JP3009201B2 - Polymer containing polyvinyl alcohol-based macromonomer unit - Google Patents

Description

The present invention relates to a polymer containing a polyvinyl alcohol-based macromonomer unit.

The graft polymer synthesized by the macromonomer method of the present invention has a highly controlled composition, structure, molecular weight, and the like. It is highly useful in various application fields.

B. Prior Art There have been many reports on a graft polymer having polyvinyl alcohol as a branch and a branched polyvinyl alcohol since ancient times, and various interesting properties are known. However, the composition of most of these polymers is only known, and the composition, structure, molecular weight, etc. were controlled by the conventional method that polymerized and saponified vinyl acetate in the presence of the core polymer. It was not possible to synthesize a polymer having a structure.

Recently, as a polymer containing a polyvinyl alcohol-based macromonomer unit, a polymer containing a polyvinyl alcohol-based macromonomer unit obtained by hydrolyzing a polymer containing a styrene-terminated polyvinyl ester-based macromonomer unit ( J. Polymer Sci., PC,
25 , 175 (1987). Hereinafter, it is abbreviated as document (A)),
Styrene-terminated polydimethylalkylsilyl vinyl ether hydrolyzate (Polymer Bulletin, 18,473 (1987))
reference. (Hereinafter abbreviated as (B)) and a polymer containing a polyvinyl alcohol-based macromonomer unit having two or more ester groups or amide groups in the linking group (see JP-A-61-89208; hereinafter, reference (C)). Abbreviated). However, in the case of the polymer containing a polyvinyl alcohol-based macromonomer unit disclosed in Reference (A), the polymer has a benzyl bond in the linking group derived from the polyvinyl alcohol-based macromonomer unit, and therefore has low weather resistance, Further, since the linking group has a cationic property, there is a problem that the range of use is greatly limited. In the case of the polymer containing a polyvinyl alcohol-based macromonomer unit disclosed in Document (B), the copolymerizability is low because the compatibility between dimethylalkylsilylvinylether, which is a raw material for synthesis, and the copolymerizable monomer is not sufficient. In some cases, the polymer obtained by hydrolyzing it is not good in composition, structure and molecular weight.

Further, in the case of the polymer containing a polyvinyl alcohol-based macromonomer unit disclosed in Reference (C), there is a problem that the alkali resistance of the linking group derived from the polyvinyl alcohol-based macromonomer unit is low.

C. Problems to be Solved by the Invention The present invention aims to provide a polymer containing a polyvinyl alcohol-based macromonomer unit having a short molecular weight distribution.

D. Means for Solving the Problems The present inventors have conducted intensive studies on the above problems,
General formula [However, R ¹ : hydrogen atom or methyl group (X): X ₁ or X ₂ bonded to S on the R ² side shown below]
Any one of the linking groups (R ² is an optionally branched alkylene group having 2 to 20 carbon atoms) (R ² represents an optionally branched alkylene group having 2 to 20 carbon atoms, and R ³ represents a hydrogen atom or an alkyl group having 4 or less carbon atoms.) (PVA): a number containing a vinyl alcohol unit It means a monovalent polyvinyl alcohol polymer having an average degree of polymerization of 3 or more. A polymer containing a polyvinyl alcohol-based macromonomer unit represented by the formula (1) and having a weight-average molecular weight of 10 ³ or more was found, and the present invention was completed.

 Hereinafter, the present invention will be described in detail.

The polymer of the present invention containing a polyvinyl alcohol-based macromonomer unit represented by the above general formula (I) is:
It refers to a homopolymer or copolymer of a polyvinyl alcohol-based macromonomer. The copolymer is a polymer composed of a polyvinyl alcohol-based macromonomer unit and at least one comonomer unit.

Since the polymer of the present invention contains a polyvinyl alcohol-based macromonomer unit in which the content of vinyl alcohol unit, the degree of polymerization and the distribution of polymerization degree are highly controlled, the content of the macromonomer unit is 3 to 5% by weight. Even when the amount is as small as a small amount, or even when the amount is as large as 50 to 100% by weight, effects such as hydrophilicity, water solubility, high concentration and low viscosity of the polymer, and strength improvement are exhibited.

The polyvinyl alcohol-based macromonomer unit constituting the polymer of the present invention is a portion constituting a polymer at one end,
It is composed of a polyvinyl alcohol-based polymer part and a part connecting both, and is represented by the above-mentioned general formula (I).
The portion constituting the polymer at one end is an acrylate ester, a methacrylate ester, an acrylamide or a methacrylamide, and is bonded to the polyvinyl alcohol-based polymer via a sulfur atom at a linking group (X) shown below. The linking group (X) is, (X): is any one linking group for X ₁ or X ₂ which binds to S by R ² side shown below.

R ² is an optionally branched alkylene group having 2 to 20 carbon atoms, and specific examples of R ² include-(CH ₂ ) ₂ -,-(C
_{H 2) 3 -, - (} CH 2) 6 -, - (CH 2) 10 -, (CH (C 6 H
₁₃ ) CH ₂ —, —CH (C ₁₀ H ₂₁ ) CH ₂ — and the like.

R ² is the same as in the above linking group (X ₁ ), and R ³ is a hydrogen atom or an alkyl group having 4 or less carbon atoms. Specific examples of R ³ include a hydrogen atom, a methyl group, Examples include an ethyl group, a propyl group, and a butyl group.

The polyvinyl alcohol-based polymer portion has a number average degree of polymerization of 3 or more, preferably 3 to 500, more preferably 5 to 300, and still more preferably the ratio of the weight average degree of polymerization to the number average degree of polymerization. A polyvinyl alcohol polymer having a polymerization degree distribution of 3.0 or less, wherein the content of vinyl alcohol homopolymer or vinyl alcohol unit is 5 mol% or more, preferably 10 mol% or more,
More preferably, it is a 30 mol% or more vinyl alcohol copolymer. When the number average degree of polymerization of the polyvinyl alcohol-based polymer portion exceeds 500, or when the ratio between the weight average degree of polymerization and the number average degree of polymerization (hereinafter, may be abbreviated as “polymerization degree distribution or w / n”) exceeds 3.0. The properties of the graft polymer containing a polyvinyl alcohol-based macromonomer unit of the present invention may not be sufficiently exhibited, which is not preferable. Here, the polymerization degree distribution is based on GPC measurement of the raw material polyvinyl ester-based macromonomer (measurement conditions: tetrahydrofuran (hereinafter abbreviated as THF) solvent, flow rate 1.0 ml / min, 25 ° C.). Further, when the content of the vinyl alcohol unit in the polyvinyl alcohol-based polymer is less than 5 mol%, the characteristics of the graft polymer containing the polyvinyl alcohol-based macromonomer unit of the present invention may not be sufficiently exhibited, which is not preferable. The monomer unit other than the vinyl alcohol unit in the polyvinyl alcohol-based polymer is not particularly limited. Depending on the use of the polymer, the following vinyl ester (hereinafter may be abbreviated as VES) unit and other comonomers may be appropriately used. (Hereinafter sometimes abbreviated as CMl) unit is used.

Vinyl ester (VES) units include vinyl formate,
Vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl valerate, vinyl caprate, vinyl versatate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl trifluoroacetate, vinyl trichloroacetate, etc. Of these, vinyl acetate is most preferred.

The other comonomer (CMl) is not particularly limited, and is selected from, for example, units that can be introduced by copolymerization or polymer reaction. Examples of such units include the following. That is, olefins such as ethylene, propylene, 1-butene, isobutene, acrylic acid or a salt thereof, methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-acrylate -Butyl, t-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, acrylates such as octadecyl acrylate, methacrylic acid or a salt thereof, methyl methacrylate,
Methacryls such as ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, and octadecyl methacrylate Acid esters,
Acrylamide, N-methylacrylamide, N-ethylacrylamide, N, N-dimethylacrylamide, diacetoneacrylamide, acrylamidepropanesulfonic acid or a salt thereof, acrylamodopropyldimethylamine or a salt thereof and a quaternary salt thereof, N-methylolacrylamide Or an acrylamide derivative such as a derivative thereof, methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, methacrylamidepropanesulfonic acid or a salt thereof, methacrylamidopropyldimethylamine or a salt thereof, and a quaternary salt thereof,
Methacrylamide derivatives such as N-methylolacrylamide or a derivative thereof, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, i-propyl vinyl ether, n-butyl vinyl ether, i
-Butyl vinyl ether, t-butyl vinyl ether,
Dodecyl vinyl ether, vinyl ethers such as stearyl vinyl ether, acrylonitrile, nitriles such as methacrylonitrile, vinyl chloride, vinylidene chloride,
Vinyl halides such as vinyl fluoride and vinylidene fluoride; allyl compounds such as allyl acetate and allyl chloride; maleic acid or its salts and esters; itaconic acid or its salts and esters; and vinylsilyl such as vinyltrimethoxysilane Compound, isopropenyl acetate, N
-Vinylpyrrolidone and the like.

The polymer of the present invention is a polymer containing a polyvinyl alcohol-based macromonomer unit as described above, and is a homopolymer or a copolymer of the macromonomer. The comonomer in the case of a copolymer (hereinafter sometimes abbreviated as CM2) unit is not particularly limited except for considering the solvolysis resistance in connection with the production method of the polymer of the present invention described later. The unit is selected from units which can be introduced by copolymerization or a polymer reaction. For convenience of use of the polymer, a comonomer (CM2) unit as exemplified below is used. That is, ethylene, propylene, 1-butene, olefins such as isobutene, methyl acrylate, methacrylic acid or a salt thereof, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate,
N-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, 2-hydroxyethyl methacrylate or its phosphoric acid ester, 2-dimethylaminoethyl methacrylate Or a salt thereof and a quaternary salt thereof, 2-diethylaminoethyl methacrylate or a salt thereof and a quaternary salt thereof, and methacrylic esters such as (2-hydroxy) dimethylaminopropyl methacrylate and 3-trimethoxysilylpropyl methacrylate; Styrene, p-methylstyrene, α-
Styrenes such as methylstyrene, chloromethylstyrene, p-styrenesulfonic acid or a salt thereof, p-hydroxystyrene or a derivative thereof, acrylamide, N-methylacrylamide, N-ethylacrylamide, N, N
-Dimethylacrylamide, diacetoneacrylamide, acrylamidepropanesulfonic acid or a salt thereof,
Acrylamidopropyldimethylamine or a salt thereof and a quaternary salt thereof, acrylamide derivatives such as N-methylolacrylamide or a derivative thereof, methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, methacrylamidopropanesulfonic acid or a salt thereof, methacryl Methacrylamide derivatives such as amidopropyldimethylamine or a salt thereof and a quaternary salt thereof, N-methylol methacrylamide or a derivative thereof,
Methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, i-propyl vinyl ether,
vinyl ethers such as n-butyl vinyl ether, i-butyl vinyl ether, t-butyl vinyl ether, dodecyl vinyl ether and stearyl vinyl ether;
Acrylonitrile, nitriles such as methacrylonitrile, vinyl chloride, vinylidene chloride, vinyl fluoride, vinyl halides such as vinylidene fluoride, allyl acetate, allyl chloride, allyl compounds such as allyl alcohol, maleic anhydride or salts thereof and In addition to its ester, fumaric acid or its salt and its ester, itaconic acid or its salt and its ester, isopropenyl acetate, N-vinylimidazole, N-vinylpyrrolidone and the like, polyoxyalkylene, polyoxyalkylene phosphate, polystyrene And macromonomers such as polymethyl methacrylate and polysiloxane.

The content of the polyvinyl alcohol-based macromonomer unit in the polymer is appropriately selected depending on the use of the polymer, but is 3% by weight or more, preferably 5% by weight, in order to sufficiently exert the effect of the polymer of the present invention. % By weight or more. Also,
The weight average molecular weight of the polymer is also appropriately selected depending on the use of the polymer, but it is necessary that the weight average molecular weight be 10 ³ or more, and 10 ³ to
10 ⁷ is more preferred. Here, the weight average molecular weight is a value obtained by GPC measurement of a polymer containing a polyvinyl ester macromonomer unit obtained by acetylating the polymer, using THF as a solvent.

Next, a method for producing a polymer containing a polyvinyl alcohol-based macromonomer unit of the present invention will be described.

The polymer of the present invention is obtained by solvolysis of a polymer containing a polyvinyl ester-based macromonomer unit or polymerization of a polyvinyl alcohol-based macromonomer. The polyvinyl ester-based macromonomer which is a raw material of the polymer containing the polyvinyl ester-based macromonomer unit is obtained, for example, by reacting a (meth) acrylic halide with a polyvinyl ester-based polymer having a hydroxyl group or an amino group at one end. . Examples of the (meth) acrylic acid halide include (meth) acrylic acid chloride and (meth) acrylic acid bromide. Among them, (meth) acrylic acid chloride is preferable. As a method of synthesizing a polyvinyl ester polymer having a hydroxyl group or an amino group at one end, a vinyl ester or a vinyl ester and a comonomer are polymerized while continuously dropping a thiol having a hydroxyl group or a protected amino group. (In the case of a protected amino group, deprotection after polymerization). The reaction of an acrylic acid halide or a methacrylic acid halide with a polyvinyl ester-based polymer having a hydroxyl group or an amino group at one end is carried out by dehydrating the polyvinyl ester-based polymer without using active hydrogen, for example, a solvent having no active hydrogen, such as methylene chloride, benzene, and toluene. , Xylene, THF or the like. Although a basic substance is used as a collecting agent for the generated hydrogen halide, a substance that may hydrolyze the vinyl ester unit cannot be used, and sodium hydrocarbon, pyridine, and triethylamine are used. The reaction is carried out, for example, while slowly dropping an acrylic acid halide or methacrylic acid halide solution into a polyvinyl ester and a basic substance,
The reaction time is 1 to 20 hours, preferably 1 to 10 hours. The reaction temperature at this time is 60 ° C to suppress side reactions.
The temperature is preferably 40 ° C or lower and -20 ° C or higher. The charge ratio of the polyvinyl ester polymer having a hydroxyl group or an amino group at one end to the (meth) acrylic halide is 100 moles of the polyvinyl ester polymer having a hydroxyl group or an amino group at one end (a hydroxyl group or an amino group at one end). (Moles per group), (meth) acrylic halide
It is 100 to 1000 mol, preferably 100 to 500 mol.

The above-mentioned monomer (CM) capable of homopolymerizing the thus obtained polyvinyl ester-based macromonomer or radically polymerizing with the polyvinyl ester-based macromonomer is used.
2) After copolymerizing with the above, the polymer is subjected to solvolysis or
Alternatively, the polymer of the present invention can be obtained by polymerizing a polyvinyl alcohol-based macromonomer obtained by solvolysis of a polyvinyl ester-based macromonomer having a linking group of (X ₂ ). As the polymerization method, a method usually used for radical polymerization can be adopted, and as a polymerization method classified by means of radical generation, a method using a usual initiator, a photopolymerization method, a radiation polymerization method, a plasma polymerization method, The bulk polymerization method, the solution polymerization method, the suspension polymerization method, and the emulsion polymerization method can be respectively adopted according to the classification of, but the bulk polymerization method using a thermal decomposition initiator, the solution polymerization method, and the suspension polymerization method are advantageously used. . Examples of the thermal decomposition initiator include azo compounds, peroxides, hydroperoxides and the like, and specifically, 2,2′-azobisisobutyronitrile,
2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), benzoyl peroxide, lauroyl peroxide, t-butyl hydroperoxide , Cumene hydroperoxide, potassium persulfate, ammonium persulfate, 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) -propionamide], 2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl)
Propane], 2,2'-azobis (2-methyl-N-phenylpropionamide) hydrochloride, 2,2'-azobis (2
-Methylpropionamide) hydrochloride and the like. A redox system using a combination of peroxide or hydroperoxide and a reducing agent can also be used, and examples thereof include a combination of hydrogen peroxide, potassium persulfate, etc. with 1-ascorbic acid, Rongalite and the like. As the polymerization solvent, any solvent can be used without particular limitation as long as it dissolves or disperses a polyvinyl ester-based macromonomer, a polyvinyl alcohol-based macromonomer, or a comonomer and dissolves the initiator. Examples of such solvents include benzene, toluene, aromatics such as xylene, methanol,
Alcohols such as ethanol, propanol and butanol, cyclic ethers such as tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate and propyl acetate, dimethyl sulfoxide, N, N-dimethylformamide , N, N-dimethylacetamide, water and the like are used alone or in combination. The polymerization operation can be any of a batch system, a semi-batch system and a continuous system, and is selected according to the combination and scale of the monomers used. The polymerization temperature is determined by the physical properties of the target polymer and the monomers used, the solvent, the type of the initiator, and the like.
Usually it is in the range of -30 ° C to 150 ° C.

As a method for obtaining a polymer containing a polyvinyl alcohol-based macromonomer unit from the solvolysis of a polymer containing a polyvinyl ester-based macromonomer, a polymer containing a polyvinyl ester-based macromonomer unit is placed in an appropriate solvent. The dissolution or decomposition is performed using a base or an acid. The solvolysis referred to in the present invention refers to hydrolysis or alcoholysis using a base or an acid, and as a solvent used for the decomposition reaction, benzene, toluene, aromatics such as xylene, Alcohols such as methanol, ethanol, propanol and butanol, cyclic ethers such as tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, dimethyl sulfoxide,
N, N-dimethylformamide, N, N-dimethylacetamide, water and the like are used alone or in combination. Examples of the acid include sulfuric acid, hydrochloric acid, and P-toluenesulfonic acid. Examples of the base include an alkali metal such as sodium hydroxide and potassium hydroxide, a hydroxide of an alkaline earth metal, sodium methylate, sodium ethylate, and the like. In addition to using alkali metal alcoholates such as potassium methylate, potassium ethylate and potassium t-butylate, and amines such as ammonia and trimethylamine, anion and cation exchange resins and exchange membranes can also be used. The reaction temperature is 5 ° C or higher and 100 ° C or lower in order to suppress side reactions.
Preferably it is 15 ° C or more and 80 ° C or less. If the above solvolysis decomposition conditions are too severe, not only the vinyl ester units but also the ester groups constituting the polyvinyl ester macromonomer units are decomposed, and the desired polymer cannot be obtained. Accordingly, in the present invention, alcoholysis with a base catalyst, particularly methanolysis is preferred.

E. Examples Hereinafter, the present invention will be described more specifically with reference examples and examples, but the present invention is not limited to the examples. “Parts” and “%” in Reference Examples and Examples are “polymerized parts” unless otherwise specified.
And "% by weight".

Reference Example 1 A reactor equipped with a stirrer, a reflux condenser, a nitrogen inlet tube and a thermometer was charged with 2400 parts of vinyl acetate monomer and methanol 60%.
0 parts were charged, and nitrogen gas was bubbled for 15 minutes to degas. Separately, an initial addition solution of thiol obtained by dissolving 0.78 part of 2-mercaptoethanol in 50 parts of methanol, a continuous addition solution of thiol having 100 parts by volume of methanol added to 60 parts of 2-mercaptoethanol, and 50 parts of methanol part Initiator solutions in which 1.81 parts of 2,2'-azobisisobutyronitrile were dissolved were respectively prepared, and nitrogen was replaced by bubbling with nitrogen gas.

When the temperature of the reactor was raised and the internal temperature reached 60 ° C., a separately prepared initial addition solution of thiol and an initiator solution were added in this order, and polymerization was started. Immediately, the addition of the thiol continuous addition liquid was started, and the polymerization was continued. The continuous addition of thiol was carried out with the target in the following table as the solid content concentration in the reactor increased with the progress of polymerization. The solid content concentration was checked by sampling.

Polymerization was performed for 3 hours while thiol was continuously added, and the polymerization was stopped by cooling. At this time, the solid concentration was 51.0%, and the thiol solution continuously added was 82.0 parts by volume. Then 30
The unreacted vinyl acetate monomer was removed while occasionally adding methanol at a temperature of 10 ° C. and a reduced pressure to obtain a polyvinyl acetate methanol solution. A part of the methanol solution was put into ether to recover polyvinyl acetate, and the precipitate was purified by reprecipitation twice with acetone-ether, and then dried under reduced pressure at 40 ° C. Proton NMR (measured by GX-500 manufactured by JEOL Ltd .; the same applies hereinafter) of the purified polyvinyl acetate using CDCl ₃ as a solvent showed that the number average degree of polymerization was 31 and a structure having a hydroxyl group at one end was obtained. Of polyvinyl acetate.

Reference Example 2 The methanol solution of polyvinyl acetate shown in Reference Example 1 was subjected to an operation of removing methanol with toluene at 40 ° C. under reduced pressure, and a toluene solution of polyvinyl acetate having a hydroxyl group at one end (concentration: 63.4%) And Into a reactor equipped with a stirrer, a reflux condenser and a dropping funnel, 100 parts of this toluene solution and 4.16 parts of pyridine were taken, and stirred well at room temperature. Then methacrylic acid chloride distilled just before 5.
After 50 parts and 10 parts of dehydrated toluene were put in a dropping funnel and mixed well, they were dropped uniformly over 1 hour with stirring at room temperature. After completion of the dropwise addition, stirring was continued at room temperature for another 3 hours. Next, 1.70 parts of methanol was added and the mixture was stirred for 1 hour, and then 400 parts of toluene was added in four portions under reduced pressure.
At 0 ° C., toluene, methanol and the like were distilled off, and the formed white precipitate was removed by filtration to obtain a 53.2% toluene solution. A part of the toluene solution was put into hexane to collect the polyvinyl acetate macromonomer, and the precipitate was purified by reprecipitation twice with acetone-hexane, and then dried at 40 ° C. under reduced pressure. Proton NMR of this purified polyvinyl acetate macromonomer was measured using CDCl ₃ as a solvent.
Was a polyvinyl acetate macromonomer having a methacrylic ester structure at one end and having the following structure.

GPC was transferred to LC-6A (manufactured by Shimadzu Corporation) using HSG-20.
H, HSG-40H and HSG-60S (manufactured by Shimadzu Corporation) were connected using a THF solvent, a flow rate of 1.0 ml / min, and 25 ° C.
(The same conditions apply to the following measurements), the ratio of the weight-average degree of polymerization to the number-average degree of polymerization was w / n = 2.2. Toluene was partially removed under reduced pressure to obtain a methanol solution having a concentration of 60.3%.

Reference Examples 3 to 6 In the same manner as shown in Reference Example 1, using polyvinyl acetate having a hydroxyl group at one end having a different number average degree of polymerization synthesized using 2-mercaptoethanol, the same as Reference Example 2 A methacrylate ester-terminated polyvinyl acetate macromonomer was synthesized by the method. First, the synthesis conditions and results
These are summarized in the table.

Reference Example 7 In the same manner as shown in Reference Example 1, using polyvinyl acetate having a hydroxyl group at one end synthesized using 1-N-dodecyl-2-mercaptoethanol, in the same manner as in Reference Example 2. Then, a polyvinyl acetate macromonomer having a methacrylic acid ester terminal having the following structure was synthesized. Table 2 summarizes the synthesis conditions and results.

Reference Examples 8 to 10 In the same manner as shown in Reference Example 1, methacrylic acid was obtained in the same manner as in Reference Example 2, using a polyvinyl acetate copolymer having a hydroxyl group at one end synthesized using 2-mercaptoethanol. A polyvinyl acetate copolymer macromonomer having the following structure having an acid ester terminal or an acrylic ester terminal was synthesized. Table 3 summarizes the synthesis conditions and results.

(Here, R ¹ represents hydrogen or a methyl group, and (CM) represents a copolymerized unit.) Example 1 A reactor equipped with a stirrer, a reflux condenser, a nitrogen inlet tube and a thermometer was charged with 50 parts of the polyvinyl acetate macromonomer synthesized in Reference Example 2, 100 parts of methyl methacrylate, and 120 parts of toluene. And nitrogen gas was replaced by bubbling nitrogen gas. When the temperature of the reactor was raised and the internal temperature reached 60 ° C, 2,2'-azobisisobutyronitrile 0.15
Was dissolved in 30 parts of toluene, and an initiator solution purged with nitrogen was added to initiate polymerization. After the polymerization was continued for 5 hours under stirring, the polymerization was stopped by cooling, and the polymerization solution was poured into excess methanol to recover 55 parts of the polymer. The resulting polymer is
It was purified by reprecipitation twice with an acetone-methanol system, and dried at 60 ° C. under reduced pressure. NMR of the purified polymer was measured with CDCl ₃ to find that the polyvinyl acetate macromonomer unit was 28.5 wt.
% Of the polymer. The polystyrene equivalent weight average molecular weight determined by GPC measurement was 54 × 10 ⁴ .

10 parts of the above purified polymer was dissolved in a mixed solvent of 75 parts of tetrahydrofuran and 13 parts of methanol. At 40 ° C., 2 parts of a 10 wt% methanol solution of sodium hydroxide was added with stirring to carry out an alcoholysis reaction. After the system was gelled, the system was crushed, 50 parts of methanol was added, and the mixture was left at room temperature for 24 hours to complete the reaction. Then 30 parts of methyl acetate and 5 parts of water
The mixture was heated at 50 ° C. for 1 hour, washed with Soxhlet in methanol, and purified to obtain poly (methyl methacrylate) containing a polyvinyl alcohol macromonomer unit. The content of the polyvinyl alcohol macromonomer unit in the polymer was determined by proton NMR measurement of a d ₆ -DMSO solvent and found to be 14.6% by weight. Further, 0.1 part of the polymer was reacted at 105 ° C. for 20 hours in a mixed solution of 8 parts of acetic anhydride and 2 parts of pyridine with occasional stirring to re-acetate. A polymer obtained by repeating reprecipitation purification in an acetone-water system three times was dissolved in THF and GPC was measured. As a result, the weight average molecular weight in terms of polystyrene was 50 × 10 ⁴ .

Examples 2 to 13 In the same manner as described in Example 1, a polymer was synthesized using the polyvinyl acetate macromonomer synthesized in Reference Examples 2 to 10, and methanol-decomposed to contain a polyvinyl alcohol macromonomer unit. A polymer was obtained. 4th result
These are summarized in the table.

Reference Example 11 A reactor equipped with a stirrer, a reflux condenser, a nitrogen inlet tube and a dropping funnel was charged with 9.25 parts of 2-aminoethanethiol,
50 parts of methyl-2-propanol were charged, and nitrogen gas was added to 30 parts.
Debubbled for a minute. While maintaining the temperature of the reactor at 0 ° C., 26.2 parts of di-tert-butyl dicarbonate was slowly added dropwise with stirring, and after completion of the addition, the mixture was heated under reflux for 30 minutes. An aqueous ammonium chloride solution was added to the reaction mixture, and the mixture was extracted with ethyl acetate. After washing with an aqueous sodium hydrogen carbonate solution, the extract was dried over magnesium sulfate, and the solvent was distilled off to obtain a crude product. The crude product was purified by distillation under reduced pressure at 0.1 mmHg and 60 ° C. to give N-tert-butoxycarbonyl-
16.1 parts of 2-aminoethanethiol were obtained.

In a reactor equipped with a stirrer, reflux condenser, nitrogen inlet tube and thermometer, 240 parts of vinyl acetate monomer and 60 parts of methanol were added.
Then, nitrogen gas was bubbled for 30 minutes to degas.
Separately, an initial addition solution of thiol obtained by dissolving 0.177 part of N-tert-butoxycarbonyl-2-aminoethanethiol in 50 parts of methanol, N-tert-butoxycarbonyl-2-
Add methanol to 30 parts of aminoethanethiol
Continuous addition solution of thiol and methanol in 50 parts by volume
Initiator solutions were prepared by dissolving 0.22 parts of 2,2'-azobisisobutyronitrile in 50 parts, respectively, and the mixture was purged with nitrogen by bubbling nitrogen gas.

When the temperature of the reactor was raised and the internal temperature reached 60 ° C., a separately prepared initial addition solution of thiol and an initiator solution were added in this order, and polymerization was started. Immediately, the addition of the thiol continuous addition liquid was started, and the polymerization was continued. The continuous addition of thiol was carried out with the target in the following table as the solid content concentration in the reactor increased with the progress of polymerization. The solid content concentration was checked by sampling.

Polymerization was carried out for 3 hours while thiol was continuously added, and the cooled polymerization was stopped. At this time, the solid concentration was 35.6%, and the thiol solution continuously added was 28.8 parts by volume. Then 30
The unreacted vinyl acetate monomer was removed while occasionally adding methanol at a temperature of 10 ° C. and a reduced pressure to obtain a polyvinyl acetate methanol solution. A part of the methanol solution was put into ether to recover polyvinyl acetate, and the precipitate was purified by reprecipitation twice with acetone-n-hexane, and then dried at 40 ° C under reduced pressure. Protonton NMR (measured by GX-500, manufactured by JEOL Ltd.) was measured for this purified polyvinyl acetate using CDCl ₃ as a solvent, and N-tert-butoxy was found to be present at one end having a number average polymerization degree of 22. It was a polyvinyl acetate having a carbonylamino group.

To 50 parts of polyvinyl acetate having an N-tert-butoxycarbonylamino group at one end, 150 parts of 98% formic acid was added and stirred to obtain a polyvinyl acetate formic acid solution. After leaving this solution at 10 ° C. for 24 hours, it was extracted twice with an aqueous solution of chloroform-sodium chloride, and the chloroform layer was dried over magnesium sulfate. Chloroform was distilled off under reduced pressure, and then dried at 40 ° C. under reduced pressure to obtain polyvinyl acetate. Proton NMR of this polyvinyl acetate was measured using CDCl ₃ as a solvent.
Was a polyvinyl acetate having an ammonium group at one end.

In a reactor equipped with a stirrer and a dropping funnel, 2.86 parts of polyvinyl acetate having an ammonium group at one end, 10 parts of methylene chloride, and 10 parts of a saturated aqueous sodium hydrogen carbonate solution
An aliquot was taken and stirred well at room temperature. Subsequently, 0.4 parts of methacrylic acid chloride distilled immediately before and 5 parts of methylene chloride were taken and mixed well, and then added dropwise over 10 minutes while stirring at room temperature. After completion of the dropwise addition, stirring was continued for another hour at room temperature. Next, a methylene chloride layer was separated by separating the reaction mixture and dried over magnesium sulfate. The solvent was distilled off to obtain crude polyvinyl acetate. This polyvinyl acetate was purified by reprecipitation twice with acetone-n-hexane, and then dried at 40 ° C. under reduced pressure.

For this purified polyvinyl acetate, use CDCl ₃ as a solvent and
When the MR was measured, it was a polyvinyl acetate macromonomer having the following structure and having a methacrylamide structure at one terminal having a number average degree of polymerization of 22.

Also GPC. HSG-20 for LC-6A (manufactured by Shimadzu Corporation)
H, HSG-40H and HSG-60S (manufactured by Shimadzu Corporation) were connected using a THF solvent, a flow rate of 1.0 ml / min, and 25 ° C.
(The same conditions apply to the following measurements), the ratio of the weight-average degree of polymerization to the number-average degree of polymerization was w / n = 2.2.

Reference Examples 12 to 14 In the same manner as shown in Reference Example 11, N-tert-butoxycarbonylamino group was added to one end having a different number-average degree of polymerization synthesized using N-tert-butoxycarbonyl-2-aminoethanethiol. Was used to synthesize a methacrylamide-terminated polyvinyl acetate macromonomer. Table 5 summarizes the synthesis conditions and results.

Reference Example 15 Except for using 0.35 part of acrylic acid chloride instead of 0.4 part of methacrylic chloride used in Reference Example 11, the number average degree of polymerization having an acrylamide group at one end in the same manner as in Reference Example 11, 22, w / n = 2.2 polyvinyl acetate macromonomer was obtained.

Example 14 A reactor equipped with a stirrer, a reflux condenser, a nitrogen inlet tube and a thermometer was charged with 50 parts of the polyvinyl acetate macromonomer synthesized in Reference Example 11, 100 parts of methyl methacrylate, and 120 parts of toluene. And nitrogen gas was replaced by bubbling nitrogen gas. When the temperature of the reactor was raised and the internal temperature reached 60 ° C, 2,2'-azobisisobutyronitrile 0.15
Was dissolved in 30 parts of toluene, and an initiator solution purged with nitrogen was added to initiate polymerization. After the polymerization was continued for 5 hours under stirring, the polymerization was stopped by cooling, and the polymerization liquid was poured into excess methanol to recover 42 parts of the polymer. The resulting polymer is
It was purified by reprecipitation twice with an acetone-methanol system, and dried at 60 ° C. under reduced pressure. NMR of the purified polymer was measured with CDCl ₃ to find that the polyvinyl acetate macromonomer unit was 20.2 wt.
% Of the polymer. The polystyrene equivalent weight average molecular weight determined by GPC measurement was 47 × 10 ⁴ .

10 parts of the above purified polymer was dissolved in a mixed solvent of 75 parts of tetrahydrofuran and 13 parts of methanol. At 40 ° C., 2 parts of a 10 wt% methanol solution of sodium hydroxide was added with stirring to carry out an alcoholysis reaction. After the system was gelled, the system was crushed, 50 parts of methanol was added, and the mixture was left at room temperature for 24 hours to complete the reaction. Then 30 parts of methyl acetate and 5 parts of water
The mixture was heated at 50 ° C. for 1 hour, washed with Soxhlet in methanol, and purified to obtain poly (methyl methacrylate) containing a polyvinyl alcohol macromonomer unit. The content of the polyvinyl alcohol macromonomer unit in the polymer was determined by proton NMR measurement of a d ₆ -DMSO solvent and found to be 11.0 wt%. Further, 0.1 part of the polymer was reacted at 105 ° C. for 20 hours in a mixed solution of 8 parts of acetic anhydride and 2 parts of pyridine with occasional stirring to re-acetate. The polymer obtained by repeating the reprecipitation purification in an acetone-water system three times was dissolved in THF and measured for GPC. As a result, the weight average molecular weight in terms of polystyrene was 45 × 10 ⁴ .

Examples 15 to 20 In the same manner as shown in Example 14, a polymer was synthesized using the polyvinyl acetate macromonomer synthesized in Reference Examples 11 to 15, and methanol-decomposed to contain a polyvinyl alcohol macromonomer unit. A polymer was obtained. Result 6
These are summarized in the table.

Reference Example 16 A solution was prepared by adding 30 parts of methanol to 1.91 parts of a polyvinyl acetate macromonomer having methacrylamide at one end shown in Reference Example 11. Separately, a solution in which 0.18 part of sodium hydroxide was dissolved in 10 parts of methanol was prepared, and both solutions were mixed. After standing at room temperature for one day, the precipitated solid was collected.
Further, the solid was subjected to Soxhlet extraction with methanol for 24 hours, and then dried at 40 ° C. under vacuum. This polyvinyl alcohol was measured proton NMR using DMSO-d ₆ as a solvent, saponification degree 99.2 mole%, a number average degree of polymerization
22 was a polyvinyl alcohol macromonomer having a methacrylamide structure at one end.

Reference Examples 17 to 19 The polyvinyl ester-based macromonomer shown in Reference Examples 12 to 14 was subjected to methanolysis in the same manner as in Reference Example 16 to obtain a polyvinyl alcohol-based macromonomer. The results are shown in Table 7.

Example 21 A reactor equipped with a stirrer, a reflux condenser, a nitrogen inlet tube and a thermometer was charged with 50 parts of the polyvinyl alcohol macromonomer synthesized in Reference Example 16 and 300 parts of distilled water, and 70
The polyvinyl alcohol macromonomer was washed with stirring at ℃. After cooling, 100 parts of acrylamide and 2-
0.1 part of mercaptoethanol was charged, and nitrogen gas was replaced by bubbling nitrogen gas at room temperature. When the internal temperature reached 70 ° C. in the reactor and the internal temperature reached 70 ° C., an initiator solution obtained by dissolving 0.30 part of potassium persulfate in 50 parts of distilled water and replacing with nitrogen was added to initiate polymerization. After the polymerization was continued for 5 hours under stirring, the polymerization was stopped by cooling. A part of the obtained polymer aqueous solution was poured into excess methanol, and the recovered polymer was purified by reprecipitation twice using a water-methanol system and dried at 60 ° C. under reduced pressure. When the NMR of the purified polymer was measured with a d ₆ -DMSO solution, it was a polymer containing 32.5 wt% of a polyvinyl alcohol macromonomer unit.

Examples 22 to 24 Polymers containing a polyvinyl alcohol macromonomer unit were synthesized using the polyvinyl alcohol macromonomer synthesized in Reference Examples 17 to 19 in the same manner as in Example 21. The results are summarized in Table 8.

Example 25 A polymer containing a polyvinyl alcohol-based macromonomer unit of the present invention, for example, in the case of a non-aqueous polymer such as those in Examples 1 and 2, has a moderate hygroscopic property, and therefore the polymer alone or It was confirmed that a blend with another resin was useful as an antistatic resin.
Also, for example, the water-soluble polymer shown in Example 10 is
It is a polyvinyl alcohol-based polymer having a so-called comb-shaped structure. It has been confirmed that the viscosity of the aqueous solution is lower than that of ordinary polyvinyl alcohol, so that it can be used in a high-concentration aqueous solution and that high-speed coating is possible. Further, it was confirmed that the polymer was easily dissolved in water, had good alkali resistance, and had good viscosity stability of the aqueous solution.

F. Effects of the Invention The polymer of the present invention is different from a graft polymer obtained by saponifying a polymer obtained by polymerizing a vinyl ester in the presence of various conventionally known polymers, Is controlled, the content of the polyvinyl alcohol unit, the degree of polymerization and the distribution of the degree of polymerization, and also the molecular weight of the copolymer. As a result, it becomes possible for the first time to control the higher-order structure of the obtained copolymer, and by introducing hydrophilic polyvinyl alcohol as a branch molecule, it becomes hydrophilic, water-soluble, high-concentration and low-viscosity of various polymers, and improves strength. Is expected to be achieved very efficiently.

The polymer containing the polyvinyl alcohol-based macromonomer unit obtained by the production method of the present invention varies widely in water-soluble to water-dispersible, water-insoluble and water-soluble properties depending on the content of the polyvinyl alcohol unit and the content of the comonomer unit and their properties. I do. Therefore, various applications corresponding to physical properties can be expected. In the case of a water-soluble or water-dispersible polymer, it is used for various uses in which a water-soluble polymer is used, such as paper processing and fiber treatment. in this case,
Because the structure of the polymer of the present invention is not a linear structure but a branched structure and the distribution of the degree of polymerization of the polyvinyl alcohol-based polymer constituting the branch molecule is sharp, the conventional polyvinyl alcohol-based polymer is The disadvantages such as the instability and poor fluidity of the aqueous solution that it had were solved.

In the case of a water-insoluble polymer, by introducing a polyvinyl alcohol-based polymer, which is a hydrophilic unit, into a hydrophobic polymer, it can be used for applications such as surface modification, antistatic, and medical materials. Also in this case, the conventional polyvinyl alcohol-based polymer is used as a branch molecule by utilizing the higher-order structure expression derived from the fact that the distribution of the polymerization degree of the polyvinyl alcohol-based polymer introduced as a branch molecule is a shear. Application development different from polymers is expected.

[Brief description of the drawings]

FIG. 1 is an NMR spectrum of a polymer containing a polyvinyl alcohol-based macromonomer unit obtained in Example 1.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-3-174425 (JP, A) JP-A-62-289084 (JP, A) JP-A-50-86588 (JP, A) JP-A 61-1986 89208 (JP, A) JP-A-1-179512 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 290/00-290/14 C08F 8/00-8/50

Claims (2)

(57) [Claims] (1) General formula [However, R ^{1 is a} hydrogen atom or a methyl group (X): any one of X _{1 and} X ₂ which is bonded to S on the R ² side shown below] (R ² is an optionally branched alkylene group having 2 to 20 carbon atoms) (R ² represents an optionally branched alkylene group having 2 to 20 carbon atoms, and R ³ represents a hydrogen atom or an alkyl group having 4 or less carbon atoms.) (PVA): a number containing a vinyl alcohol unit It means a monovalent polyvinyl alcohol polymer having an average degree of polymerization of 3 or more. A weight of 3 to 100% by weight of a polyvinyl alcohol-based macromonomer unit and 0 to 97% by weight of a comonomer unit and a weight-average molecular weight of 10 ³ or more. Coalescing. 2. A monovalent polyvinyl alcohol polymer (PV)
2. The polymer according to claim 1, wherein the ratio of the weight average degree of polymerization to the number average degree of polymerization of A) is 3.0 or less.