copolymer of the monomer unit represented by formula (3) and the monomer unit represented by formula (2) may be random, block or alternate, depending on polymerization conditions. In consideration for improvement in compatibility with various resins, random mode is preferred. It is true of a case where the copolymer contains a third monomer unit.

In the allyl alcohol copolymer of the present invention, the composition of each monomer unit can be controlled by changing blending ratios between the allyl ester corresponding to the monomer unit represented by formula (1), the olefin compound corresponding to the monomer unit represented by formula (2) and a radically polymerizable olefin compound; and polymerization

conditions at the time of producing allyl ester

copolymers .

In consideration for achieving a good balance between compatibility of the allyl alcohol copolymer with various resins and adhesiveness, it is preferred that the concentration of the monomer unit represented by formula

(1) be from 3 to 60 moll based on the total monomer units, more preferably 4 to 40 moll, most preferably 10 to 30 moll. If the concentration of the monomer unit

represented by formula (1) is less than 3 moll,

adhesiveness markedly decreases, and if it exceeds 60 mol%, compatibility with resins having low polarity decreases .

In a case where monomer units of a radically polymerizable olefin compound are contained in the allyl alcohol copolymer of the present invention, it is

preferred that the concentration of such monomer units be from 0.1 to 20.0 moll in consideration for improvement in compatibility with various resins, more preferably 0.5 to 15.0 moll, most preferably 2.0 to 10.0 moll. If the concentration of monomer units of a radically

polymerizable olefin compound is less than 0.1 moll, compatibility with resins having high polarity decreases and if it exceeds 20.0 moll, compatibility with resins having low polarity decreases.

It is preferred that the hydroxyl value of the allyl alcohol copolymer of the present invention be from 10 to 300 mgKOH/g in consideration for achieving a good balance between compatibility with various resins and adhesiveness, more preferably 50 to 250 mgKOH/g, most preferably 100 to 200 mgKOH/g. If the hydroxyl value of the copolymer is less than 10 mgKOH/g, adhesiveness decreases and if it exceeds 300 mgKOH/g, compatibility with resins having low polarity decreases. Here, the hydroxyl value is measured according to the method

described in JIS K0070.

There is no particular limitation on the number average molecular weight of the copolymer of the present invention. The molecular weight in terms of polystyrene (Mn) , which is measured by gel permeation chromatography (GPC), is preferably from 500 to 8000, more preferably 500 to 5000, most preferably 650 to 3000 in consideration for compatibility with various resins. If the number average molecular weight (Mn) in terms of polystyrene is less than 500, compatibility with solid resins decreases and if it exceeds 8000, compatibility with liquid resins decreases.

[Production Method]

Next, the methods for producing the allyl alcohol copolymer of the present invention are explained. The allyl alcohol copolymer of the present invention can be produced by either of the two methods, Method A and Method B, described below.

Method A:

An aliphatic 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 radically polymerizable olefin compound as a type of the third monomer unit, are

copolymerized in the presence of a radical polymerization initiator; and the thus-generated allyl ester copolymer (precursor A) is subjected to transesterification in the presence of alcohol and a catalyst.

Method B:

A copolymer of aliphatic acid allyl ester and radically- polymerizable aromatic monomer is hydrogenated; and the thus-generated allyl ester copolymer (precursor B) is subjected to transesterification in the presence of alcohol and a catalyst. Method A: A method of subjecting precursor A prepared by radical copolymerization between aliphatic acid allyl ester, an olefin compound corresponding to the monomer unit represented by formula (2) and a radically

polymerizable olefin compound to transesterification in the presence of alcohol and a catalyst.

There is no particular limitation on the olefin compound corresponding to the monomer unit represented by formula (2) used for producing precursor A in the method for producing copolymer of the present invention as long as the compound can be radically polymerizable. Examples of olefin compounds corresponding to the structures as explained in the above detailed description on the allyl ester copolymer include straight chain terminal olefins such as 1-butene, 1-pentene, 1-hexene, 1-heptene, 1- octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and 1-tricosens, terminal olefins having a branched terminal such as 3-methyl-l-butene, 4- methyl-1-pentene, 3-methyl-l-pentene, 4 , 4-dimethyl-l- pentene, 3-methyl-l-heptene, 3-methyl-l-nonene and 3- methyl-1-undecene, and terminal olefins having a cyclic structure such as cyclohexyl ethylene, 3-cyclohexyl-l- propene, 4-cyclohexyl-l-butene, decahydronaphthalenyl ethylene and 4-vinyl-l-cyclohexene . In case of using olefin compound having an unsaturated bond at 2-position, such as 2-decene, polymerization is difficult due to resonance stabilization of living radicals.

Among them, particularly preferred in consideration for enhancement in compatibility with various resins are 1-butene, 1-pentene, 1-hexene, 1- heptene, 1-octene, 1-decene, 1-dodecene and

cyclohexylethylene.

As for amounts of the aliphatic acid allyl ester and radically-polymerizable olefin compound

corresponding to the monomer unit represented by formula (2) used for producing the copolymer of the present invention, it is preferred that the amount of the

aliphatic acid allyl ester be from 0.05 to 2.0 mol based on 1 mol of the olefin compound corresponding to the monomer unit represented by formula (2), particularly preferably 0.10 to 1.0 mol. If the amount of the

aliphatic acid allyl ester is less than 0.05 mol, the hydroxyl value of the obtained precursor A after

undergoing transesterification becomes too low, which leads to decrease in compatibility with resins, and if it exceed 2.0 mol, the molecular weight of the precursor A tends to decrease.

It is preferable that the amount of the

radically-copolymerizable olefin compound as a third monomer used here is from 0.005 to 0.3 mol based on 1 mol of the olefin compound corresponding to the monomer unit represented by formula (2), particularly preferably 0.01 to 0.1 mol. If the amount of the radically-polymerizable olefin compound as a third monomer is less than 0.005 mol, the yield of the obtained precursor A decreases and if the amount exceeds 0.2 mol, solid matter having a high

molecular weight is generated in precursor A in some cases, which leads to white turbidity of the product.

Here, since monomers differ in reactivity from each other, generally, the blending ratio of the monomers does not correspond with the quantitative ratio of the monomer units in the obtained polymer.

This copolymerization reaction for producing precursor A may be conducted without a solvent or

conducted with a solvent which does not react with the substrates and which has a small chain transfer constant. Example of such solvents include hydrocarbon solvents such as toluene, benzene and t-butylbenzene; ketone solvents such as acetone; and halogen solvents such as

dichloromethane, chloroform and chlorobenzene . One of these solvents may be used independently or two or more of them may be used in combination.

This copolymerization reaction for producing precursor A may be conducted by using a radical

polymerization initiator. Any radical polymerization initiator may be used as long as it can generate radicals by heat, ultraviolet ray, electron beam, radiation or the like. Preferred are those having a half-life of 1 hour or more at the reaction temperature.

Examples of heat radical polymerization

initiator include azo compounds such as 2,2'- azobisisobutyronitrile, 2,2' -azobis (2,4- dimethylvaleronitrile ), 2, 2' -azobis (2- methylbutyronitrile) , dimethyl 2 , 2 ' -azobisisobutyrate, 4 , 4 ' -azobis ( 4-cyanopentanoic acid), and 2,2'- azobis ( 2 , 4 , 4-trimethylpentane) ;

ketone peroxides such as methylethyl ketone peroxide, methylisobutylketone peroxide and cyclohexanone peroxide; diacyl peroxides such as benzoyl peroxide, decanoyl peroxide and lauroyl peroxide;

dialkyl peroxides such as dicumyl peroxide, t-butylcumyl peroxide and di-t-butyl peroxide;

peroxyketals such as 1 , 1-di (t-hexylperoxy) -3, 3 , 5- trimethylcyclohexane, 1 , 1-bis (t-hexylperoxy) cyclohexane, 1, 1-di-t-butylperoxycyclohexane and 2,2-di(t- butylperoxy) butane;

alkylperoxy esters such as t-butylperoxypivalate, t- butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, di-t-butylperoxyhexahydroterephthalate, di-t- butylperoxyazelate, t-butylperoxy-3 , 5, 5- trimethylhexanoate, t-hexylperoxy-2-ethylhexanoate,

1,1,3, 3-tetramethylbutylperoxy-2-ethylhexanoate, t- butylperoxyacetate, t-butylperoxybenzoate, di-t- butylperoxytrimethyladipate, t- hexylperoxyisopropylmonocarbonate, t-butylperoxylaurate, and t-hexylperoxybenzoate;

peroxycarbonates such as diisopropylperoxydicarbonate, di- sec-butylperoxydicarbonate, and t-butylperoxyisopropyl carbonate; and hydrogen peroxides, but are not limited to these examples. One of these heat radical polymerization initiators may be used independently or two or more of them may be used in combination.

Examples of initiator for radical

polymerization with UV, electron beam or radiation include acetophenone derivatives such as acetophenone, 2,2- dimethoxy-2-phenylacetophenone, diethoxyacetophenone, 1- hydroxy-cyclohexylphenylketone, 2-methyl-l- [4- (methylthio) phenyl] -2-morpholinopropanone-l , 2-benzyl-2- dimethylamino-1- ( 4-morpholinophenyl) -butanone-1, and 2- hydroxy-2-methyl-l-phenylpropane-l-one;

benzophenone derivatives such as benzophenone, 4,4'- bis (dimethylamino) benzophenone, 4- trimethylsilylbenzophenone and 4-benzoyl-4 ' - methyldiphenylsulfide;

benzoin derivatives such as benzoin, benzoinethylether, benzoinpropylether, benzoinisobutylether and

benzoinisopropylether;

methylphenylglyoxylate, benzoindimethylketal , and 2,4,6- trimethylbenzoyldiphenylphosphineoxide, but are not limited to these examples. One of these initiators for radical polymerization with UV, electron beam or radiation may be used independently or two or more of them may be used in combination.

The use amount of the polymerization initiator varies depending on the reaction temperature and

composition ratio of monomers and cannot be flatly

defined. Generally, it is preferred that the amount be 0.1 to 15 parts by mass based on 100 parts by mass of the total amount of radically polymerizable monomers,

particularly preferably 1.0 to 10 parts by mass. If the amount of the radical polymerization initiator to be added is less than 0.1 parts by mass, polymerization reaction does not readily proceed and if it exceeds 15 parts by mass, the molecular weight of the obtained precursor A becomes too low and such an excessive amount of the initiator is not preferred in consideration for the cost.

The reaction temperature (polymerization temperature) may be appropriately determined according to the type of the polymerization initiator. The temperature may be gradually changed in conducting the reaction

(polymerization) . In case of UV polymerization, room temperature may be employed. In case of heat

polymerization, it is preferable that the reaction

temperature be determined appropriately according to decomposition temperature of the initiator and generally, a preferred range is from 50 to 180 ⁰C and a particularly preferred range is from 70 to 170 °C. If the temperature is lower than 50 ⁰C, the reaction speed becomes extremely low and if it exceeds 180 °C, not only decomposition of the radical initiator but also chain transfer proceeds too fast, which tends to reduce the molecular weight of the obtained precursor A.

After the reaction is completed, the allyl ester copolymer (precursor A) as reaction product is isolated by known operations and treatments (such as neutralization, solvent extraction, washing with water, liquid separation, distilling-off of solvent and

reprecipitation) .

Transesterification reaction can be performed by bringing precursor A into contact with an alcohol compound in the presence of a catalyst.

There is no particular limitation on the alcohol compound used for transesterification as long as the compound is reactive with ester and primary alcohol is preferable. In consideration for the affinity with

precursor A, alkyl alcohol having 1 to 10 carbon atoms is preferred, and ethanol and 1-propanol are particularly preferred.

Examples of a catalyst which can be used for transesterification reaction include inorganic acid, inorganic base and organic acid. Specific examples of inorganic acid include sulfuric acid, phosphoric acid, nitric acid and hydrochloric acid. Specific examples of inorganic base include lithium hydroxide, sodium

hydroxide, potassium hydroxide, magnesium hydroxide and calcium hydroxide. Specific examples of organic acid include acetic acid, benzenesulfonic acid and p- toluenesulfonic acid. Among these, inorganic base is preferable as a catalyst. Particularly preferred are lithium hydroxide, sodium hydroxide and potassium

hydroxide and the most preferred is sodium hydroxide.

Though the transesterification reaction can be carried out either in the presence or absence of a

solvent, it is preferable to carry out the reaction in the liquid phase using a solvent for the purpose of removing reaction heat. Any solvent can be used in the reaction as long as the solvent does not disturb the reaction.

Specific examples thereof include one selected from halogenated hydrocarbons such as dichloromethane,

chloroform and 1, 2-dichloroethane; aliphatic hydrocarbon solvents such as pentane, hexane, heptane and octane;

ether solvents such as diethylether, dipropylether, diisopropylether, dibutylether, ethyleneglycol

dimethylether, ethyleneglycol diethylether, ethyleneglycol dibutylether, diethyleneglycol dimethylether,

diethyleneglycol diethylether, diethyleneglycol

dibutylether, tetrahydrofuran and 1, 4-dioxane ; alcohol solvents such as methanol, ethanol, 1-propanol, 2- propanol, 1-butanol, 2-butanol, isobutyl alcohol and cyclohexanol ; and a mixture solvent containing two or more of these solvents.

Alcohol solvents are preferred among these due to the advantage that they double as an alcohol compound used for transesterification . More preferred are ethanol, 1-propanol and 1-butanol, and particularly, ethanol and 1- propanol in consideration for solubility of precursor A.

Within a range that does not decrease the reaction efficiency of the catalyst, any temperature may be employed in the transesterification reaction. A

general temperature range is 0 to 200 °C, preferably 50 to 150 °C, more preferably 70 to 120 °C. If the temperature is too high, it makes a reaction product susceptible to tinting and if the temperature is too low, practically useful reaction speed cannot be obtained.

As for the reaction mode of the

transesterification reaction, any reaction mode used in general transesterification reaction, such as a batch reaction and a flow reaction, may be employed according to the reaction process. From the viewpoint of improving the reaction rate, it is preferable to carry out the reaction while distilling off the ester compound generated by the reaction outside the reaction system. The amount of the catalyst used in the reaction varies depending on the reaction mode and there is no particular limitation on the amount. In a batch process, generally a range of the amount of the catalyst is 0.001 to 10 parts by mass based on 100 parts by mass of precursor A as the substrate, preferably 0.01 to 5 parts by mass, more preferably 0.05 to 1 part by mass. If the amount is too small,

practically sufficient reaction speed cannot be obtained and if the amount is too large, it may cause a problem of the product tinting and an increase in the catalyst cost.

After completion of the transesterification reaction, the catalyst residue can be removed by

subjecting the reaction liquid to the ion exchange resin treatment. As the ion exchange resin to be used, strong acid cation exchange resin is preferable. In

consideration for the catalyst residue removal efficiency, a porous strong acid cation exchange resin (sulfonic acid type) is particularly preferable. The ion exchange resin degraded through the catalyst residue treatment can be recycled and reused by a known operation and treatment method (e.g. the treatment using an aqueous solution of hydrochloric acid) .

After removing the residue of the catalyst, the allyl alcohol copolymer as the reaction product is

isolated by known procedures and treatment (such as filtration, eluting out with solvent, washing with water, separation, distilling-off of solvent and

reprecipitation) .

There is no particular limitation on the conversion of the transesterification reaction, which can be controlled by the alcohol amount to be used, reaction temperature and the like. The conversion requirement may differ depending on the usage of the reaction product. In the case of the usage as polyol, conversion is preferably 70% or more, more preferably, 90% or more. In consideration for the reactivity, conversion of 100% is most preferable. The allyl alcohol copolymer obtained with conversion of transesterification reaction less than 100% shall contain a monomer unit derived from a structure represented by formula (2). By controlling the

conversion, the monomer unit derived from a structure represented by formula (2) may function as a substitute of a third monomer unit. Method B: A method for subjecting hydrogenating copolymer of aliphatic acid allyl ester and radically-polymerizable aromatic monomer; and subjecting the thus-generated allyl ester copolymer (precursor B) to transesterification in the presence of alcohol and a catalyst

In Method B, first, a copolymer of an aliphatic acid allyl ester and a radically polymerizable aromatic monomer is obtained. After the aromatic ring of the copolymer is hydrogenated (hydrogenation) , the copolymer is subjected to transesterification . Such a copolymer of an aliphatic acid allyl ester and a radically

polymerizable aromatic monomer can be produced according to the method described in US Patent No. 5444141 and using aliphatic acid allyl ester (preferably allyl acetate) as a substitute of allyl alcohol in the method.

Examples of radically polymerizable aromatic monomer include styrene and vinyl toluene.

The hydrogenation reaction can be carried out by allowing an aliphatic acid allyl ester, a radically polymerizable aromatic monomer and hydrogen gas to contact with each other in the presence of a catalyst.

Examples of catalyst used in the hydrogenation reaction include those containing as a catalyst component at least one metal element selected from Groups 6 to 12 in the periodic table. Specific examples thereof include catalysts comprising a combination selected from sponge nickel, Ni-diatomite, Ni-alumina, Ni-silica, Ni-silica- alumina, Ni-zeolite, Ni-titania, Ni-magnesia, Ni-chromia, Ni-Cu, Ni-Cu-Co, sponge Co, Co-diatomite, 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 alumina and Pd- zeolite. Preferred among them are catalysts containing Rh, Ru or Pd as the catalyst component and particularly preferred are catalysts of Rh-carbon, Ru-carbon, Ru- alumina, Pd-carbon, and Pd-alumina.

There is no particular limitation on the method of preparing the catalyst and generally used method may be employed. Examples of the method include a method in which a carrier impregnated with a solution of a salt of a metal to serve as the catalyst is subjected to reduction treatment by using a reducing agent;

a method in which a carrier is impregnated with a solution of a salt of a metal to serve as the catalyst, allowed to contact with an alkali solution or the like to thereby precipitate metal hydroxide or oxide on the carrier, followed by calcination; a method in which a carrier is impregnated with a solution of a salt of a metal to serve as the catalyst, allowed to contact with an alkali

solution or the like to thereby precipitate metal

hydroxide or oxide on the carrier, followed by

calcination, and then the resultant is subjected to reduction treatment by using a reducing agent; and a method in which an alloy of a metal^' and Al is prepared and the alloy is subjected to alkali treatment to thereby elute out Al. The present invention is not limited by these examples.

It is preferred that the hydrogenation reaction be conducted in liquid phase with a solvent for the purpose of removing reaction heat and reducing diffusion efficiency of hydrogen due to increase in viscosity. Any solvent can be used in the reaction as long as the solvent does not disturb the reaction. Specific examples thereof include one selected from halogenated hydrocarbons such as dichloromethane, chloroform, and 1 , 2-dichloroethane;

aliphatic hydrocarbon solvents such as pentane, hexane, heptane and octane; ether solvents such as

diethylether, dipropylether, diisopropylether,

dibutylether, ethyleneglycol dimethylether, ethyleneglycol diethylether, ethyleneglycol dibutylether,

diethyleneglycol dimethylether, diethyleneglycol

diethylether, diethyleneglycol dibutylether,

tetrahydrofuran, and 1,4-dioxane; ether alcohol solvents such as 2-methoxyethanol , 2-ethoxyethanol, 2- propoxyethanol , 2-isopropoxyethanol, 2-butoxy ethanol, diethyleneglycol monomethylether , diethyleneglycol

monoethylether, propyleneglycol monomethylether and propyleneglycol monoethylether; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2- butanol, isobutyl alcohol and cyclohexanol ; water; and a mixture solvent containing two or more of these solvents.

Preferred among them in consideration for solubility of hydrogen or the copolymer of an aliphatic acid allyl ester and a radically polymerizable aromatic monomer are ether solvents and halogenated hydrocarbon solvents, and particularly preferred are tetrahydrofuran, 1,4-dioxane and chloroform.

As for hydrogen pressure in the hydrogenation reaction, the reaction may be carried out under normal pressure or increased pressure. In order for the reaction to proceed efficiently, increased pressure is preferred. Generally the reaction is carried out under a gauge pressure of 0 to 30 MPaG, preferably 1 to 20 MPaG, more preferably 2 to 15 MPaG.

Within a range that does not decrease the reaction efficiency of the catalyst, any temperature may be employed in the hydrogenation reaction. A general temperature range is 0 to 300 °C, preferably 50 to 250 °C, more preferably 70 to 220 °C. If the temperature is too high, side-reactions readily occur and if the temperature is too low, practically useful reaction speed cannot be obtained.

As for the reaction mode of the hydrogenation reaction, any reaction mode generally used in general liquid-phase hydrogenolysis reaction or liquid-phase hydrogenation reaction, such as suspension bed batch reaction, fixed bed flow reaction and fluid bed flow reaction, may be employed according to the reaction process. The amount of the catalyst used in the reaction varies depending on the reaction mode and there is no particular limitation on the amount. In a batch process using a suspension bed, generally a range of the amount of the catalyst is 0.01 to 100 parts by mass based on 100 parts by mass of the copolymer of the aliphatic acid allyl ester and the radically polymerizable aromatic monomer as the substrate, preferably 0.1 to 50 parts by mass, more preferably 0.5 to 20 parts by mass.

If the amount is too small, practically

sufficient reaction speed cannot be obtained and if the amount is too large, side-reactions increase and costs for the catalyst also increases.

After completion of the hydrogenation reaction, the hydrogenated product of allyl ester copolymer as the reaction product is isolated by known procedures and treatment (such as filtration, eluting out with solvent, washing with water, separation, distilling-off of solvent and reprecipitation) .

Transesterification reaction can be performed by bringing- the hydrogenated product of allyl ester copolymer into contact with an alcohol compound in the presence of a catalyst.

Transesterification reaction can be performed under the similar conditions as those described in the section on Method A except that a hydrogenated product of allyl ester copolymer is used in place of precursor A.

EXAMPLES

Hereinafter, the present invention is described in greater detail by referring to Examples and Comparative Examples. The present invention is by no means limited thereto .

Properties of products synthesized in Examples and Comparative Examples were measured as follows.

1. FT-IR

Apparatus used: Spectrum GX

(manufactured by PerkinElmer, Inc.)

Measurement method: measured by liquid membrane technique using a KBr plate

2. ¹H-NMR, ¹³C-NMR

Apparatus used: JEOL EX-400

(400MHz, manufactured by JEOL, LTD.)

Measurement method: measured by dissolving samples in deuterated chloroform or deuterated methanol and using tetramethylsilane as internal standard.

3. Gel permeation chromatography (GPC)

Apparatus used:

Column: Shodex GPC K-G+K-802+K-802.5+K-801 (manufactured by SHOWA DENKO K.K.),

Detector: Shodex SE-61 (manufactured by SHOWA DENKO

K. K.) ,

Measurement conditions Solvent: Chloroform or tetrahydrofuran,

Measurement temperature: 40 ⁰C,

Flow rate: 1.0 ml/minute,

Sample concentration: 1.0 mg/ml,

Injection amount: 1.0 μl,

Calibration curve: Universal Calibration curve, Analysis program: SIC 480II (product of System Instruments, Inc.) 4. Hydroxyl Value

The value was measured according to the method described in JIS K0070.

5. Mol% of the allyl alcohol monomer unit

The value was determined from the number average molecular weight and hydroxyl value.

Example 1: Production of copolymer of allyl alcohol and 1- decene

In a 300 ml-volume stainless-steel made

autoclave (manufactured by Taiatsu Techno Corporation) , allyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd., 12.00 g, 0.120 mol), 1-decene (manufactured by Wako Pure Chemical Industries Co., Ltd., 84.16 g, 0.600 mol), and di-t-butylperoxide (Kishida Chemical Co., Ltd., 4.81 g, 0.0329 mol) were placed. After a flange was attached, the inside of the reaction system was

substituted with nitrogen three times. Next, the

temperature was increased while stirring the content at 400 rpm, and reaction was carried out at 145 ⁰C for six hours. After the content was cooled to room temperature, depressurization was carried out. The

reaction container was opened to take out the content.

From the content, the allyl acetate and 1-decene that had remained unreacted and the remaining initiator were removed at 100 °C under reduced pressure to thereby obtain 42.11 g of an oily substance having high viscosity.

20.0Og of the oily substance, 250 ml of ethanol and sodium hydroxide (manufactured by Wako Pure Chemical Industries Co., Ltd., 0.04 g, 0.001 mol) were placed in a 500 ml-volume two-neck flask. After substituting the inside of the reaction system with nitrogen, reaction was carried out while stirring the content at 80 °C for four hours. After the content was cooled to room temperature, the content was passed through a column packed with 30 g of ion exchange resin (manufactured by Mitsubishi Chemical Corporation, DAIAION PK208H) to remove the sodium residue. Next, ethanol was removed under reduced pressure and 17.87 g of a pale yellow oily substance was obtained. The recovery rate of the raw materials was 41.7%.

The ¹H-NMR, ¹³C-NMR and IR spectra of the obtained oily substance were measured and it was confirmed that the substance was the target copolymer. Spectrum peaks derived from allyl acetate almost disappeared. The number average molecular weight of the copolymer (Mn) was 1640, the hydroxyl value was 88 mgKOH/g, and the

concentration of the allyl alcohol monomer unit was 19.5 mol% . Also, the evaluation results on solubility in hexane, heptane, chloroform, methanol, ethanol and acetone are shown in Table 2. Example 2: Production of copolymer of allyl alcohol and 1- decene

Reaction and a subsequent treatment were carried out in the same way as in Example 1 except that allyl acetate (manufactured by Tokyo Chemical Industry

Co., Ltd., 18.02 g, 0.180 mol), 1-decene (manufactured by Wako Pure Chemical Industries Co., Ltd., 84.16 g, 0.600 mol), and di-t-butylperoxide (Kishida Chemical Co., Ltd., 5.10 g, 0.0349 mol) were placed in the autoclave; and 18.16 g of pale yellow oily substance was obtained. The recovery rate of the raw materials was 44.0%.

The ¹H-NMR, ¹³C-NMR and IR spectra of the obtained oily substance were measured and it was confirmed that the substance was the target copolymer. Spectrum peaks derived from allyl acetate almost disappeared. The number average molecular weight of the copolymer (Mn) was 1630, the hydroxyl value was 129 mgKOH/g, and the

concentration of the allyl alcohol monomer unit was 27.5 mol%. Also, the evaluation results on solubility in various solvents are shown in Table 2.

Example 3: Production of copolymer of allyl alcohol and 1- decene

In a 1 1-volume glass made autoclave (manufactured by Taiatsu Techno Corporation) , allyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd., 100.10 g, 1.000 mol), 1-decene (manufactured by Wako Pure Chemical Industries Co., Ltd., 280.60 g, 2.000 mol), and di-t-butylperoxide (Kishida Chemical Co., Ltd., 19.00 g, 0.1299 mol) were placed. After a flange was attached, the inside of the reaction system was substituted with nitrogen three times. Next, the temperature was increased while stirring the content at 400 rpm, and reaction was carried out at 145 °C for six hours.

After the content was cooled to room temperature, depressurization was carried out. The

reaction container was opened to take out the content.

From the content, the allyl acetate and 1-decene that had remained unreacted and the remaining initiator were removed at 100 °C under reduced pressure to thereby obtain 180.50 g of an oily substance having high viscosity.

The ¹H-NMR, ¹³C-NMR and IR spectra of the obtained oily substance were measured and it was confirmed that the substance was the target copolymer. Spectrum peaks derived from allyl acetate almost disappeared. The measurement results of the ¹H-NMR and IR spectra are shown in Fig. 1 and Fig. 2.

50.0Og of the oily substance, 600 ml of ethanol and sodium hydroxide (manufactured by Wako Pure Chemical Industries Co., Ltd., 0.10 g, 0.0025 mol) were placed in a 1 1-volume two-neck flask. After substituting the inside of the reaction system with nitrogen, reaction was carried out while stirring the content at 80 ⁰C for five hours. After the content was cooled to room temperature, the content was passed through a column packed with 100 g of ion exchange resin (manufactured by Mitsubishi Chemical Corporation, DAIAION PK208H) to remove the sodium residue. Next, ethanol was removed under reduced pressure and 39.99 g of a pale yellow oily substance was obtained. The recovery rate of the raw materials was 45.2%. The ¹H-NMR, ¹³C-NMR and IR spectra of the obtained oily substance were measured and it was confirmed that the substance was the target copolymer. The

measurement results of the ¹H-NMR and IR spectra are shown in Fig. 3 and Fig. 4. The number average molecular weight of the copolymer (Mn) was 1880, the hydroxyl value was 207 mgKOH/g, and the concentration of the allyl alcohol monomer unit was 39.7 moll. Also, the evaluation results on solubility in various solvents are shown in Table 2.

Example 4: Production of copolymer of allyl alcohol and 1- decene

Reaction and a subsequent treatment were carried out in the same way as in Example 3 except that allyl acetate (manufactured by Tokyo Chemical Industry

Co., Ltd., 140.14 g, 1.400 mol), 1-decene (manufactured by Wako Pure Chemical Industries Co., Ltd., 280.60 g, 2.000 mol), and di-t-butylperoxide (Kishida Chemical Co., Ltd., 21.00 g, 0.144 mol) were placed in the autoclave; and 41.39 g of pale yellow oily substance was obtained. The recovery rate of the raw materials was 52.3%.

The ¹H-NMR, ¹³C-NMR and IR spectra of the obtained oily substance were measured and it was confirmed that the substance was the target copolymer. Spectrum peaks derived from allyl acetate almost disappeared. The number average molecular weight of the copolymer (Mn) was 1770, the hydroxyl value was 256 mgKOH/g, and the

concentration of the allyl alcohol monomer unit was 46.6 moll. Also, the evaluation results on solubility in various solvents are shown in Table 2. Example 5: Production of copolymer of allyl alcohol and 1- decene

Co., Ltd., 200.20 g, 2.000 mol), 1-decene (manufactured by Wako Pure Chemical Industries Co., Ltd., 280.60 g, 2.000 mol), and di-t-butylperoxide (Kishida Chemical Co., Ltd., 24.00 g, 0.164 mol) were placed in the autoclave; and 35.50 g of pale yellow oily substance was obtained. The recovery rate of the raw materials was 53.4%.

The ¹H-NMR, ¹³C-NMR and IR spectra of the obtained oily substance were measured and it was confirmed that the substance was the target copolymer. Spectrum peaks derived from allyl acetate almost disappeared. The number average molecular weight of the copolymer (Mn) was 1650, the hydroxyl value was 350 mgKOH/g, and the

concentration of the allyl alcohol monomer unit was 57.8 mol% . Also, the evaluation results on solubility in various solvents are shown in Table 2.

Example 6: Production of copolymer of allyl alcohol and vinylcyclohexane

In a 300 ml-volume stainless-steel made

autoclave (manufactured by Taiatsu Techno Corporation) , allyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd., 50.06 g, 0.500 mol), styrene (manufactured by Wako Pure Chemical Industries Co., Ltd., 52.08 g, 0.500 mol), and di-t-butylperoxide (Kishida Chemical Co., Ltd., 5.11 g, 0.0349 mol) were placed. After a flange was attached, the inside of the reaction system was substituted with nitrogen three times. Next, the

temperature was increased while stirring the content at 400 rpm, and reaction was carried out at 155 °C for five hours .

After the content was cooled to room temperature, depressurization was carried out. The reaction container was opened to take out the content.

From the content, the allyl acetate and styrene that had remained unreacted and the remaining initiator were removed at 100 °C under reduced pressure to thereby obtain 75.08 g of an oily substance having high viscosity.

6.Og of the obtained oily substance, 1,4- dioxane (manufactured by Wako Pure Chemical Industries Co., Ltd., 55.0 ml) and 5% Rh-carbon in powder form

(manufactured by Wako Pure Chemical Industries Co., Ltd., 0.7 g) were placed in a 120 ml-volume stainless-steel made autoclave (manufactured by Taiatsu Techno Corporation) . After a flange was attached, the inside of the reaction system was substituted with nitrogen three times and then with hydrogen gas. Finally, a hydrogen pressure of 4.5 MPaG (gauge pressure) was applied thereto. Next, the temperature was increased while stirring the content at 400 rpm, and reaction was carried out at 200 ⁰C for seven hours. During the reaction, hydrogen was introduced so that the reaction pressure was -constant.

After the content was cooled to room temperature, depressurization and substitution with nitrogen were carried out. The reaction container was opened to take out the content and the content was subjected to filtration to thereby remove catalyst. From the obtained filtrate, 1,4-dioxane was distilled under reduced pressure, to thereby obtain 6.0 g of an oily substance having high viscosity.

5.0O g of the oily substance, 60 ml of ethanol and sodium hydroxide (manufactured by Wako Pure Chemical Industries Co., Ltd., 0.01 g, 0.00025 mol) were placed in a 100 ml-volume two-neck flask. After substituting the inside of the reaction system with nitrogen, reaction was carried out while stirring the content at 80 °C for four hours. After the content was cooled to room temperature, the content was passed through a column packed with 10 g of ion exchange resin (manufactured by Mitsubishi Chemical Corporation, DAIAION PK208H) to remove the sodium residue. Next, ethanol was removed under reduced pressure and 4.36 g of a pale yellow oily substance was obtained. The recovery rate of the raw materials was 65.5%.

The ¹H-NMR, ¹³C-NMR and IR spectra of the obtained oily substance were measured and it was confirmed that the substance was the target copolymer. Spectrum peaks derived from allyl acetate almost disappeared. The number average molecular weight of the copolymer (Mn) was 2560, the hydroxyl value was 82 mgKOH/g, and the

concentration of the allyl alcohol monomer unit was 15 mol%. Also, the evaluation results on solubility in various solvents are shown in Table 2.

Example 7: Production of copolymer of allyl alcohol and 1- octene

In a 120 ml-volume stainless-steel made autoclave (manufactured by Taiatsu Techno Corporation) , allyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd., 20.00 g, 0.200 mol), 1-octene (manufactured by Wako Pure Chemical Industries Co., Ltd., 44.83 g, 0.400 mol), and di-t-butylperoxide (Kishida Chemical Co., Ltd., 3.24 g, 0.022 mol) were placed. After a flange was attached, the inside of the reaction system was

substituted with nitrogen three times. Next, the

From the content, the allyl acetate and octene that had remained unreacted and the remaining initiator were removed at 100 °C under reduced pressure to thereby obtain 28.92 g of an oily substance having high viscosity.

10.00 g of the oily substance, 120 ml of ethanol and sodium hydroxide (manufactured by Wako Pure Chemical Industries Co., Ltd., 0.02 g, 0.0005 mol) were placed in a 300 ml-volume two-neck flask. After

substituting the inside of the reaction system with nitrogen, reaction was carried out while stirring the content at 80 °C for four hours. After the content was cooled to room temperature, the content was passed through a column packed with 15 g of ion exchange resin

(manufactured by Mitsubishi Chemical Corporation, DAIAIMON PK208H) to remove the sodium residue. Next, ethanol was removed under reduced pressure and 8.49 g of a pale yellow oily substance was obtained. The recovery rate of the raw materials was 42.5%.

The ¹H-NMR, ¹³C-NMR and IR spectra of the obtained oily substance were measured and it was confirmed that the substance was the target copolymer. Spectrum peaks derived from allyl acetate almost disappeared. The number average molecular weight of the copolymer (Mn) was 1180, the hydroxyl value was 248 mgKOH/g, and the

concentration of the allyl alcohol monomer unit was 46.7 mol%. Also, the evaluation results on solubility in various solvents are shown in Table 2.

Example 8: Production of copolymer of allyl alcohol and 1- hexene

In a 120 ml-volume stainless-steel made

autoclave (manufactured by Taiatsu Techno Corporation) , allyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd., 14.00 g, 0.140 mol), 1-hexene (manufactured by Wako Pure Chemical Industries Co., Ltd., 39.23 g, 0.466 mol), and di-t-butylperoxide (Kishida Chemical Co., Ltd., 2.66 g, 0.018 mol) were placed. After a flange was attached, the inside of the reaction system was

substituted with nitrogen three times. Next, the

From the content, the allyl acetate and 1-hexene that had remained unreacted and the remaining initiator were removed at 100 ⁰C under reduced pressure to thereby obtain 16.56 g of an oily substance having high viscosity.

substituting the inside of the reaction system with nitrogen, reaction was carried out while stirring the content at 80 ⁰C for four hours. After the content was cooled to room temperature, the content was passed through a column packed with 15 g of ion exchange resin

(manufactured by Mitsubishi Chemical Corporation, DAIAION PK208H) to remove the sodium residue. Next, ethanol was removed under reduced pressure and 7.69 g of a pale yellow oily substance was obtained. The recovery rate of the raw materials was 29.6%.

The ¹H-NMR, ¹³C-NMR and IR spectra of the obtained oily substance were measured and it was confirmed that the substance was the target copolymer. Spectrum peaks derived from allyl acetate almost disappeared. The number average molecular weight of the copolymer (Mn) was 1120, the hydroxyl value was 222 mgKOH/g, and the

concentration of the allyl alcohol monomer unit was 37.2 mol% . Also, the evaluation results on solubility in various solvents are shown in Table 2.

Example 9: Production of copolymer of allyl alcohol and 1- tetradecene

In a 300 ml-volume stainless-steel made autoclave (manufactured by Taiatsu Techno Corporation), allyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd., 35.00 g, 0.350 mol), 1-tetradecene

(manufactured by Wako Pure Chemical Industries Co., Ltd., 114.43 g, 0.583 mol), and di-t-butylperoxide (Kishida

Chemical Co., Ltd., 7.47 g, 0.051 mol) were placed. After a flange was attached, the inside of the reaction system was substituted with nitrogen three times. Next, the temperature was increased while stirring the content at 400 rpm, and reaction was carried out at 145 °C for six hours .

reaction container was opened to take out the content.

From the content, the allyl acetate and 1-tetradecene that had remained unreacted and the remaining initiator were removed at 160 ⁰C under reduced pressure to thereby obtain 94.27 g of an oily substance having high viscosity.

93.00 g of the oily substance, 280 ml of ethanol and sodium hydroxide (manufactured by Wako Pure Chemical Industries Co., Ltd., 0.19 g, 0.0048 mol) were placed in a 300 ml-volume two-neck flask. After

substituting the inside of the reaction system with nitrogen, reaction was carried out while stirring the content at 80 °C for four hours. After the content was cooled to room temperature, the content was passed through a column packed with 100 g of ion exchange resin

(manufactured by Mitsubishi Chemical Corporation, DAIAION PK208H) to remove the sodium residue. Next, ethanol was removed under reduced pressure and 83.11 g of a pale yellow oily substance was obtained. The recovery rate of the raw materials was 60.1%.

The ¹H-NMR, ¹³C-NMR and IR spectra of the obtained oily substance were measured and it was confirmed that the substance was the target copolymer. Spectrum peaks derived from allyl acetate almost disappeared. The number average molecular weight of the copolymer (Mn) was 2350, the hydroxyl value was 150 mgKOH/g, and the

concentration of the allyl alcohol monomer unit was 38.4 moll. Also, the evaluation results on solubility in various solvents are shown in Table 2.

Example 10: Production of copolymer of allyl alcohol, 1- decene and 2-norbornene

In a 120 ml-volume stainless-steel made

autoclave (manufactured by Taiatsu Techno Corporation) , allyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd., 19.49 g, 0.195 mol), 1-decene (manufactured by Wako Pure Chemical Industries Co., Ltd., 30.00 g, 0.214 mol), 2-norbornene (manufactured by Tokyo Chemical

Industry Co., Ltd., 6.04 g, 0.064 mol) and di-t- butylperoxide (manufactured by Kishida Chemical Co., Ltd., 2.78 g, 0.019 mol) were placed. After a flange was

attached, the inside of the reaction system was

substituted with nitrogen three times. Next, the

temperature was increased while stirring the content at 400 rpm, and reaction was carried out at 145 ⁰C for five hours .

From the content, the allyl acetate, 1-decene and 2- norbornene that had remained unreacted and the remaining initiator were removed at 100 °C under reduced pressure to thereby obtain 30.34 g of an oily substance having high viscosity.

5.00 g of the oily substance, 30 ml of ethanol and sodium hydroxide (manufactured by Wako Pure Chemical Industries Co., Ltd., 0.02 g, 0.0005 mol) were placed in a 100 ml-volume two-neck flask. After substituting the inside of the reaction system with nitrogen, reaction was carried out while stirring the content at 80 ⁰C for four hours. After the content was cooled to room temperature, the content was passed through a column packed with 10 g of ion exchange resin (manufactured by Mitsubishi Chemical Corporation, DAIAION PK208H) to remove the sodium residue. Next, ethanol was removed under reduced pressure and 4.00 g of a pale yellow oily substance was obtained. The recovery rate of the raw materials was 52.0%.

The ¹H-NMR, ¹³C-NMR and IR spectra of the obtained oily substance were measured and it was confirmed that the substance was the target copolymer. Spectrum peaks derived from allyl acetate almost disappeared. The number average molecular weight of the copolymer (Mn) was 1650 and the hydroxyl value was 220 mgKOH/g. Also, the evaluation results on solubility in various solvents are shown in Table 2.

Example 11: Production of a copolymer of allyl alcohol and 1-decene 50.00 g of the copolymer of allyl acetate and 1-decene prepared in Example 3, 600 ml of ethanol and sulfuric acid (manufactured by Wako Pure Chemical

Industries Co., Ltd., 0.20 g) were placed in a 1 1-volume two-neck flask. After substituting the inside of the reaction system with nitrogen, reaction was carried out while stirring the content at 80 °C for five hours. After the content was cooled to room temperature, the sulfuric acid residue was neutralized by adding sodium hydroxide. After the generated salt was filtrated, ethanol was removed under reduced pressure to thereby obtain 44.75 g of a pale yellow oily substance.

From the measurement results of the ¹H-NMR, ¹³C- NMR and IR spectra of the obtained oily substance,

conversion of the transesterification reaction was 52% and an ester structure remained in the reaction product. The number average molecular weight of the copolymer (Mn) was 2050, the hydroxyl value was 95 mgKOH/g, and the

concentration of the allyl alcohol monomer unit was 20.0 moll. Also, the evaluation results on solubility in various solvents are shown in Table 2.

Example 12: Production of a copolymer of allyl alcohol and 1-decene (reduction in the ethanol amount in

transesterification reaction)

In a 1 1-volume glass made autoclave

(manufactured by Taiatsu Techno Corporation) , allyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd., 16.00 g, 0.360 mol), 1-decene (manufactured by Wako Pure Chemical Industries Co., Ltd., 360.00 g, 2.567 mol), and di-t-butylperoxide (Kishida Chemical Co., Ltd., 19.80 g, 0.1354 mol) were placed. After a flange was attached, the inside of the reaction system was substituted with nitrogen three times. Next, the temperature was increased while stirring the content at 600 rpm, and reaction was carried out at 155 °C for five hours.

reaction container was opened to take out the content.

From the content, the allyl acetate and 1-decene that had remained unreacted and the remaining initiator were removed at 160 °C under reduced pressure to thereby obtain 174.52 g of an oily substance having high viscosity.

150.0Og of the oily substance, 450 ml of ethanol and sodium hydroxide (manufactured by Wako Pure Chemical Industries Co., Ltd., 0.30 g, 7.50 mmol) were placed in a 1 1-volume three-neck flask. After

substituting the inside of the reaction system with nitrogen, reaction was carried out while stir-ring the content at an oil bath temperature of 85 ⁰C for five hours. After the content was cooled to room temperature, the content was passed through a column packed with 300 g of ion exchange resin (manufactured by Mitsubishi Chemical Corporation, DAIAION PK216LH) to remove the sodium

residue. Next, ethanol was removed under reduced pressure and 137.22 g of a pale yellow oily substance was obtained. The recovery rate of the raw materials was 44.1%.

The ¹H-NMR, ¹³C-NMR and IR spectra of the obtained oily substance were measured and it was confirmed that the substance was the target copolymer. Spectrum peaks derived from allyl acetate almost disappeared. The number average molecular weight of the copolymer (Mn) was 1720, the hydroxyl value was 74 mgKOH/g, and the

concentration of the allyl alcohol monomer unit was 16.7 mol%. Also, the evaluation results on solubility in various solvents are shown in Table 2.

Example 13: Production of a copolymer of allyl alcohol and 1-decene (reduction in the ethanol amount in

transesterification reaction and distillation of ester generated in the reaction)

175.47 g of an oily substance having high viscosity was obtained by the same operation in Example 12.

substituting the inside of the reaction system with nitrogen, reaction was carried out while stirring the content at an oil bath temperature of 88°C for two hours. During the operation, ethyl acetate generated by the reaction was distilled off outside the reaction system. After the content was cooled to room temperature, the content was passed through a column packed with 300 g of ion exchange resin (manufactured by Mitsubishi Chemical Corporation, DAIAION PK216LH) to remove the sodium

residue. Next, ethanol was removed under reduced pressure and 138.65 g of a pale yellow oily substance was obtained. The recovery rate of the raw materials was 44.3%. The ¹H-NMR, ¹³C-NMR and IR spectra of the obtained oily substance were measured and it was confirmed that the substance was the target copolymer. Spectrum peaks derived from allyl acetate almost disappeared. The number average molecular weight of the copolymer (Mn) was 1760, the hydroxyl value was 72 mgKOH/g, and the

concentration of the allyl alcohol monomer unit was 16.3 mol%. Also, the evaluation results on solubility in various solvents are shown in Table 2.

Comparative Example 1: Production of copolymer of allyl alcohol and 1-decene

In a 120 ml-volume stainless-steel made

autoclave (manufactured by Taiatsu Techno Corporation) , allyl alcohol (manufactured by SHOWA DENKO K. K., 8.00 g, 0.138 mol), 1-decene (manufactured by Wako Pure Chemical Industries Co., Ltd., 38.64 g, 0.275 mol), and di-t- butylperoxide (Kishida Chemical Co., Ltd., 2.33 g, 0.0159 mol) were placed. After a flange was attached, the inside of the reaction system was substituted with nitrogen three times. Next, the temperature was increased while stirring the content at 400 rpm, and reaction was carried out at 140 °C for five hours.

From the content, the allyl acetate and 1-decene that had remained unreacted and the remaining initiator were removed at 100 °C under reduced pressure to thereby obtain 9.08 g of an oily substance having high viscosity. The recovery rate of the raw materials was 18.5%.

The ¹H-NMR, ¹³C-NMR and IR spectra of the obtained oily substance were measured and it was confirmed that the substance was the target copolymer. The number average molecular weight of the copolymer (Mn) was as low as 830, the hydroxyl value was 217 mgKOH/g, and the concentration of the allyl alcohol monomer unit was 41.2 moll. Also, the evaluation results on solubility in various solvents are shown in Table 2.

Comparative Example 2: Production of a copolymer of allyl alcohol and 1-decene

50.00 g of the copolymer of allyl acetate and 1-decene prepared in Example 3, 600 ml of pure water and sodium hydroxide (manufactured by Wako Pure Chemical

Industries Co., Ltd., 0.10 g, 0.0025 mol) were placed in a 1 1-volume two-neck flask. Reaction was carried out while stirring the content at 80 °C for five hours. After the content was cooled to room temperature and allowed to stand, the content caused two-phase separation. After separating the aqueous phase using a separating funnel, another 500 ml of pure water was added to thereby wash an organic phase. The operation was repeated three times till the organic phase was neutralized. Subsequently, the content was left at 100 °C under reduced pressure for two hours to thereby obtain 49.15 g of a pale yellow oily substance .

From the measurement results of the ¹H-NMR, ¹³C-NMR and IR spectra, the obtained oily substance was found to be a copolymer of allyl acetate and 1-decene, and hydrolysis reaction had not proceeded at all. The

measurement results of the ¹H-NMR and IR spectra are shown in Fig. 5 and Fig. 6, respectively.

Table 1

en

O

* Note: Though the presence of each monomer unit was confirmed by ¹H-NMR spectrum, it was unquantifiable due to the overlap of the peaks.

Table 2

O: Soluble x : Not soluble

INDUSTRIAL APPLICABILITY

The allyl alcohol copolymer obtained by the method of the present invention has excellent

compatibility with various resins and excellent

adhesiveness thanks to its having a polar group and also, the copolymer has excellent electric insulation property, low water absorption, excellent thermal stability and excellent surface-active effects thanks to its having a hydrophobic group. Therefore, the copolymer is useful, for example, when used in resin improver, coating component, ink component, adhesive component, primer component, high-performance wax, compatibilizer, surfactant, urethane material and polyester material .

Claims

1. 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.

2. The method for producing an allyl alcohol copolymer as claimed in claim 1, wherein the alcohol used in transesterification reaction is alkyl alcohol having 1 to 10 carbon atoms.

3. The method for producing an allyl alcohol copolymer as claimed in claim 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 as claimed in claim 1, wherein the catalyst used in transesterification reaction is sodium hydroxide, lithium hydroxide or potassium hydroxide.

5. The method for producing an allyl alcohol copolymer as claimed in claim 4, wherein the catalyst used in transesterification reaction is sodium hydroxide.

6. The method for producing an allyl alcohol copolymer as claimed in claim 1, wherein the aliphatic hydrocarbon group having 1 to 10 carbon atoms represented by R¹ is a linear aliphatic hydrocarbon group having 1 to 5 carbon atoms .

7. The method for producing an allyl alcohol copolymer as claimed in claim 6, wherein the linear aliphatic hydrocarbon group having 1 to 5 carbon atoms is methyl group, ethyl group or n-propyl group.

8. The method for producing an allyl alcohol copolymer as claimed in claim 7, wherein the linear aliphatic hydrocarbon group having 1 to 5 carbon atoms is methyl group.

9. The method for producing an allyl alcohol copolymer as claimed in claim 1, wherein R² in formula (2) is a linear aliphatic hydrocarbon group having 2 to 10 carbon atoms or an alicyclic hydrocarbon group having 6 to 10.

10. The method for producing an allyl alcohol copolymer as claimed in claim 9, wherein R² in formula (2) is ethyl group, n-propyl group, n-butyl group, n- pentyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group or cyclohexyl group.

11. The method for producing allyl alcohol

copolymer according to claim 1, wherein the copolymer comprises as monomer units the structures represented by formulae (1) and (2) only.

12. The method for producing allyl alcohol

copolymer according to claim 1, wherein the copolymer comprises as a third monomer unit the structure obtained by copolymerizing radically copolymerizable olefin compounds .

13. The method for producing 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 allyl alcohol

copolymer according to claim 1, wherein the copolymer comprises 3 to 60 mol% of the monomer unit represented by formula (1) to the total monomer units.

15. The allyl alcohol copolymer according to claim 12, comprising 0.1 to 20.0 moll of the unit of radically polymerizable olefin compound to the total monomer units.