JPH09286851A - Modifier for polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a modifier effective for modifying polymers, especially vinyl polymers by using a compound having a specified chemical structure. SOLUTION: This modifier comprises a compound represented by the formula (wherein R<1> and R<2> are each hydrogen or methyl; R<3> is methylene or carbonyl; R<4> is a hydrocarbon group; X is hydrogen or a hydrophilic group; and m is 1-1,000, provided that the case where R<1> is hydrogen, R<3> is methylene; and X is SO3 M is excluded). In the formula, X is desirably a hydrophilic group represented by SO3 M, R<5> -COOM, PO3 M2 , PO3 MH or CO-R<6> -COOM (wherein M is hydrogen, an alkali metal, ammonium or the like; R<5> is an alkylene; and R<6> is a residue (except carbonyl) of a dibasic acid or its anhydride).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel polymer modifier. More specifically, a polymer modification having a polymerizable group and a hydrophilic group in the molecule, which is suitable for modifying a polymer having a monomer having one or more ethylenic carbon-carbon double bonds as a constituent unit. It is related to agents.

[0002]

2. Description of the Related Art Generally, vinyl chloride, vinylidene chloride,
A synthetic resin containing styrene, (meth) acrylic acid or the like as a monomer cannot satisfy various physical properties required for the resin simply by polymerizing a monomer component. That is, the required properties of synthetic resins differ depending on their various uses. The physical properties required for synthetic resins are:
Water resistance, adhesiveness, antistatic property, antifogging property, dyeing property, compatibilizing property, film forming property, weather resistance, blocking resistance and the like can be mentioned. Since these various physical properties cannot be obtained by simply polymerizing a monomer, various resin modifiers have been conventionally proposed in order to impart these physical properties.

Among the modifiers for resins proposed so far, so-called reactive modifiers having a radically polymerizable reactive group capable of copolymerizing with the constituent monomer units of the synthetic resin in the molecule are excellent. Due to its excellent performance, its application is now widely expected. For example, JP
-1811010 discloses a sulfosuccinate ester (or salt) having a (meth) acrylic group as a reactive group.
A polymer modifier comprising the following is disclosed. JP 60
No. 181111 discloses a sulfosuccinate ester (or salt) having a (meth) acrylic group as a reactive group.
A polymer modifier comprising the following is disclosed. JP 61
-212550 discloses a modifier for a polymer comprising a sulfamide (or salt) having a (meth) acrylic group as a reactive group. Japanese Patent Laid-Open No. 1-144406
In the publication, it has a (meth) acrylic group as a reactive group,
A glycidyl acrylate-based modifier having a polyether chain as a hydrophilic group and a sulfate ester group is disclosed. JP-A-1-174511 discloses an allyl glycidyl ether-based modifier having a (meth) allyl group as a reactive group and a polyether chain as a hydrophilic group. JP-A-4-331217 discloses a glycidyl acrylate-based modifier having a (meth) acrylic group as a reactive group, a polyether chain as a hydrophilic group, and a sulfate ester group and a phosphate ester group. There is.
Japanese Patent Publication No. 47608/1995 discloses an allyl glycidyl ether-based modifier having a (meth) allyl group as a reactive group and a polyether chain and a sulfate ester group as a hydrophilic group. JP-A-1-144406 discloses a glycidyl acrylate-based modifier having a (meth) acrylic group as a reactive group and a polyether chain as a hydrophilic group.

Further, Japanese Patent Publication No. 3-80806 discloses that
A modifying agent has been proposed in which alkylene oxides are added to (meth) allyl alcohol and the binding terminal thereof is converted to a sulfuric acid ester, and the dyeability and antistatic property are improved.
Further, in JP-A-57-98539, a compound obtained by adding an alkylene oxide to (meth) allyl alcohol or (meth) acrylic acid improves the hardness and tensile strength of urethane foam and acrylonitrile-styrene polymer. The technology to do is proposed.

[0005]

However, the Japanese Patent Publication No. 3-8
Since the modifier and the like described in Japanese Patent No. 0806 have poor compatibility with the constituent monomers of the synthetic resin, it is difficult for the modifier to be incorporated into the resin during the synthetic resin production process, and a sufficient modifying effect can be obtained. There wasn't. Further, the glycidyl acrylate-based modifier and the allyl glycidyl ether-based modifier tend to be expensive because the manufacturing process of the modifier itself is complicated.

[0006]

The inventors of the present invention have made extensive studies and found that a compound having a relatively simple chemical structure is effective as a modifier of a polymer, particularly a vinyl-based polymer, and It came to completion. That is, the present invention provides a compound represented by the general formula (1):

[0007]

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(Wherein R ¹ and R ² represent a hydrogen atom or a methyl group, R ³ represents a methylene group or a carbonyl group, R ⁴ represents a hydrocarbon group, and X represents a hydrogen atom or a hydrophilic group. , M represents a number from 1 to 1000, provided that
At the same time, R ¹ is a hydrogen atom, R ³ is a methylene group, and X is SO.
_The present invention provides a polymer modifier comprising a compound represented by ₃ M group). Furthermore, the present invention provides the following general formula (2):

[0009]

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There is provided a polymer modifier represented by the formula: wherein R ^{1 to} R ⁴ , M and m are as defined above.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The polymer modifier of the present invention has a polymerizable group such as an allyl group, a methallyl group, an acryl group, a methacryl group, a crotonic acid residue or a croton alcohol residue, and a hydrophilic group in its molecule, and has a polymer constitution. It is a polymer modifier that reacts with a monomer that is a unit to modify it. As described above, in the general formula (1) or (2), R ¹ and R
² represents a hydrogen atom or a methyl group, and R ³ represents a methylene group or a carbonyl group. In the general formula (1) or (2), R ⁴ is one or more hydrocarbon groups, which may be linear, branched, cyclic, saturated or unsaturated, but preferably has 2 carbon atoms. ~ 4 alkylene groups such as ethylene, propylene, butylene and isobutylene groups, or phenylethylene groups (styrene oxide residues).

(R ⁴ —O) _{m of the} general formula (1) or (2)
The part can be obtained by addition-polymerizing alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide and epichlorohydrin, styrene oxide and the like. R ⁴ is determined by the alkylene oxide, styrene oxide, etc. to be added, and the alkylene oxide, styrene oxide, etc. to be added may be homopolymerization, two or more types of random polymerization, block polymerization, or random / block polymerization. The adding method may be a usual method. R ⁴ is preferably an ethylene group, and when two or more kinds of alkylene oxide, styrene oxide and the like are used, one of them is preferably ethylene oxide. This is because when added to a polymer polymerized in an aqueous system, compatibility with water as a medium is obtained, and hydrophilicity is imparted to the modified polymer.

The polymer modifier of the present invention, by using a compound containing an ether chain in its structure, exhibits excellent compatibility with the monomer which is a constituent unit of the polymer when polymerizing the polymer. It reacts easily with the monomer and is easily incorporated into the polymer. The portion represented by (R ⁴ —O) _m is, if necessary, the chain length of R ^{4 such as} the chain length of the alkylene oxide chain and the constituent R ⁴ such as the type of alkylene oxide and the degree of polymerization m. The hydrophilicity imparted to the polymer to be modified can be easily adjusted by selection according to various conditions such as the purpose of the quality and the compatibility with the monomer which is a constitutional unit of the polymer. In the general formula (1), m representing the degree of polymerization of (R ⁴ —O) is 1 to 1000, preferably 1 to
It is 500, more preferably 1 to 100.

In the general formula (1), X is a hydrogen atom or a hydrophilic group. The hydrophilic group e.g., -SO ₃ M, -
^{_{R 5 -COOM, -PO 3 M 2}} , -PO 3 MH or -C
O-R ⁶ -COOM, and the like. In the formula, M is a hydrogen atom or an alkali metal atom such as lithium, sodium and potassium, quaternary ammonium of ammonia, quaternary ammonium of alkylamine such as monomethylamine, monoethylamine, dimethylamine, diethylamine and dipropylamine, or monoethanol. 4 of alkanolamines such as amines, diethanolamine and triethanolamine
Represents primary ammonium. When X is a hydrogen atom, the hydroxyl group acts as a hydrophilic group.

In the above formula representing the hydrophilic group, R ⁵ represents an alkylene group such as methylene, ethylene, propylene, butylene, pentene, pentamethylene and hexamethylene. Above all, if the carbon chain of R ⁵ is too long, the reactivity becomes poor at the time of synthesizing the polymer modifier of the present invention, and the synthesis becomes difficult. Therefore, methylene, ethylene, propylene or the like having a carbon number of 1 to 3 is synthesized. Alkylene groups are preferred.

In the above formula representing the hydrophilic group, R ⁶ is the residue of the dibasic acid used in the reaction for introducing the dibasic acid which is a hydrophilic group when the polymer modifier of the present invention is synthesized. is there. In this case, an acid anhydride of the dibasic acid can be used instead of the dibasic acid. Examples of the dibasic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid and tetradecanedioic acid. Saturated alicyclic dicarboxylic acids such as saturated aliphatic dicarboxylic acids, cyclopentanedicarboxylic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, tolylenedicarboxylic acid, xylylenedicarboxylic acid, etc. Of unsaturated dicarboxylic acids such as aromatic dicarboxylic acids, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, nadic acid (endomethylenetetrahydrophthalic acid), methylnadic acid Acid, methylbutenyl tetrahydrophthal , And the like unsaturated alicyclic dicarboxylic acids such as methyl pentenyl tetrahydrophthalic acid.

Among these dibasic acids, those having a polymerizable carbon-carbon double bond in the molecule are those reactive groups of the polymer modifier represented by the general formula (1) such as allyl group and acryl group. At the same time, since it reacts with the monomer that is a constitutional unit of the polymer to be modified, it is easily incorporated into the polymer chain of the polymer. Examples of the dibasic acid having a polymerizable carbon-carbon double bond in the molecule include unsaturated aliphatic dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid and mesaconic acid, tetrahydrophthalic acid and methyl. Examples thereof include unsaturated alicyclic dicarboxylic acids such as tetrahydrophthalic acid, nadic acid, endomethylenetetrahydrophthalic acid, and methyl nadic acid.

(Production of Modifier) The method for producing the polymer modifier of the present invention may be a known method. For example, alkylene oxides such as ethylene oxide and propylene oxide are subjected to addition polymerization with a raw material compound that constitutes the reactive group portion of the polymer modifier of the present invention, such as allyl alcohol, acrylic acid, and crotonic acid. The reaction conditions at that time are not particularly limited, but usually at room temperature to 150 ° C., a pressure of 0.1 to 10 kg / cm ² G, and if necessary, an alkali such as sodium hydroxide or potassium hydroxide can be used as a catalyst. . The compound obtained by this reaction corresponds to the compound in which X is a hydrogen atom in the general formula (1).

Thereafter, when introducing a hydrophilic group into the compound obtained by the above reaction, an introducing reaction is carried out. In the formula representing a hydrophilic group, when sulfation is carried out to introduce a group represented by —SO ₃ M, as a hydrophilizing agent, for example, sulfamic acid,
Sulfuric acid, sulfuric anhydride, fuming sulfuric acid, chlorosulfonic acid, etc. can be used. The reaction conditions for sulfation are not particularly limited, but the normal temperature is room temperature to 150 ° C., and the pressure is 1
The reaction time is 1 to 10 under a pressure of about 5 kg / cm ² G.
About an hour.

In the formula representing a hydrophilic group, --PO ₃ M ₂ or-
When phosphorylation is performed to introduce a group represented by PO ₃ MH, examples of the hydrophilizing agent include diphosphorus pentoxide, polyphosphoric acid, phosphorus oxychloride and the like. In the case of phosphorylation, when introducing a phosphate group represented by —PO ₃ M ₂ into the hydrophilic group, the monoester type represented by the general formula (1) and the diester type represented by the general formula (2) are used. Obtained as a mixture. Each of these alone,
Alternatively, it can be used as a polymer modifier even as a mixture of a monoester type and a diester type.

The monoester type compound represented by the general formula (1) and the diester type compound represented by the general formula (2) are obtained as a mixture, which are separated and used as the polymer modifier of the present invention. They may be used, or if separation is difficult, they may be used as a mixture as they are as the polymer modifier of the present invention. The reaction conditions for phosphorylation are not particularly limited, but the normal temperature is room temperature to 150 ° C,
The pressure is normal pressure, and the reaction time is about 1 to 10 hours.

When carboxylic oxidation is carried out to introduce a group represented by --R ⁵ --COOM in the formula representing a hydrophilic group, examples of the hydrophilizing agent include chloroacetic acid (R ⁵ corresponds to a methylene group), chloro. Propionic acid (R ⁵ corresponds to an ethylene group) or salts thereof can be used. The reaction conditions for the carboxylic acid oxidation are not particularly limited, but the temperature is usually room temperature to 150 ° C., the pressure is atmospheric pressure to 5 kg / cm ² G, and the reaction time is about 1 to 10 hours. If necessary, an alkali such as sodium hydroxide or potassium hydroxide may be used as a catalyst.

In the formula representing a hydrophilic group, --CO--R ⁶ --CO
When dibasic oxidation is carried out to introduce a group represented by OM, the above-mentioned dibasic acid or its anhydride can be used as the hydrophilizing agent. For example, maleic acid (R ⁶ corresponds to ethylene group), phthalic acid (R ⁶ corresponds to phenylene group)
Alternatively, salts thereof, anhydrides thereof and the like can be mentioned. The reaction conditions for the dibasic oxidation are not particularly limited,
Normal temperature is room temperature to 150 ° C, pressure is normal pressure, reaction temperature is 1
About 10 hours. If necessary, an alkali such as sodium hydroxide or potassium hydroxide may be used as a catalyst. In addition, when hydrophilization is performed, it may be subsequently neutralized with alkali, ammonia, alkylamine, alkanolamine, or the like.

(Use) The polymer modifier of the present invention can impart the following various physical properties to the polymer to be modified. For example, adjustment of hydrophilicity, improvement of compatibility, improvement of antistatic property, improvement of antifogging property, improvement of water resistance, improvement of adhesiveness, improvement of dyeability, improvement of film-forming property, improvement of weather resistance or Examples include improvement in blocking resistance. As a specific example, when the polymer modified by the polymer modifier of the present invention is powdered and is packed in a transportation container or the like, the antistatic property is improved, and therefore the bulk at the time of packing is small. Becomes
The filling amount per unit becomes large, and the transportation cost can be reduced. In addition, since molded articles and films produced by using these modified polymers have antistatic properties, it is possible to obtain housings of electronic devices, films without blocking, and the like.

The polymer modifier of the present invention is added during the polymerization process of the above-mentioned polymer to be modified, and chemically reacts with the monomer and the polymer chain which are the constituent units of the polymer to give the polymer various physical properties. It is a polymer modifier characterized by being added. Further, the same effect can be obtained by adding it to the polymer after polymerization by, for example, kneading. Therefore, the polymer modifier of the present invention can simultaneously achieve compatibility with the monomer, which is a constituent unit of the polymer, and the effect of modifying the polymer.

The amount of the polymer modifier of the present invention to be used can be variously changed depending on the kind of the monomer constituting the polymer, the purpose of modifying the polymer and the required performance. It can be used in an amount of 0.1 to 80% by weight with respect to the unit monomer, and is a constituent unit of a polymer, especially when a water-soluble polymer having insufficient hydrophilicity is to be made into a highly hydrophilic polymer. It is preferable to use 1 to 80% by weight based on the total amount of the monomers. For other purposes such as water resistance, adhesiveness, antistatic property, antifogging property, dyeing property, film forming property, weather resistance, blocking resistance, etc., or compatibilization with polymers for polymer alloys When it is intended to add 0.1 to 0.1 to the total amount of monomers that are the constitutional units of the polymer.
It is preferable to use 60% by weight.

When the polymer modifier of the present invention is used, a known modifier such as a crosslinkable divinyl compound such as divinylbenzene, ethylene glycol dimethacrylate or methylenebisacrylamide may be used to further modify the physical properties of the polymer. It can be optionally used within the range of the usual amount used.

Polymers suitable for using the polymer modifier of the present invention are polymers composed of homopolymers or copolymers of vinylic monomers. For example, vinyl acetate, vinyl propionate, vinyl benzoate, vinyl (meth) acrylate, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, phenyl vinyl ether, methoxy butadiene, methyl vinyl ketone, ethyl vinyl ketone. Or vinyl compounds such as propyl vinyl ketone, phenyl vinyl ketone, divinyl phthalate, allyl acetate, diallyl phthalate, (meth) acrylic acid, (meth)
Methyl acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, phenyl (meth) acrylate,
Glycidyl (meth) acrylate, (meth) acrylic acid 2
-Acrylic compounds such as ethylhexyl, hydroxyethyl (meth) acrylate, hydroxybutyl (meth) acrylate, (meth) acrylonitrile, (meth) acrylamide, methylenebisacrylamide, ethylene, propylene, 1-butene, 1-pentene, 1 -Hexane, 1
-Heptene, 1-octene, 1-nonene, 1-decene,
1-undecene, 1-dodecene, 1-tridecene, 1-
Tetradecene, butadiene, aliphatic unsaturated compounds such as isoprene, styrene, α-methylstyrene, chlorostyrene, aromatic vinyl compounds such as vinyltoluene, vinyl chloride, vinylidene chloride, halogenated olefin compounds such as chloroprene, maleic anhydride, Maleic acid esters, itaconic acid, itaconic acid esters, crotonic acid,
Examples thereof include unsaturated carboxylic acids such as crotonic acid esters and esters thereof.

These polymers are usually used as synthetic fiber, synthetic rubber, synthetic resin, synthetic resin emulsion or synthetic resin rubber latex. For example, synthetic fibers include acrylonitrile and copolymers of vinyl acetate, (meth) acrylic acid ester, styrene, vinyl chloride, vinylidene chloride, etc., and synthetic resins include AS.
Examples thereof include resins, ABS resins, (meth) acrylic resins and the like.

The polymer modifier of the present invention may be added to the polymerization system during the polymerization of the polymer. Polymerization conditions are not particularly limited, and may be any of bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization and the like. Examples of the polymerization initiator that can be used include hydrogen peroxide, ammonium persulfate, lauroyl peroxide, potassium persulfate, azobisisobutylnitrile, and benzoyl peroxide. Further, redox initiators such as sulfites and peroxide compounds, hydrogen peroxide and Fe ²⁺ salts, and the like can also be used. Further, as the polymerization accelerator, sodium hydrogen sulfite,
Examples include ferrous ammonium sulfate. As the polymerization regulator, dodecyl mercaptan or the like can be added. The temperature at the time of polymerization varies depending on the polymer, but is generally from room temperature to 200 ° C. In the case of emulsion polymerization, known emulsifiers for emulsion polymerization such as sodium dodecylbenzenesulfonate, sodium lauryl sulfate ester, polyoxyethylene alkylphenyl ether, polyalkylene glycol monoalkyl ether, etc. can be added. Also, a medium can be added as necessary during the polymerization. Examples thereof include water, methanol, 2-propanol, acetone, dimethylformamide, dimethylacetamide, dimethylsulfoxide, and an aqueous zinc chloride solution.

[0031]

EXAMPLES The present invention will be described in more detail by way of examples. In the following notation, each abbreviation indicates the following group:

[0032]

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(Production Example 1) After dissolving 0.3 g of potassium hydroxide in 58 g of allyl alcohol in a pressure-resistant autoclave, 220 g of ethylene oxide was added at a temperature of 80-100.
The addition reaction was carried out by inserting the mixture at 5 ° C. and a pressure of 0.5 kg / cm ² G for 5 hours. 1 g of the adsorption treatment agent KYOWARD 700 (manufactured by Kyowa Chemical Industry Co., Ltd.) was charged to the obtained reaction product 9
Adsorption treatment was performed at 0 to 100 ° C. for 1 hour, and filtration was performed to obtain the target product. Hereinafter, the polymer modifiers (2) to (6) of the present invention were obtained by the same method. However, in (2), the amount of EO is changed, and in (3), BO and EO are used together, (4)
Then, methallyl alcohol was used instead of allyl alcohol, and EO and PO were used together. In (5), SO and EO were also used together, and in (6), croton alcohol and EO / PO system were used. did.

(Production Example 2) Ethylene oxide and propylene oxide were added to acrylic acid in the same manner as in Production Example (1), and 1972 g of the obtained reaction product was reacted with 97 g of sulfamic acid by a conventional method. A polymer modifier (7) according to the present invention was obtained. Hereinafter, polymer modifiers (8) to (10) of the present invention were obtained by the same method. However, in (8), EO was used, in (9), EO was used, phosphoric anhydride was used to introduce a hydrophilic group, and then neutralized with sodium hydroxide. In (10), EO and chloroacetic acid were used, and then neutralized with sodium hydroxide.

(Production Example 3) Ethylene oxide was added to allyl alcohol in the same manner as in Production Example (1),
98 g of maleic anhydride was added to 1378 g of the obtained reaction product, and after neutralization reaction with 40 g of sodium hydroxide,
The polymer modifier (11) of the present invention, which was the target product, was obtained by dehydration under reduced pressure and reacting in a conventional manner. The reactive modifiers of the present invention used in the test are summarized in Table 1.

[0036]

[Table 1]

For comparison, the following three modifiers were used. Comparative modifier 1

[0038]

[Chemical 6]

Comparative Modifier 2 Sodium Dodecylbenzene Sulfonate Comparative Modifier 3 Dimethylstearylamide

Example 1 100 g of xylene was charged into a reaction vessel equipped with a reflux condenser, a stirrer, a dropping funnel and a thermometer, and the system was replaced with nitrogen gas. Separately styrene 15
0 g, polymer modifiers (1) to (11) of the present invention and comparative modifiers (1) to (3) 7.5 g, benzoyl peroxide 2
g, and a mixed solution of 1 g of di-tertiarybutyl peroxide was prepared, and the mixed solution was continuously dropped into the reactor at a reaction temperature of 130 ° C. for 2 hours. Further, a mixed solution of 10 g of xylene, 0.5 g of benzoyl peroxide and 0.5 g of di-tertiarybutyl peroxide was added dropwise and the reaction was carried out for 2 hours. Then, the mixture was cooled and 90 g of xylene was added to obtain a polymer solution. 0.2 gm for each polymer solution obtained
An m-thick polymer film was prepared by a conventional method, and water resistance, antifogging property and antistatic property were evaluated by the following methods.
Table 2 shows the results.

Example 2 100 g of xylene was charged into a reaction vessel equipped with a reflux condenser, a stirrer, a dropping funnel and a thermometer, and the system was replaced with nitrogen gas. Acrylic acid 2 separately
75 g of ethylhexyl, 75 g of methacrylic acid, 15 g of the polymer modifiers (1) to (11) of the present invention and 15 g of the comparative modifiers (1) to (3), 2 g of benzoyl peroxide, di-tert-butyl-peroxide. 0.5 g of a mixed solution was prepared, and the mixed solution was continuously added dropwise to the reactor at a reaction temperature of 130 ° C. over 2 hours. Furthermore, xylene 10
g, 0.5 g of benzoyl peroxide and 0.5 g of di-tert-butyl-peroxide were added dropwise and reacted for 2 hours. Then cool, add 90 g of xylene,
A polymer solution was obtained. 0.2 mm in the obtained polymer solution
A thick polymer film was prepared by a conventional method, and water resistance, antifogging property and antistatic property were evaluated by the following methods. The results are shown in Table 3.

<Measurement / Evaluation Method> Water Resistance of Film 1 g of the film produced in Examples 1 and 2 was placed in hot water, boiled for 24 hours and then dried at 105 ° C. for 2 hours, and the change in the film was observed. The marks in the columns of water resistance in Tables 2 and 3 correspond to the following evaluations, respectively. ⊚: No change Δ: Part of the film was deformed ×: Entire film was deformed ・ Anti-fog property of the film The contact angle of water with respect to the polymer film was measured. -Antistatic property of film The polymer film was allowed to stand in an atmosphere having a temperature of 20 ° C and a humidity of 35% for 24 hours, and then the surface resistivity was measured.

[0043]

[Table 2]

[0044]

[Table 3]

As can be seen from Tables 2 and 3, the polymers modified with the modifier of the present invention show excellent water resistance, and also have excellent antifogging properties and antistatic properties.

Example 3 A glass-lined autoclave was charged with 150 g of deionized water and 0.2 g of di-2-ethylhexyl peroxydicarbonate, and the autoclave was degassed to 50 mmHg to remove oxygen. 100 g of vinyl chloride monomer was charged, and the temperature was raised to 57 ° C. under stirring at a rotation speed of 500 rpm to carry out polymerization. When the polymerization rate reaches 50%, the polymer modifiers (1) to (11) and the comparative modifiers (1) to (3) of the present invention.
2g was added and the polymerization was continued. Since it is the time of polymerization initiation pressure in the autoclave was 8.0 kg / cm ² G, the pressure in the autoclave became 4.0 kg / cm ² G at the time of the lapse of the polymerization initiator after about 7 hours, which time Polymerization was stopped by, the unreacted vinyl chloride monomer was recovered, and the contents were taken out and dehydrated and dried. A bulk specific gravity measurement test was performed on the obtained polyvinyl chloride by the following method. The results are shown in Table 4.

<Measurement / Evaluation Method> Bulk Density Measurement Test After leaving the polyvinyl chloride obtained in Example 3 in a thermostatic chamber at a temperature of 25 ° C. and a relative humidity of 50% for 48 hours, JIS K 6
Bulk specific gravity was measured by the method of 721. Further, the polyvinyl chloride prepared under the same conditions as above was stirred at 60 rpm for 2 minutes with a Brabender planetary mixer, and the bulk specific gravity was measured by the above method.

[0048]

[Table 4]

As can be seen from Table 4, since the polyvinyl chloride using the modifier of the present invention is less likely to be charged, the bulk specific gravity does not change even after mixing. On the other hand, since the comparative product is easily charged, the value of the bulk specific gravity changes greatly before and after mixing.

(Example 4) Styrene, methacrylic acid, vinyl acetate and acrylonitrile (10 g each) and the polymer modifiers (1) to (11) and comparative modifiers (1) to (11) of the present invention.
(3) 2g was mixed and the compatibility was evaluated. Table 5 shows the results. In Table 5, marks correspond to the following respective evaluations. A: Completely dissolved. Δ: Partially dissolved or partly dispersed.

[0051]

[Table 5]

As can be seen from Table 5, the polymer modifier of the present invention has excellent compatibility with various polymeric monomers.

[0053]

The effect of the present invention is to provide a polymer modifier capable of imparting various physical properties to a polymer by reacting at the time of polymerizing the polymer.

Claims (6)

[Claims] 1. The following general formula (1): (In the formula, R ¹ and R ² represent a hydrogen atom or a methyl group, R ³ represents a methylene group or a carbonyl group, and R ⁴
Represents a hydrocarbon group, X represents a hydrogen atom or a hydrophilic group, and m represents a number from 1 to 1000. However, at the same time R ¹
Is a hydrogen atom, R ³ is a methylene group, and X is a SO ₃ M group). 2. In the general formula (1), X is —SO _{3
^{M, -R 5 -COOM, -PO 3}} M 2, -PO 3 during MH or -CO-R ⁶ -COOM (wherein, M represents a hydrogen atom, ammonium alkali metal atom, ammonium, ammonium of an alkylamine or an alkanolamine Wherein R ⁵ represents an alkylene group, and R ⁶ represents a hydrophilic group represented by a dibasic acid or a residue of its anhydride (group excluding a carbonyl group). Agent. 3. The following general formula (2): A polymer modifier represented by the formula: wherein R ^{1 to} R ⁴ , M and m are as defined above. 4. In the general formula (1) or (2), R ⁴
There polymer modifier of any one of claims 1 to 3 is an alkylene group or phenylethylene group 2-4 carbon atoms. 5. The polymer modifier according to any one of claims 1 to 5, which modifies a polymer containing a monomer having one or more ethylenic carbon-carbon double bonds in the molecule as a constituent unit. 6. A polymer modified by the polymer modifier according to any one of claims 1 to 5.