JPS60181110A - Modifier and modification method - Google Patents

Abstract

PURPOSE:To provide a modifier composed of a specific anionic sulfosuccinic acid ester, 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 sulfosuccinic acid ester (salt) of formula I [one of R1 and R2 is group of formula II (R is H or hydrocarbon group) and the other is (substituted) hydrocarbon group; A, A1 and A2 are 2-4C (substituted) alkylene; l and m are 0 or positive integer; M is univalent or bivalent cation; n is valence of M and is 1 or 2]. An ethylenic unsaturated monomer such as (meth)acrylonitrile 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 10-60% 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 sulfosuccinate (salt) and a method for modifying the polymer.

Conventionally, polymers such as (meth)acrylonitrile (abbreviated as acrylonitrile and/or methacrylonitrile) are used.

Similar expressions will be used below. ), (meth)acrylic acid and its salts or esters.

Alcohols having an aromatic nucleus or their alkylene oxide adducts (meth) for the purpose of modifying polymers of ethylenically unsaturated monomers (hereinafter referred to as monomers) such as vinyl chloride, vinylitine chloride, and styrene. It is known to use sulfonated esters with 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 provides (where B, 1
, 112 is CIJ22c-coo-,4- and the other is a hydrocarbon group or a hydrocarbon group having a substituent) R
is hydrogen and is a hydrocarbon group; A, A, and A2 are alkylene groups having 2 to 4 carbon atoms or substituted alkylene groups; 'j' + m is 0 or a positive number.

M is a monovalent or divalent cation. 1] is 1 and 2, which shows the valence of the cation M. ) A modifier for polymers consisting of a sulfosuccinic acid ester (salt) (first invention); This is a method for modifying a polymer (@2 invention) characterized in that the method uses a sulfosuccinate ester (-) represented by the general formula (1) as an anionic monomer.

In the present invention, modifiers include not only those used for the purpose of modifying the polymer, but also those used for other purposes (for example, as an emulsifier for emulsion polymerization) and resulting in modification of the polymer. -A- and It is hydrogen or a hydrocarbon group.

Examples of the hydrocarbon group include a C, -tO hydrocarbon group, such as an alkyl group having a straight chain or a side chain (methyl, etc.).

Ethyl, propyl, butyl, heptyl, octyl.

nonyl, tehsil, untenle, dotesil, tritesil,
Tetradecyl, pencdecyl, hexadefur group),
Alkenyl! , (hegysenyl, octenyl, tesenyl,
Examples include dodecenyl group, alkylaryl group (methylphenyl, dimethylphenyl, butylphenyl, octylphenyl, nonylphenyl group, etc.), aralgyl group (methylbenzyl, butylphenyl group, etc.), and the like.

It, still R2 hydrocarbon groups or hydrocarbon groups having substituents include ILs and 113COOA3-, i
(,, -N' -A3 + ands CON A 3 + (H(OA)
q O) r A4-91゜('In the formula, R3 is a hydrocarbon group, 几. is H, a hydrocarbon group or -4AO)9H, A3 is an alkylene group having 2 to 4 carbon atoms, A4 is a 2 to 8 valent group (q is an integer of 0 or 1 or more, and r is an integer of 1 to 7).

It, and the hydrocarbon groups of melon include C, -2O alkyl groups (methyl group, ethyl group,
Butyl group, octyl group, decyl group, dodecyl group, tetradecyl group, hegisatecyl group, octadecyl group etc.)C2
-20 alkenyl group (propenyl group).

butenyl group, octenyl group, decenyl group, dodecenyl group, octadecenyl group, etc.), ncroalkyl group (cyclohexyl group, etc.), aryl group (phenyl group, naphthyl group, etc.), alkylaryl group (methylphenyl group, butylphenyl group, octyl group, etc.) Examples include phenyl group, nonylphenyl group, dodecylphenyl group), aralgyl group (benzyl group, phenethyl group, methylbenzyl group, etc.).

The hydrocarbon group having a substituent is acytoxyalkyl, mono- or dialkylaminoalkyl.

N-hydroxyalkyl substituted alkylaminoalkyl,
Examples include alkylamidoalkyl and hydroxyalkyl groups.

The types of hydrocarbon groups and hydrocarbon groups having substituents are not particularly limited, but when 几 is ■ or a methyl group, hydrocarbon groups preferably have 6 to 20 carbon atoms, particularly preferably 8 to 18 carbon atoms. It is.

In the case of a hydrocarbon group having less than 6 carbon atoms, the compatibility with the monomer to be copolymerized tends to be poor, and in the case of a carbon number of 21 or more, the intended reforming effect is small.

When it is a long chain (C1-16) hydrocarbon group, one with a small number of carbon atoms is preferred.

A, A, and A2 are alkylene groups or substituted alkylene groups having 1 carbon number 2 to 4, and are ethyl, L/n groups,
Examples include propylene group, butylene group, and phenylethylene group. The alkylene group or substituted alkylene group of A1 and A2 forms an oxygen trioxyalkylene group or a substituted oxyalkylene group, and when a plurality of the oxyalkylene groups are present, they may be of the same type. The blocks may be of different types (the blocks may be random). Preferred are oxyethylene group and oxypropylene group.

Oxyethylene group/oxypropylene group (combined use of oxyethylene group and oxypropylene group, block, random).

l and m are 0 or a positive number, preferably 0 or 1
The monovalent or divalent cation of OM which is an integer of 1 to 15, particularly preferably 0 or 1 to 10, includes hydrogen alkali metals (sodium, potassium, etc.), alkaline earth metals (calcium, magnesium, etc.). ).

Ru. Preferred among these are alkali metals (especially sodium and potassium) and ammonium.

Table 1 shows specific examples of compounds represented by general formula (1).
Examples include the compounds shown below.

In Table-1, EO is C2I-1,0, PO is C311,0
BO is Table-1 Table-1 (continued) Sulfosuccinate esters represented by general formula (1) are (') 411 Succinate esters and acidic sulfites.

A method of reacting a metasulfite, a sulfite, or a mixture thereof to form a sulfonate, and if necessary, performing salt exchange to form the desired salt; (ii) 4″ product lower alkyl sulfosuccinate [general formula (1) ) in It,
-o(A,,o), -,B,,,-〇(one or both of A20 fortunes are replaced with a lower alkoxy group) and gourd-〇(A+0), p ■J', , R2-0(A
20) Method by ff-7 tell exchange with one or both mH; (iiD +1-1 equivalent of sulfosuccinic acid.
・-Diester (salt) C In general formula (1), ■, 1
-O-(A, 0), QC- or i(,2-0-
(A20),,10 G- is -COOΔ'1 [
] and li, , -0(A, 0 ), H
Still J, L2-0-(A20)11. ] Method l by esterification with l. C I can do 11).

Moreover, the salt formation method can be varied depending on the type of sulfonating agent. For example, acidic sodium sulfite is converted into salt by metasulfite. Acid j: l: Potassium sulfite or potassium metasulfite to form the potassium salt; acidic ammonium sulfite or ammonium sulfite to form the ammonium salt. Acidic calcium sulfite.

Calcium metasulfite is converted into a calcium salt by adding calcium sulfite; examples include a method of converting into an amine salt by using a sulfite of an organic amine or an organic quaternary ammonium base. A desired salt can also be obtained by a single salt exchange reaction. For example, a thorium salt can be obtained by reacting an ammonium salt with sodium hydroxide.

As the polymer to be modified using the modifier of the present invention, polymers used as synthetic fibers, synthetic resins, synthetic combs, synthetic resin emulsions, and synthetic rubber latexes can be used. In closing, the following ethylenically unsaturated monomer h1 polymers may be mentioned: (a) Nitrile group-containing monomer.

(meth)acrylonitrile, etc. (1) Esters of unsaturated carboxylic acids [(meth)acrylic acid, maleic acid, fumaric acid, itaconic acid, etc.]: Alkyl groups having 1 to 20 carbon atoms (methyl, ethyl, etc.).

butyl, 2-ethylhexyl group, etc.), di(ivy)acrylate-I of glycol (ethylene glycol, 1,4-bucundiol, polypropylene glycol, etc.); maleic acid, fumaric acid, or itacon Acid diesters/half esters, etc. (c) Amides of unsaturated carboxylic acids (Tsuku) Acrylamide, etc. ((1) Halokene-containing monomers: J:;'17L vinyl chloride, vinylidene chloride, chlorobrene 7 .1 and ('') yJr d-group vinyl-Ill, :!i-styrene, (l'-methylstyrene, chlorostyrene, vinyltoluene, etc. (1') I-digital group hydrocarbon mono711-diethylene , propylene, butadiene, imblen 4r, etc.(g) Vinyl ester or (meth)allyl ester: Vinyl acetate, vinyl propionate, divinyl phthalate, allyl acetate 1-.diallyl fucre-1, etc. (1)) Unsaturated carboxylic acid or its salt : (meth)acrylic acid, maleic acid, fumaric acid.

Itaconic acid, etc. and their salts, etc.

Specific examples of polymers include polymerized resins described in "Basic Synthetic Resin Chemistry, New Edition" (written by Tadahiro Miba, published by Gihodo on November 25, 1975, pages 7 and 113-217).

The amount of the modifier used in the present invention can be varied depending on the type of polymer, monomer composition, purpose, required performance, etc. When producing a hydrophobic polymer for the purpose of dyeing property, antistatic property, etc., the modifier of the present invention is added to the polymer! The OI content is usually 10% to 10%, preferably 02 to 5%, based on I'i'. If it exceeds 10%, the affinity for water becomes too large, which is often disadvantageous. On the other hand, when producing a hydrophilic polymer (for example, a water-soluble resin), the modifier of the present invention is contained in the polymer in an amount of usually 2 to 80%, preferably 10 to 60% by weight.
%.

Modification of a polymer with the modifier of the present invention can be carried out in various ways.

The polymerization method may be any of bulk polymerization, solution polymerization, suspension polymerization, and 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,
It may also be mixed into a monomer-polymer mixture or polymer and subjected to granite or block polymerization. Also, polymer molded products (
The film can also be polymerized on the surface of textiles, textile products, etc., as well as cast products.

The modifier of the present invention is particularly useful as a polymerizable emulsifier used in emulsion polymerization of monomers. 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, after the modifier of the present invention has been prepolymerized with the monomer to be polymerized, the monomer to be polymerized may be further polymerized with the modifier of the present invention. Polymerization can also be carried out by adding the above to the polymerization system.

In the various polymerization methods described above, polymerization can be initiated by irradiation with electron beams, carbon rays, or ultraviolet rays, by heating, and by using an initiator. In the method using an initiator,
Persulfates (such as ammonium perate) as initiators;
Peroxy compounds (benzoyl peroxide, lauroyl peroxide, hydrogen peroxide, etc.); Azo initiators (azobisin butyronitrile, etc.) Niredox initiators (sulfites and peroxy compounds, hydrogen peroxide and Fe2+
Initiators such as salts, etc.) can be used.

In the above various polymerization methods, during polymerization, the medium [solvents commonly used in solution polymerization: dimethylolmamide, dimethylacetamide, dimethyl sulfoxide, concentrated zinc chloride aqueous solution, etc.; commonly used in emulsion polymerization and suspension polymerization; Aqueous medium: water! A mixed solvent of water and a water-soluble organic solvent (methanol, isopol, acetone, etc.).

Polymerization regulators [such as chain transfer agents such as various mercaptans (eg dodecyl mercaptan)].

A dispersant (partially dispersed non-polyvinyl alcohol) can be used if necessary. In addition, in the case of emulsion polymerization, an ordinary emulsifier that does not have copolymerizability [anionic active Mll
(sodium dodecylbenzene sulfonate, sodium lauryl sulfate, ammonium polyoxyethylene alkyl ether sulfate, sodium dialkyl sulfosuccinate, sodium alkyl diphenyl ether disulfonate, etc.) and/or nonionic activators (polyoxyethylene alkyl ether .

Polyoxyethylene alkylphenyl ether.

It is also possible to use polypropylene glycol ethylene oxide (fl) in combination, but it is not preferable to use a large amount because it goes against the purpose of the present invention.

In the above-mentioned various polymerization methods, the polymerization temperature varies depending on the polymerization method, the type of monomer to be copolymerized, etc., but is usually from -5 to 150"0.

In the various polymerization methods described above, in addition to the modifier of the present invention, other anionic monomers [Lua having an aromatic nucleus /I/
A sulfonated product of ester of coal or its alkyleneoxy M additive and (meth)acrylic acid, sulfopropyl (meth)acrylate, styrene sulfonate, etc. can also be used in combination. When used together, the amount of the modifier of the invention is usually 30% or more, preferably 50% or more, based on the total weight of the modifier of the invention and other anionic monomers.

The modifier of the present invention has lower monomer ratio than known modifiers made of anionic monomers: performance (degree of polymerization, dyeability, antistatic property, etc.). ) are obtained: the polymer emulsions obtained have good mechanical and chemical stability and have low foaming properties; films and coatings obtained from the polymer emulsions have It has excellent water resistance and adhesive properties.

In addition to the above effects, the modifier of the present invention has no devitrification; improves hydrophilicity; and prevents sludge, oil, grime, etc.
71 It gives a polymer that has the performance of being easily removed even if it sticks, and has a small amount of coagulum.If the polymer is to be extracted from the emulsion, an emulsifier is added to the waste water. It also has the effect of producing a polymer emulsion with properties such as almost no leakage.

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

Emulsions of these polymers can also be used in the production of adhesive, coating, impregnating and dispersing compositions, water-based paints and adhesives, 2 paper processing applications, textile processing applications (sizing agents, binders for non-woven fabrics, etc.), For fiber modification, floor polishing,
It can be advantageously used for soil erosion prevention, concrete J-1-, mortar mixing, and the like. In addition, synthetic resins such as polyvinyl chloride and ABS resin 1 synthetic rubber,
It can be used in the production of synthetic fibers, etc.

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 Compound No. I in Table 1 was used as a modifier of the present invention, and was used to modify a polymer.

Akrikoni 1 to Lil 20, 9. 1 g of methyl acrylate.

04g of compound No. of Table 1, azobisisobutyroni!・Lil O, 82. ! 7. Oxalic acid 0.1g, ethylenediamine 0.05. @ * A mixture of titanium oxide o, osg, and dimethyl sulfoxide (79.9 g) was polymerized at 42° C. for 10 hours. 1. The polymerization temperature was raised to 50° C., and the mixture was further polymerized for 15 hours. The polymerization rate was 995%, and the ratio of 2 polymers was 1.80.

After collecting unreacted monomers, this polymer solution was used as a spinning dope and was spun in an aqueous solution of 30 g of dimethyl sulfoxide at 30°C. The obtained undrawn yarn was drawn five times in an aqueous solution containing 6% dimethyl sulfoxide (temperature: 95° C.).

This drawn yarn was washed with water, dried, and heat treated to obtain a glossy white fiber without devitrification. Base 1':I:, Dyeing y,:4Pasic Blue Go was used in an amount of 3% of the fiber weight, and the bath ratio was 1:
When dyeing was carried out at 98° C. for 1 hour at 100° C., the dye Ft absorption rate was 985%.

Example 2 Compounds No. and XI in Table 1 were used as modifiers of the present invention to modify a polymer.

1-50 g of Methyl Mekkryle under a chlorine atmosphere.

Compound No. XI in Table-1 was added to 2. ! 9. and lauroyl peroxide 01g in a crow mold,
Polymerization was carried out at 60°C for 4 hours, and a 2 ynm thick polymer plate was prepared. The polymer taken out from the mold after cooling was a glass-like resin with a polymerization rate of 909% and a good transparency of 1". The surface specific resistance of this resin plate is Jl, S K69
5X10" as measured by the method of 11/1979.
Ω and 'J': j'f ton prevention property was good.

Example 3 Compounds No. and Xll in Table 1 were used as modifiers of the present invention to modify a polymer.

117.5% of ion-exchanged water was placed in a reaction vessel equipped with a stirrer, 2 dropping funnels, a nitrogen inlet, a thermometer, and a reflux condenser. !
;l 1 Compound No., Xll in Table-1 is 1.6. ! 9
．． Sodium bicarbonate o, 08gt Ammonium permate 0.16! q, 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. Continuing, ion exchange water 1B4.5.9, compound No.
g, sodium bicarbonate 0289 t 7 ammonium persulfate 0.56. An emulsion containing J9', 77 g of styrene, and butyl acrylate 1-68.9 was added dropwise from a dropping funnel over 2 hours, and polymerization was carried out at 80°C with stirring. After adding 1 cup of ammonium persulfate and 18 g of an aqueous solution, the mixture was heated to 85°C. The temperature was raised to C and polymerization was carried out for 2 hours. Monomer polymerization conversion rate; amount of coagulum produced; mechanical stability of emulsion;
Chemical stability.

Foaming property; film surface] Table 1 shows the results of the aqueous and adhesive tests.

Comparative Example 1 In Example 3, the same amount of sodium sulfobyl methacrylate was used in place of Compounds No. and X11 in Table 1, and polymerization was carried out according to the method of Example 3. was generated and no emulsion was obtained.

Comparative Example 2 In Example 3, the same BI amount of sodium dodecylbenzenesulfonate was used in place of the compound NnXII in Table 1, and polymerization was carried out according to the method of Example 3 to obtain an emulsion. Table 1 shows the performance test results for mono 7-' polymerization, conversion, and polymerization.

Table-1 (Note-1) Monomer polymerization conversion rate 1.5 g of polymer emulsion was taken at 180"O.
The weight of the evaporated residue after drying for several hours was measured and calculated as a percentage of the theoretical solid weight at 100% polymerization.

(Note-2) It was filtered through a wire mesh with a coagulum content of 150.71 tsh, and the filtration residue was washed with water and dried at 1180°C for 5 hours to obtain a coagulum. M ffi, %, was calculated by converting this dry weight into the monomer used.

(Note-32 Emulsion Mechanically Stable Polymer Emulsion 200g was placed in a beaker and heated in a homomixer for 10.
The resulting coagulated product was stirred at 0.00 rpm for 30 minutes, separated with a 150-mesh wire mesh, washed with cold water, and dried at 180° C. for 5 hours. The weight of this dry matter was collected and calculated based on the weight of solids in the emulsion. (Note-4) Chemical stability of emulsion Solids content 0.5
The volume (m) of N/1o CaCI2 required to coagulate and separate 50 mi of the polymer emulsion diluted with water to 50% was prepared.

(Note'5) Polymer emulsion 80 diluted with water to a foamable solid content of emulsion of 8%.
The mixture was placed in a ml lx 100 rrJ cylinder with a stopper and shaken vigorously 10 times to obtain a foam volume (mi) after 5 minutes.

(Note-6) Spread the water-resistant polymer emulsion of the film on a slide glass and hold it at 60°C.
for 8 hours, then dried for 24 hours at 20'O.
A film of two thicknesses was made. The water resistance of this film was tested according to the water drop test method of JIS K-6828.

(Note 7) Film Adhesion A cellophane adhesive tape was attached to the film prepared by the method described in Note 6, and the adhesive strength between the film and the cellophane adhesive tape was measured by a 1800 peel test at 20"0.

Claims (1)

[Claims] 1. General formula (in the formula, one of “++horse” is CH2==♂−Coo−,
A- and the other is a hydrocarbon group or a hydrocarbon group having a substituent, ■ is hydrogen or a hydrocarbon group; A, , A,
and A2 is an alkylene group having 2 to 4 carbon atoms or a substituted alkylene group, and m is 0 or a positive number. M is a monovalent or divalent cation. n is 1 but not 2
, and the valence of the cation M is hail. ) A modifier for polymers consisting of a sulfoconophosphate ester (salt). 2. In a method of modifying using an anionic monomer during the production of a polymer of ethylenically unsaturated monomers, the anionic monomer has the general formula (where R1, l (2) One is (J12= C-C00
-A- and the other is a hydrocarbon group or a hydrocarbon group having a substituent, ■ is hydrogen and is a hydrocarbon group; A, A,
and A2 is an alkylene group having 2 to 4 carbon atoms or a substituted alkylene group, l, n] are 0 or a positive number, and 0M is a monovalent or divalent cation. 11 is 1 and is 2, which shows the valence of the cation M. ) A method for modifying a polymer characterized by using a sulfosuccinic acid ester (Y). The modification method according to claim 2. 4. The modification method according to claim 2 or claim 3, wherein an ethylenically unsaturated monomer is emulsion polymerized in the presence of the sulfosuccinate salt.