JPS60181111A - Modifier and modification method - Google Patents

Abstract

PURPOSE:To provide a modifier composed of a specific anionic sulfo ester (salt), capable of improving the devitrification resistance and dyeability of polymer when used in the emulsion polymerization of an ethylenic unsaturated monomer, and suitable also as an emulsifier for emulsion polymerization. CONSTITUTION:The objective modifier is composed of the unsaturated carboxylic acid ester (salt) containing anionic sulfo group and represented by formula I (R is 7-16C hydrocarbon group; n is 1-4; M is univalent or bivalent cation; m is valence of M and is 1 or 2). An ethylenic unsaturated monomer such as (meth) acrylic acid ester is polymerized by emulsion polymerization in the presence of said modifier in an amount of preferably 0.1-80(wt)%. The amount of the modifier is selected to give a polymer containing 0.2-5% modifier in the case of a hydrophobic polymer and 10-50% modifier for a hydrophilic polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a modifier and a modification method. More specifically, the present invention relates to a polymer modifier comprising a specific anionic sulfo group-containing unsaturated carboxylic acid ester (salt) and a method for improving the polymer.

Conventional dipolymers such as (meth)acrylonitrile (abbreviated to acrylonitrile and/or methacrylonitrile).

Similar expressions will be used below. )・Aromatic nuclei for the purpose of modifying polymers of ethylenically unsaturated monomers (hereinafter referred to as monomers) such as (meth)acrylic acid or its salts or esters, vinyl chloride, vinylidene chloride, and styrene. with an alcohol or its alkylene oxide adduct (
It is known to use sulfonated esters with meth)acrylic acid. Problems such as devitrification of the polymer thus obtained have been solved. However, the polymerization rate of the monomer does not increase; the performance of the polymer, such as dyeability, and the properties of the emulsion and the film obtained from the emulsion are not necessarily satisfactory.

Under these circumstances, the inventors of the present invention have made extensive studies and have arrived at the present invention.

That is, the present invention is based on the general formula (In the formula, I is a hydrocarbon group having 7 to 16 carbon atoms.

n is an integer from 1 to 4. M is a monovalent or divalent cation. 1n is an integer of 1 to 2 and represents the valence of 2@ion M. ) Sulfoester (salt)
A modifier for polymers comprising (first invention); A method for modifying a polymer (second invention) characterized by using a sulfoester (salt) represented by general formula (1).

In the present invention, modifiers include not only those used for the purpose of modifying polymers, but also those used in other ways (for example, as emulsifiers for emulsion polymerization) and resulting in modification of polymers. Quality is carried out and conflict is also included.

In general formula (1), the hydrocarbon group having 7 to 16 carbon atoms for R is an alkyl group having a straight chain or a side chain (heptyl, octyl, nonyl, decyl, unde(hexenyl,
octenyl, decenyl, dodecenyl groups, etc.) alkylaryl groups (methylphenyl.

Examples include dimethylphenyl, butylphenyl, octylphenyl, nonylphenyl groups, etc.) aralkyl groups (methylbenzyl, butylphenethyl groups, etc.). Among these, preferred are alkyl groups, alkylaryl groups and aralkyl groups, and particularly preferred are alkyl groups.

The carbon number of the hydrocarbon group constituting I is 7 to 16. Preferably it is 8-14. If the number of carbon atoms in R is less than 7, the compatibility with the monomer to be copolymerized is poor and a good copolymer cannot be obtained, and if the number of carbon atoms in R exceeds 17, modification to a copolymer is required. No effect is obtained.

1] is an integer of 1 to 4, preferably 2 to 3.

The monovalent or divalent cation of M is monohydrogen.

Alkali metals (storium, potassium, etc.), alkaline earth metals (calcium, magnesium, etc.).

Examples include ammonium and organic amine cations (alkanolamines, lower alkylamines, etc.). Preferred among these are alkali metals (especially sodium and potassium) and ammonium.

Specific examples of compounds represented by the general formula (]n include compounds in which R, n, m, and Δ1 of the general formula (1) are shown in Table 1.

The sulfo ester (salt) represented by the general formula (1) can be obtained by, for example, (1) a method of esterifying α-substituted acrylic acid with human or loxyalkane sulfonic acid (salt) and converting it into a salt if necessary; It can be produced by a method in which a substituted acrylate is esterified with a halogenated alkanesulfonic acid (salt) to form a salt if necessary, and a method in which a 11Dα-substituted acrylate is converted into a sulfoalkyl ester salt with an aliphatic sultone.

In the methods of (1) to (110), the α-substituted ac, lylic acid (salt) is, for example, J , OlC,, 4'O, & 2
1, 4147-4151 ('81).

The hydroxyalkanesulfonic acid (salt) in (+) is 2-hydroxyethanesulfonic acid (salt).

2-hydroxy-2-propanesulfonic acid c salt).

2-Hydroxy-1-butanesulfonic acid (salt), 1
-Hydroxy-2-butanesulfonic acid (salt), 3-hydroxy-2-butanesulfonic acid, and the like.

In (11), the halogenated alkanesulfonic acid (salt) is 2-chloroethanesulfonic acid (salt).

2-chloro-2-propanesulfonic acid (salt), 3-chloro-1-propanesulfonic acid (salt), 2-chloro-1-
Butanesulfonic acid (salt), 1-chloro-2-butanesulfonic acid (salt), 3-chloro-2-butanesulfonic acid (salt), 2-bromoethanesulfonic acid (salt), 2-bromo-
2-propanesulfonic acid ((2).

'3-bromo-7-propanesulfonic acid (salt), 2-bromo-1-butanesulfonic acid (salt), 1. -brome-2
-butanesulfonic acid (salt), 8-bromo-2-butanesulfonic acid (salt), and the like.

(In 110, the aliphatic sultone is 1.8-
Examples include propane sultone and 1,4-butane sultone.

In addition, there is a method of making salt. -C is a hydroxide of an alkali metal or an alkaline earth metal, or aqueous ammonia.

Examples include methods of neutralization with organic amines, methods of salt exchange, etc.

As the polymer to be modified using the modifier of the present invention, there can be used polymers used as synthetic fiber 1 synthetic resin 1 synthetic rubber, synthetic resin emulsion, and synthetic rubber latex. Examples include the following ethylenically unsaturated single star polymers: (a) Nitrile group-containing monomers: (meth)acrylonitrile, etc. (b) Unsaturated carboxylic acids [(meth)acrylic acid, maremonosun, etc. fumaric acid, itaconic acid, etc.]: Alkyl group having 1 to 20 carbon atoms (methyl, ethyl, etc.).

butyl, 2-ethylhexyl groups, etc.); glycols (ethylene glycol, 1,4 butanediol);

Di(meth)acrylates such as polypropylene glycol; (C) Amides of unsaturated carboxylic acids such as diesters or half-esters of maleic acid, fumaric acid, or itaconic acid; : ;1. Vinyl a-chloride, vinylidene chloride, chloroprene, etc. (e) Aromatic vinyl monomers: styrene, α-methylstyrene, chlorostyrene, vinyltoluene, etc. (f) Aliphatic hydrocarbon monomers: ethylene, propylene , butadiene, isofrene, etc. (g) Vinyl ester or (meth)allyl ester: vinyl acetate, vinyl propionate, divinyl phthalate, allyl acetate, diallyl phthalate, etc. (11) Unsaturated carboxylic acid or its salt: (meth)acrylic acid, maleic acid, fumaric acid.

Specific examples of polymers such as itaconic acid and their salts include 1. Chemistry of Basic Synthetic Resins (New Edition) (written by Tadahiro Miba, published by Gihodo on November 25, 1975, pages 7 and 11.9-217) Examples include polymerizable resins described in .

The amount of the modifier used in the present invention can be varied depending on the type of polymer, the composition of the monomer, the performance required for the purpose 1, etc. When producing a hydrophobic polymer for the purpose of dyeing property, antistatic property, etc., the modifier of the present invention is usually contained in the polymer in an amount of 01 to 10% by weight, preferably 02 to 5%.
It is better to include it. If the amount increases by more than 10%, the affinity for water becomes too large, which is often disadvantageous. on the other hand.

When producing a hydrophilic polymer (such as a water-soluble resin), the modifier of the present invention is added to the polymer in a polymer concentration [usually 2 to 80%, preferably 10 to 50% on a fake basis]. %.

Modification of polymers with the modifiers of the present invention can be carried out in one variety of ways.

The polymerization method may be bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization.

When carrying out polymerization using the modifier of the present invention, the polymerization may be carried out by mixing it into the monomer (mixture), or partially polymerized,
1. It may be mixed into a polymer mixture or polymer and subjected to graft or block polymerization. Also, polymer molded articles (fibers, textile products, etc.).

It can also be polymerized to improve the surface of films or cast products.

The modifier of the present invention is particularly useful as a polymerizable emulsifier used in emulsion polymerization of one monomer. Such use as an emulsifier can be achieved in various ways. For example, in an emulsion polymerization method using a conventional emulsifier, the modifier of the present invention can be used in place of the conventional emulsifier.

In addition, the modifier of the present invention may be further polymerized after the modifier is prepolymerized with the monomer to be polymerized, or the monomer to be polymerized with the monomer of the present invention. Polymerization can also be carried out by adding a modifier to the polymerization system.

In the various polymerization methods described above, polymerization can be initiated by irradiation with electron beams, gamma rays, or ultraviolet rays, by heating, and by using an initiator.

In the method using an initiator, persulfates (such as ammonium persulfate); peroxy compounds (
benzoyl peroxide, lauroyl"-oxide, hydrogen peroxide, etc.); azo initiators (azobisisobutyronitrile, etc.); redox initiators (sulfites and peroxy compounds, hydrogen peroxide and Fe" salts, etc.) Such initiators can be used.

In the various polymerization methods described in 1 above, during polymerization, the medium [solvents commonly used in solution polymerization, such as dimethylformamide, dimethylacetamide, dimethyl sulfoxide, and concentrated zinc chloride aqueous solution; emulsion polymerization and suspension polymerization] Commonly used aqueous media: water (mixed solvents of water and water-soluble organic solvents (methanol, isopropanol, acetone, etc.)), polymerization regulators, and chains such as various mercaptans (e.g. dodecyl mercaptan). A transfer agent] and a dispersant (partially saponified polyvinyl alcohol, etc.) can be used as necessary. In addition, in the case of emulsion polymerization, ordinary emulsifier t-anion activators that do not have copolymerizability (storium dodecylbenzenesulfonate, sodium lauryl sulfate).

polyoxystyrene alkylphenyl ether ammonium sulfate, sodium dialkyl sulfosuccinate, sodium alkyldiphenyl ether disulfonate, etc.) and/or nonionic activators (polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polypropylene glycol ethylene oxide). Although it is also possible to use a large amount of these substances, it is not preferable to use a large amount because it goes against the purpose of the present invention.

In the above various polymerization methods, the polymerization temperature is 1 polymerization method,
It varies depending on the type of monomer to be copolymerized, but 1
It is usually -5 to 150°C.

8. In the various polymerization methods mentioned above, 1. In addition to the modifier of the present invention, "
The modifier described in "Modifying agent and modification method" can be used in combination. When used in combination, the weight ratio can be varied over a wide range, for example 1 (invention) - 9:l.

Mat and other anionic monomers [sulfopropyl (meth)
Acrylate, styrene sulfonate, alcohol having an aromatic nucleus or its alkylene oxide adduct (
Sulfonated products of esters with meth)acrylic acid, etc.] can also be used in combination. When used in combination, the amount of the modifier of the present invention is usually 30% or more, preferably 50% or more, based on the total weight of the modifier of the present invention and other anionic monomers.

The modifier of the present invention has a higher polymerization rate of monomers than known modifiers made of anionic monomers; improved performance (degree of polymerization, dyeability, antistatic property, etc.). A polymer is obtained; the resulting polymer emulsion has excellent mechanical stability and low foaming; films and coatings obtained from the polymer emulsion have excellent water resistance and adhesion, etc. It has the effect of

In addition to the above effects, the modifier of the present invention has no devitrification; improves hydrophilicity; stains such as flakes, oil, grime, etc. are easily removed, and even when they are attached, they are easy to remove. It provides a polymer that has the performance of being able to be removed easily, and has a small amount of ε lumps.
In addition, when the polymer is extracted from the emulsion, it is possible to obtain a polymer emulsion having such properties that almost no emulsifier flows out into waste water.

Polymers modified by the method of the present invention are useful as synthetic fibers, fiber treatment agents, synthetic resins, paper processing agents, hair spray resins, and the like.

In addition, emulsions of these polymers can be used for adhesion, coating,
Can be used for the production of impregnation and dispersion compositions, water-based paints, adhesives, 2 paper processing, fiber processing (sizing agents, binders for non-woven fabrics, etc.), fiber modification, floor polish, soil erosion. It can be advantageously used for purposes such as prevention and mixing with concrete and mortar.

Furthermore, it can be used in the production of synthetic resins such as polyvinyl chloride and ABS resin, synthetic rubber, and synthetic fibers.

The present invention will be further explained below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples and Comparative Examples.

Example 1 Ammonium α-octylacryloxypropanesulfonate was used as a modifier of the present invention, and was used to modify a polymer.

Acrylonitrile 20g, Methyl acrylate Igα-octyl acryloxypropanesulfonic acid ammonium triglyceride 0
4g, azobisisobutyronitrile 0.82g, oxalic acid 0.1g, ethylenediamine o, o5g.

Titanium oxide 0.08g and dimethyl sulfoxide 79g
A mixture of g was polymerized at 42°C for 10 hours.

The polymerization temperature was raised to 50° C., and the polymerization was further continued for 15 hours. The polymerization rate was 99%, and the polymer weight was 1.70.

After collecting unreacted monomers, this polymer solution was used as a spinning stock solution and was spun in an aqueous solution of 30% dimethyl sulfoxide at 30°C. The obtained undrawn yarn was mixed with 6% dimethyl sulfoxide.
The film was stretched 5 times in an aqueous solution (temperature: 95°C). This drawn yarn was washed with water, dried, and heat treated to obtain a glossy white fiber without devitrification. When the basic dye PASIC BLUE GO was used in an amount of 3% by weight of the fiber at a bath ratio of 1:100 and dyed at 98° C. for 1 hour, the dye absorption rate was 97.5%.

Example 2 Sodium α-dodecyl acryloxyethanesulfonate was used as the modifier of the present invention, and a polymer was modified using the same.

50 g of methyl methacrylate under nitrogen atmosphere.

2 g of sodium α-dodecyl acryloxyethanesulfonate and 01 g of lauroyl peroxide were placed in a glass mold and polymerized at 160° C. for 4 hours to obtain a glassy resin. The surface specific resistance of this resin plate is JIS K6
1.5X10 when measured according to 911-1979
”Ω, and the antistatic properties were good.

Example 3 Sodium α-decyl acryloxypropanesulfonate was used as the modifier of the present invention, and a polymer was modified using the same.

117.5 g of ion-exchanged water, α
-Sodium decyl acryloxypropanesulfonate 1
．． 6 g, sodium bicarbonate') '7 A '0.08 g
.

0.16 g of ammonium persulfate, 22 g of styrene and 18 g of butyl acrylate were charged and emulsified with stirring, and after nitrogen substitution, polymerization was carried out at 75° C. for 30 minutes with stirring. Subsequently, an emulsion consisting of 184.5 g of ion-exchanged water, 5.6 g of sodium α-decyl acryloxypropanesulfonate, 0.28 g of sodium hydrogen carbonate, 0.56 g of ammonium persulfate, 77 g of styrene, and 68 g of butyl acrylate was poured into the dropping funnel for 2 hours. Dropwise over 80 minutes while stirring
Polymerization was carried out at .degree. C., and after adding 18 g of a 1% ammonium persulfate aqueous solution, the temperature was raised to 85.degree. C. and polymerization was carried out for 2 hours. Table 1 shows the test results for monomer polymerization conversion rate; amount of coagulum produced; mechanical stability and foaming properties of the emulsion; and water resistance and adhesion of the film.

Comparative Example 1 In Example 3, the same weight of sodium sulfopropyl methacrylate was used instead of sodium α-decyl acryloxypropanesulfonate, and polymerization was carried out according to the method of Example 3, but a large amount of coagulum was produced. The emulsion was obtained and dried.

Comparative Example 2 In Example 3, the same weight of sodium dodecylbenzenesulfonate was used instead of sodium 1α-decyl acryloxypropanesulfonate, and polymerization was carried out according to the method of Example 3 to obtain an emulsion. Performance test results such as monomer polymerization conversion rate are shown in Table 1.

Table-1 (Note-1) Monomer polymerization conversion rate Polymer emulsion, 5ge was taken and the weight of the evaporation residue after drying at 180℃ for 1.5 hours was measured and expressed as a percentage of the theoretical solid content weight at 100% polymerization. .

(Note-2) It was filtered through a wire mesh with a coagulum mass of 150 mesh, and the filtration residue was washed with water and dried at 130° C. for 5 hours to obtain a coagulum. The weight of the dry matter was calculated as a weight % based on the monomer used.

(Note-3) Mechanical stability of the emulsion Take 200g of the polymer emulsion in a beaker and use a homomixer for 10.
The solidified material produced by stirring at 0.00 rpm for 30 minutes was heated to 150 rpm.
The mixture was separated in a furnace using a mesh wire mesh, washed with cold water, and dried at 180°C for 5 hours. The weight of the dry matter was expressed as a percentage of the weight of solids in the collected emulsion.

(Note-4) J copolymer emulsion So
Pour 100m of water into a 100m cylinder and add 10m of water.
The amount of foam (m e ) after 5 minutes of vigorous shaking was determined.

<r:l-5) Film water resistance 71? A/Thu-r z II/ S/ E y h
? -F16-f(q 7 I-IT '1+,' +
It was dried at 460° C. for 8 hours and then at 20° C. for 24 hours to form a film with a thickness of 0.2 mm. The water resistance of this film was tested according to the water drop test method of JIS K-6828.

(Note 6) Film Adhesion A cellophane adhesive tape was applied to the film prepared by the method described in Note 5, and the adhesive strength between the film and the cellophane adhesive tape was measured by a 1800 peel test at 20°C.

(Note-7) Freeze-destroy the COD polymer emulsion in the emulsion waste liquid by freezing it at -10°C for 24 hours.
After melting at 30°C, the polymer was separated from P.

Measure the COD of P liquid according to JIsKo1o2-1971.

Claims (1)

[Claims] 1. General formula (wherein R is a hydrocarbon group having 7 to 16 carbon atoms, n is an integer of 1 to 4, M is a monovalent or divalent cation A modifier for polymers comprising a sulfoester represented by m is an integer of 1 to 2, and represents the valence of the cation M. 2. In a method of modifying using an anionic monomer during the production of a polymer of ethylenically unsaturated monomers, the anionic monomer is of the general formula (wherein R has a carbon number of 7" to 16
is a hydrocarbon group. n is an integer from 1 to 4. M is 1
It is a valent or divalent cation. -n] is an integer of 1 to 2 and represents the valence of the cation M. ) A method for modifying a polymer characterized by using a sulfoester (salt). The modification method according to item 2. 4. The ethylenically unsaturated monomer is converted into the sulfoester (salt).
The modification method according to claim 2 or 3, wherein emulsion polymerization is carried out in the presence of.