CA1161581A - Aqueous solution or dispersion of a styrene/maleic anhydride copolymer and process for the preparation thereof - Google Patents
Aqueous solution or dispersion of a styrene/maleic anhydride copolymer and process for the preparation thereofInfo
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- CA1161581A CA1161581A CA000360619A CA360619A CA1161581A CA 1161581 A CA1161581 A CA 1161581A CA 000360619 A CA000360619 A CA 000360619A CA 360619 A CA360619 A CA 360619A CA 1161581 A CA1161581 A CA 1161581A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F8/44—Preparation of metal salts or ammonium salts
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Abstract
AQUEOUS SOLUTION OR DISPERSION OF A
STYRENE/MALEIC ANHYDRIDE COPOLYMER AND PROCESS
FOR THE PREPARATION THEREOF
Abstract of the disclosure:
After hydrolysis and partial neutralization, copoly-mers of styrene and maleic anhydride are soluble or dis-persible in water. Suitable copolymers have a molar ratio of styrene to maleic anhydride in the range of from 1.5:1 to 6:1 and a molecular weight of from 500 to 80,000. Hy-drolysis and neutralization are carried out in the presence of an inorganic neutralizing agent at a temperature of from 75 to 250°C, thus neutralizing from 1 to 50 percent of the carboxyl groups of the corresponding copolymer. The copo-lymer solution or dispersion is suitable especially for stabilizing aqueous dispersions of inorganic or organic substances.
STYRENE/MALEIC ANHYDRIDE COPOLYMER AND PROCESS
FOR THE PREPARATION THEREOF
Abstract of the disclosure:
After hydrolysis and partial neutralization, copoly-mers of styrene and maleic anhydride are soluble or dis-persible in water. Suitable copolymers have a molar ratio of styrene to maleic anhydride in the range of from 1.5:1 to 6:1 and a molecular weight of from 500 to 80,000. Hy-drolysis and neutralization are carried out in the presence of an inorganic neutralizing agent at a temperature of from 75 to 250°C, thus neutralizing from 1 to 50 percent of the carboxyl groups of the corresponding copolymer. The copo-lymer solution or dispersion is suitable especially for stabilizing aqueous dispersions of inorganic or organic substances.
Description
- 2 - HOE 79/F 253 The inver.tion relates to an aqueous solution or dis-persion of a styrene/maleic anhydride copolymer and a process for the prep~ration thereof.
Preparation of copGlymers of maleic anhydride ~ith vinyl compounds such as styrene is known for a long time (see for example Ind.Eng.Chem. 41 (1949), p. 1509). These copolymers are dissolved in water with addition of alkali, because their action as pigment dispersing agent, protec-tive colloid, thickener or sizing agent requires salt ~or-mation.
Furthermore, there are described copolymers of s~yrene and maleic anhydride having a molar ratio of styrene to maleic anhydride of from 1:1 to 4:1. an average molecular weight of from 400 to 100,000, and a melting point of from 80 to 300C (see for example U.S. Patent No. 3,444,151).
These copolymers are reacted with amines to yield nitrogen-containing copolymers being nearly insoluble in water or aqueous alkaline media; they are used as emulsifiers in the emulsion po'ymerization of vinyl monomers.
It is also disclosed to use styrene/maleic anhydride copolymers having a molar ratio of styrene to maleic anhy dride of from 1:1 to 3:1 and a molecular weight of from 1,600 to 50,000 for the manufacture of adhesives on the ba-sis of starch (see U.S. Patent ~lo. 3,939,108). These copo-lymers are normally manufactured by solution polymerization in an aromatic hydrocarbon, in the presence of a free radi-cal-forming agent as catalyst, at a temperature of from 75 to 300C. After addition of ammonia or alkali metal hy-droxide until a pH of 8 to 11 is adjusted, they can be dissolved in water under heat.
It is the object of the invention to provide an aque-ous solution or dispersion of a maleic anhydride copolymer which solution or dispersîon does not have an alkaline reaction and i3 suitable as emulsifier solution or emulsi-fier dispersion for plastics dispersions.
lhe inveIItioil relates to an aqueous solution or dis-persion of a hydrolyzed copolymer of styrene and maleic 5~
anhydride wherein the molar ratio of styrene to maleic anhydride is in the range of from 1.5:1 to 6:1~ the molecular weight (number average) is from 500 to 80,000, 1 to 60 percent of the carboxyl groups of the copolymer are neutralized, and the pH of the solution or dispersion is below 7.
The invention relates furthermore to a process for the preparation of an aqueous solution or dispersion of a hydrolyzed copolymer of styrene and maleic anhydride by hydrolysis of a styrene/maleic anhydride copolymer and partial neutralization with an inorganic neutralizing agent, which comprises heating a copolymer having a molar ratio of styrene to maleic anhydride of from 1.5:1 to 6:1 and a molecular weight (number average) of from 500 to 80,000 to a temperature of from 75 to 250C in the presence of water and in the presence of an amolmt of ammonia, an alkali metal hydroxide or alkaline earth metal hydroxide, or zinc oxide that is sufficient to neutralize 1 to 60 percent of the carboxyl groups of the copolymer.
Moreover, the invention provides the use of the cited solution or dispersion as stabilizer solution or dispersion for aqueous dispersions, and for the dispersion polymerization of vinyl compounds.
The styrene/maleic anhydride copolymer used in accordance with the invention has a molecular weight (number average) of from 500 to 80,000 preferably ~00 to 30,000. The molar ratio of styrene to maleic anhydride is from 1.5:1 to 6:1, preferably 1.6:1 to 4:1.
In accordance with the invention, the styrene/maleic anhydride copolymer is heated to a temperature of from 75 to 250 C, preferably 85 to 180 C, in the presence of water and of an inorganic neutralizing agent, and hydrolyzed. The free carboxyl groups of the copolymer so formed are thus neutralized in a percentage of from 1 to 60, preferably 6 to 50, %.
_3_ ~ - ~IOE 79/F 253 In this alkaline treatment of the copolymer, its concentra-tion is from 5 to 50, preferably 10 to 30, ~ by weight (re-lative to the total amount of water and copolymer). Depend-ing on the concentration and composition of the copolymer and the temperature chosen, this treatment takes from 5 mi nu~es to 5 hours, preferably 10 to 200 minutes. Large sty-rene amounts in the copolymer, high copolymer concentra-tion and low treating temperature require generally a pro-longed treatment time; that is, the treatment time can be influenced by varying the above parameters. It is recom-mended to operate under inert gas, for example nitrogen.
The styrene/maleic anhydride copolymer may contail1 additionally one or more further comonomers in an amGunt of up to 20 mol % (relative to the total monomer amount), incorporated by polymerization. Suitable are olefinically unsaturated compounds such as vinyl es~ers, vinyl ethers, acrylic esters, or unsaturated carboxylic acids such as acrylic, methacrylic, itaconic, crotonic, vinylsulfonic or N-rnethacryloyl-aminopropanesulfonic acid.
As inorganic neutralizing agent, there may be used ammonium hydroY~ide or an alkali metal hydroxide such as lithium hydroxide, sodium hydroxide or potassium hydroxide, or an alkaline earth metal hydroxide such as magnesium hy-droxide or calcium hydroxide, and furthermore zinc oxide.
Instead of one of these agents, a mixture of several of them may be employed alternatively. The arnount has to be chosen in such a manner that the intended neutralization degree is attained; it is in the range of from 0.02 to 1.2, preferably 0.12 to 1, base equivalent (relative to 1 mol of maleic anhydride in the copolymer). Depending on the kind and amount of neutralizing agent, a copolymer solution or dispersion is obtained; for the preparation of a solutioll, a larger amount of neutralizing agent is used than for the preparation of a dispersion.
For preparing an acidic solution of a hydrolyzed sty-rene/maleic anhydride copolymer it is recommended to carry out the alkaline treatme!lt in the presence of an emulsi ~ 5 - HOE 79/F_253 fier, preferably an aniorlic emulsifier. Suitable emulsi-fiers are especially alkali metal salts or ammonium salts of alkylsulfonic, arylsulfonic or alkylarylsulfonic acids or the corresponding sulfuric, phosphoric or phosphonic acids, the cited compounds possibly containing ethylene oxide units between the hydrocarbon radical in question (having preferably from 10 to 18 carbon atoms) and the an-ionic group, the oxethylated compounds contain preferably from 5 to 30 ethylene oxide units. Examples of suitable emulsifiers are sodium laurylsulfate, sodium octylphenol-glycol ether sulfate, sodium dodecylbenzene sulfonate, sodium lauryldiglycol sulfate, and the ammonium salts of oxethylated and sulfated tri-t.-butylphenol, t.-butylphenol and nonylphenol.
The emulsifier is used in an amount of from 3 to 100, preferably 5 to ~5, % by weight (relative to the styrene/
maleic anhydride copolymer).
The copolymer dispersion may be converted to a solu-tion by heating it to a temperature within the abovemen-tioned range of treatment temperature after having addedan emulsifier of the cited kind.
The aqueous solution or dispersion of a hydrolyzed co-polymer of styrene and maleic anhydride according to the invention has an acidic reaction. Its pH is below 7, pre-ferably below 6; especially advantageous is a solution ordispersion having a pH of from 2.0 to 5.7. The copolymer content of the solution or dispersion is in the range of from 5 to 50, preferably 10 to 30, % by weight, and its viscosity is from 20 to 20,000, preferably 50 to 3,000 mPa.s (measured according to Epprecht).
The copolymer solution or dispersion of the invention is applied as emulsifying, dispersing, sizing, gluing, thickening, flocculating or hydrophobizing agent, and as coating or binder in the fields of textile, paint and varnish, adhesives and paper manufacture. The dissolved or disperseà copolymer is fixed to materials such as wood, paper, ceramics, metals or plasti.cs by applying the ~6 ~
solution or dispersion thereto and removing the water, o, by electrochemical deposition.
The solution or dispersion is excellently suitable for stabilizing aqueous dispersions of natural or synthe-tie, i.norganie or organie substances, for example cellu-lose, plasties, pigments or fi.llers. It is furthermore a~pplied for the suspension or emulsion polymerization of vinyl compounds, especially vinyl esters and aerylic esters.
The plastics dispersions so stabiliæed have an inereased stability to shearing forces and pigments. The moment of adding the stabilizer solution or dispersion is irrelevant;
it may be added with similar results during or after the preparation of the dispersion to be stabilized.
The eopolymer solution or dispersion of the invention is applied above all in the polymerization of vinyl com-poutlds in an aqueous medium under aeidie eondition3. Espe-eially suitable monomers are olefinieally unsaturated com-pounds of the formula H2C = C - R1 in whieh R1 is a hydrogen atom or a methyl radical, and R2 is a) an alkylcarboxyl radical having from 2 to 1~, preferably 2 to 12, carbon atoms, b) an alkoxy radical having from 1 to 4 earbon atoms, e) a nitrile group, d) a halogen atom, preferably chlorine, e) a carboxyl or sulfo group, ~) an alkoxyearbonyl radieal having from 2 to 12, prefer-ably 2 to 9, carbon atoms, g) an aminocarbonyl radical, h) a hydrogen atom, i~ a phenyl radical, or k) a vinyl radleal.
B~.
- 7 - ~OE 79/F ~53 E~amples of such olefinically unsaturated compounds are a) vinyl esters of aliphatic carboxylic acids having ~rom 2 to 18, preferably 2 to 12, carbon atoms, such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl piva-late, vinyl isononate, vinyl laurate or vinyl decanates,furthermore vinyl esters of a mixture of monocarboxylic acids having from 9 to 11 carbon atoms;
b) vinyl ethers, such as vinylmethyl ether, vinylethyl ether or vinyl-n-butyl ether;
c) acrylonitrile or methacrylonitrile;
d) vinyl halides, such as vinyl chloride or allyl chloride;
e) unsaturated monocarbGxylic acids such as acrylic, meth-acrylic or vinylsulfonic acid;
f) acrylic esters or methacrylic esters of monohydric alka-nols having from 1 to 11, prefrably 1 to 8, carbon atoms, such as ~ethyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methylmethacrylate, ethylmeth-acrylate, butylmethacrylate, hexylmethacrylate, octyl-methacrylate or 2-ethylhexylmethacrylate;
g) acrylic or methacrylic acid amides such as acrylic, N
methylolacrylic, methacrylic or N-methylolmethacrylic acid amide;
h) ethyletle;
i) styrene or methylstyrene; or k) butadiene or isoprene.
Especially suitable monomers are the vinyl esters a), the vinyl ethers b), the vinyl halides d) and the acrylic and methacrylic esters f). ~he monomers are used per se or as mixtures with one another; monomer combinations are for e~ample obtained from an acrylic ester and a methacry-lic ester, an acrylic or methacrylic ester and a vinyl ester, a mixture of different vinyl esters, especially vinyl acetate and vinyl esters of a mixture of monocarboxy-lic acids having from 9 to t1 carbon atoms, furthermore from vinyl acetate and ethylene, or from vinyl acetate, ethylene and vinyl chloride.
The polymerization is usually carried out in the pre.-- 8 ~ _HOE 79/F 253 sence of a free radical-forming initiator, prefer~bly a peroxide compound or an aliphatic azo compoundO The ini~
tiator is oil-soluble or, preferably, water-soluble, and used in an amount of from 0.05 to 2, prefer~bly 0.1 to 1, % by weight (relative to the total amount Or monomers).
Suitable are especially hydrogen peroxide, alkali metal or ammonium salts of persulfuric, peroxydisulfuric or peroxy-diphosphoria acid, for example sodium persulfate, potassium peroxydisulfate or ammonium peroxydisulfate; furthermore alkylhydroperoxides such as t.-butyl hydroperoxide; dialkyl peroxides such as di-t.-butyl peroxide; diacyl peroxides such as diacetyl peroxide, dilauroyl peroxide or dibenzoyl peroxide; furthermore azo-di-isobutyric acid nitrile, azo-dicarbonamide or azo-~ ~ bis(4~cyanovaleric acid). The initiator i5 optionally used in combination with a reducing agent, especially an ammonium salt, alkali metal salt or alkaline earth metal salt of a sulfur-containing acid hav-i.ng a reducing action; suitable are preferably sulfites, ~isulfites, pyrosulfites, dithionites, thiosulfates or formaldehyde sulfoxylates. The amount of reducing agent is from 0.05 to 20, preferably 0.5 to 10, % by weight (relative to the styrene/maleic anhydride copolymer).
For increasing the polymerization speed, it is advan-tageous to use a solution or dispersion of a hydrolyzed styrene/maleic anhydride copolymer which has been prepared in the presence of a sulfite. Suitable sulfites are neu-tral or acidic salts of sulfurous or pyrosulfurous acid, especially ammonium t alkali metal or alkaline earth metal salts, and the amounts to be used are from 0.05 to 20, pre-ferably 0.5 to 10, ~ by weight (relative to the styrene/ma-leic anhydride copolymers).
In emulsion polymerization, the solution or dispersion of the hydrolyzed styrene/maleic anhydride copolymer is used in such an amount that the copolymer is present in a ~uantity`of from 0.1 to 10, preferably 0.5 to 5, ~ by weight ~relative to the total amount of monomers). In suspension polymerization, from 0.01 to 2 and preferably 0.05 to 1, ~
by weight ~relative to the total amoutlt of monomers) are sufricie!lt. Polymerization is carried out at a tempera-ture of from 25 to 90C, preferably 40 to 75C. Depending on the kind and amount of the monomers in question the po-lymerization time is in the range of from 2 to 8, p~efer-ably 2.5 to 5, hours.
The resulting polymer dispersions are excellently stable to shearing forces and have a very good pigment-birding capacity. Therefore, they are applied above all as binder dispersions in paints, especially dispersion paints, and paper coating compositions. The paper so coated is distinguished by high wet pick resistance and water re-sistence of crating (determined be measuring the wet rub in a so called Taber-Abraser).
The following examples illustrate the invention, the percentages beillg by ~leight in all cases.
X _ M P L E 1:
In a vessel provided with agitator and reflux conden-ser, 150 g of a copolymer of styrene and maleic anhydride(molar ratio 2:1) having an average molecular weight of 1,700 are heated for 2 hours at a temperature of 95 -100C together with 790 g of water and 7.05 g of caustic soda, and then cooled to room temperature. A clear solu-tion having a pH of 4.7 and a polymer content of 16.5 p isobtained. lhe carboxyl groups of the hydrolyzed copolymer are neutraliæed to an extent of 18 ~.
E X A M P L E` 2;
___ 30 a) Example 1 is repeated; ho~ever, instea~ of 7.05 g of caustic soda, 3.52 g only are used and the water amount is 720 g instead of 790 g. Moreover, the reac-tion mixture is filtered after cooling to room tempera-ture, thus obtaining a residue of 30.9 g (after drying).
hs filtrate, a dispersion having a pH of 4.1 and a poly-mer content of 14.9 % is obtained.
b) 8 g of the dispersion obtained according to a) are - 10 - H0~ 79/F 253 heated to 70C toge'her with 2 g of a 15 ~ aqueous solu-tion of sodium laurylsulfate, thus causing the copolymer to be dissolved.
c) 8 g of the dispersion obtained according to a) are heated to 80C together with 2 g of a l5 ~ aqueous solu-tion of the ammonium salt of a nony'phenol oxethylated with 25 mol of ethylene oxide and then sulfated as emul-sifier, thus dissolvlng the copolymer.
10 E X A M P L E 3:
In a vessel provided with agitator and reflux conden-ser, 300 g of a copolymer of styrene and maleic anhydride (molar ratio 3:1) having an average mo1ecular weight of 1,900 are heated for 2 hours at a temperature of 96C to-gether with 1,680 g of water and 29.3 g of caustic soda,and then cooled to room temperature. A solution having a pH of 6.8 and a polymer content of 16.7 % is obtained. 50 %
of the carboxyl groups of the hydrolyzed copolymer are neu-tralized.
E X A M P L E 4:
In a vessel provided with agitator and reflux conden-ser, 150 g of a copolymer of styrene and maleic anhydride (molar ratio 3:1) having an average molecular weight of 1,900 are heated for 2 hours at a temperature of 100C to-gether with 790 g of water and 25 g of a 25 % aqueous ammo-nia solution, and then cooled to room temperature. A solu-tion having a pH of 6.8 and a polymer content of 16.1 ~ is obtained. 50 ~ of the carboxyl groups of the hydrolyzed copolymer are neutralized.
E X A M P L E 5:
a) In a vessel provided with agitator and reflux con-denser, 150 ~ of a copolymer of styrene and maleic an~
hydride (molar ratio 3:1) havirg an average molecular weight of 1,900 are heated f`or 3 hours at a temperature of 97C toget'ner with 720 g of water and 7.3 g of caustic ~ HOE 79/F 253 soda, and then cooled to room temperature. A dispersion having a pH of 5.6 and a polymer content of 17.6 ~ i9 obtained. 25 % of the carboxyl grcups of the hydrolyzed copolymers are neutralized. The mean diameter of the dispersed polymer particles is 0.038 /um.
b) 8 g of the dispersion obtained according to a) are heated to 85C together with 2 g of a 15 % aqueous solu-tion of sodium laurylsulfate, thus dissolving the copo-lymer.
c) 8 g of the dispersion obtained according to a) are heated to 90C together with 2 g of the 15 % aqueous so-lution of the emulsifier of Example 2c), thus dissolving the copolymer.
~5 E X A M P L_E S 6 to 8:
In a vessel provided with agitator and reflux conden-ser, 150 g each of a copolymer of styrene and maleic anhy-dride (molar ratio 3:1) having an average molecular weight of 1,900 are heated for varying periods of time to a tem-perature of 97C together with 720 g each of water anddifferent amounts of lithium hydroxide, and then cooled to room temperature. Details and properties of the solution or dispersion in question are listed in Table 1.
Table 1 Example 6 7 8 amount LiOH (g) 4.4 3.3 2.2 time of treatment (h) 2 2 3 result solution dispersion dispersion pH 5.3 5.1 11.7 polyrner content (%) 17.6 17.3 16.9 neutralized 25 18.7 12.5 carboxyl groups (%) __ ~ 12 - 0 _79/~ 253 E X A ~5 P L E J-In a vessel provided with agitator anà reflux conden~
ser, 150 g of a copolymer of styrene and maleic anhydride (molar ratio 3:1) having an average molecular weight of 1,900 are heated under a nitrogen blanket for 2 hours at a temperature of 96C iogether with 1,300 g of water~ 7.3 g of caustic soda, ,25 g of a 30 ~ solution of the emulsifier of Example 2c) and 12 g of sodium pyrosulfite, and then oooled to room temperatur~. A solution having a pH of 5.3 and a polymer content of 13.3 % is obtained. 25 % of the carboxyl groups of the hydrolyzed copolymer are neutralized.
The solution is adjusted with water to a concentration of 7.8 ~, for application in the polymerization of viny1 acetate.
E X A M P L E 10:
In a vessel provided with agitator and reflux conden-ser, 150 g of a copolymer of styrene and maleic anhydride (molar ratio 2:1) having an average molecular weight of 1,700 are heated for 2 hours under a nitrogen blanket to a temperature of 96C together with 1,300 g of water, 7.3 g of caustic soda, 12~ g of a 30 ~ aqueous solution of the emulsifier of Example 2c) and 12 ~ of sodium pyrosulfite, and then cooled to room temperature. A solution having a pH of 4.3 and a polymer content of 13 % is obtained. 18.6 ~
of the car~oxyl groups of the hydrolyzed copolymer are neu-tralized.
The solution is adiusted with water to a concentration o~ 7.8 % for use in the polymerization of vinyl acetate.
3o EXAMPLE OF APPLICATION 1:
510 g ¢f water, 1.77 g of a 6 % aqueous sodiu~ alkyl-sulfonate solution (mean chain leng~h of the alkyl group:
12 to 14 carbon atoms), and 2 g of a 30 % aqueous solution of the ammonium salt of nonylphenol oxethylated with 25 mols of ethylene oxide and then sulfatQd are intr-oduced into a vessel provlded with agitator t and then flushed with nitro~-- l3 ~ HOE 79/F 253 gen. After having added a solution of 2.25 g of ammoniurn persulfate in 20 g of water, the mixture is heated to a tem~erature of 50C. While rnaintaining this temperature, 750 g of vinyl acetate and a solution of 0.39 g of sodium formaldehyde-sulfoxylate in 50 g of water are added sepa-rately and uniformly within 3 hours to the mixture. With-in the 1st hourj the same amount of the emulsifier combi-nation is added again to t,he batch; withln the following 2 hours, 100 g of the copolymer solution obtained according to Example 9 and 1.87 g of the above alkylsulfonate solu-tion and 21.2 g of the above 30 % ammonium sa;t solution are added in corresponding doses. Subsequently 9 a solution of 0.75 g of ammonium persulfate in 30 g of water is added to the mixture, and the batch is heated for 30 minutes to 75C and then cooled to room temperature.
A coagulate-free polyvinyl acetate dispersion is ob-tailled whicn is adjusted to pH 6 with 3.2 g of 12.5 %
ammonia solution. The solids content of the dispersion is 50.8 ~, and the polymer particles have a mean diameter of 0.22 /um. The dispersion is stable to shearing;after a 2 minutes' agitation by means of a high-speed agitator (5000 rpm) no coagulate formation can be observed, and the mean particle size of the polymer has not changed.
EXAMPLE OF APPLICATION 2:
Example of application 1 is repeated; however, the co-pol.ymer solution of Example 10 is used instead of that of Example 9. The polyvinyl acetate dispersion obtained is coagulate-free. The solids content of the dispersion is 50.~ ~, and the polymer particles have a mean diameter of 0.18 /um. The dispersion is stable to shearing (test ac-cording to Example of application 1).
0MPARATIVE EXAMPI,E 1:
1,620 g oF the styrene/maleic anhydride copolymer used in Example 3 are a~itated for 6 hours 3/4 at a temperature of ~0C in 8,024 g of water with addition of 316 g of 14 - _OE ~9/F 253 caustic soda. Tne suspension obtained after coolinx to room temperature is filtered, thus obtaining a solid resi-due of 47 g. The filtrate has a pH of 10.0 and a polymer content of 18.7 %. 100 ~ of the carboxyl groups of the hydrolyzed copolymer are neutralized.
COMPARATIVE EXAMPLE 2:
Example 4 is repeated; however, the temperature of heating is 70C only. 50 ~ only of the styrene/maleic anhydride copolymer are dissolved; the solution has a pH
of 5.2.
COMPARATIVE EXAMPLE 3:
Example 4 is repeated, the temperature of heating be-ing only 70C, and the double amount of ammonia solutionis used. The solution obtained has a pH of 9.3.
COMPA~ATIVE EXAMPLE 4:
Example of application 1 is repeated while replacing the copolymer solution obtained in Example g by water.
The polyvinyl acetate dispersion obtained coagulates in the test for stability to shearing, COMPARATIVE EXAMPLE 5~
_ Example of application 1 is repeated while replacing the copolymer solution obtained in Example 9 by a corres-pondingly prepared solution of a styrene~maleic anhydride copolymer (molar ratio 1:1) having an average molecular weight of 1,600, the carboxyl groups of which being neu-tralized to an extent of 12.3 % after hydrolysis. The polyvinyl acetate dispersion obtained coagulates in the test for stability to shearing.
Preparation of copGlymers of maleic anhydride ~ith vinyl compounds such as styrene is known for a long time (see for example Ind.Eng.Chem. 41 (1949), p. 1509). These copolymers are dissolved in water with addition of alkali, because their action as pigment dispersing agent, protec-tive colloid, thickener or sizing agent requires salt ~or-mation.
Furthermore, there are described copolymers of s~yrene and maleic anhydride having a molar ratio of styrene to maleic anhydride of from 1:1 to 4:1. an average molecular weight of from 400 to 100,000, and a melting point of from 80 to 300C (see for example U.S. Patent No. 3,444,151).
These copolymers are reacted with amines to yield nitrogen-containing copolymers being nearly insoluble in water or aqueous alkaline media; they are used as emulsifiers in the emulsion po'ymerization of vinyl monomers.
It is also disclosed to use styrene/maleic anhydride copolymers having a molar ratio of styrene to maleic anhy dride of from 1:1 to 3:1 and a molecular weight of from 1,600 to 50,000 for the manufacture of adhesives on the ba-sis of starch (see U.S. Patent ~lo. 3,939,108). These copo-lymers are normally manufactured by solution polymerization in an aromatic hydrocarbon, in the presence of a free radi-cal-forming agent as catalyst, at a temperature of from 75 to 300C. After addition of ammonia or alkali metal hy-droxide until a pH of 8 to 11 is adjusted, they can be dissolved in water under heat.
It is the object of the invention to provide an aque-ous solution or dispersion of a maleic anhydride copolymer which solution or dispersîon does not have an alkaline reaction and i3 suitable as emulsifier solution or emulsi-fier dispersion for plastics dispersions.
lhe inveIItioil relates to an aqueous solution or dis-persion of a hydrolyzed copolymer of styrene and maleic 5~
anhydride wherein the molar ratio of styrene to maleic anhydride is in the range of from 1.5:1 to 6:1~ the molecular weight (number average) is from 500 to 80,000, 1 to 60 percent of the carboxyl groups of the copolymer are neutralized, and the pH of the solution or dispersion is below 7.
The invention relates furthermore to a process for the preparation of an aqueous solution or dispersion of a hydrolyzed copolymer of styrene and maleic anhydride by hydrolysis of a styrene/maleic anhydride copolymer and partial neutralization with an inorganic neutralizing agent, which comprises heating a copolymer having a molar ratio of styrene to maleic anhydride of from 1.5:1 to 6:1 and a molecular weight (number average) of from 500 to 80,000 to a temperature of from 75 to 250C in the presence of water and in the presence of an amolmt of ammonia, an alkali metal hydroxide or alkaline earth metal hydroxide, or zinc oxide that is sufficient to neutralize 1 to 60 percent of the carboxyl groups of the copolymer.
Moreover, the invention provides the use of the cited solution or dispersion as stabilizer solution or dispersion for aqueous dispersions, and for the dispersion polymerization of vinyl compounds.
The styrene/maleic anhydride copolymer used in accordance with the invention has a molecular weight (number average) of from 500 to 80,000 preferably ~00 to 30,000. The molar ratio of styrene to maleic anhydride is from 1.5:1 to 6:1, preferably 1.6:1 to 4:1.
In accordance with the invention, the styrene/maleic anhydride copolymer is heated to a temperature of from 75 to 250 C, preferably 85 to 180 C, in the presence of water and of an inorganic neutralizing agent, and hydrolyzed. The free carboxyl groups of the copolymer so formed are thus neutralized in a percentage of from 1 to 60, preferably 6 to 50, %.
_3_ ~ - ~IOE 79/F 253 In this alkaline treatment of the copolymer, its concentra-tion is from 5 to 50, preferably 10 to 30, ~ by weight (re-lative to the total amount of water and copolymer). Depend-ing on the concentration and composition of the copolymer and the temperature chosen, this treatment takes from 5 mi nu~es to 5 hours, preferably 10 to 200 minutes. Large sty-rene amounts in the copolymer, high copolymer concentra-tion and low treating temperature require generally a pro-longed treatment time; that is, the treatment time can be influenced by varying the above parameters. It is recom-mended to operate under inert gas, for example nitrogen.
The styrene/maleic anhydride copolymer may contail1 additionally one or more further comonomers in an amGunt of up to 20 mol % (relative to the total monomer amount), incorporated by polymerization. Suitable are olefinically unsaturated compounds such as vinyl es~ers, vinyl ethers, acrylic esters, or unsaturated carboxylic acids such as acrylic, methacrylic, itaconic, crotonic, vinylsulfonic or N-rnethacryloyl-aminopropanesulfonic acid.
As inorganic neutralizing agent, there may be used ammonium hydroY~ide or an alkali metal hydroxide such as lithium hydroxide, sodium hydroxide or potassium hydroxide, or an alkaline earth metal hydroxide such as magnesium hy-droxide or calcium hydroxide, and furthermore zinc oxide.
Instead of one of these agents, a mixture of several of them may be employed alternatively. The arnount has to be chosen in such a manner that the intended neutralization degree is attained; it is in the range of from 0.02 to 1.2, preferably 0.12 to 1, base equivalent (relative to 1 mol of maleic anhydride in the copolymer). Depending on the kind and amount of neutralizing agent, a copolymer solution or dispersion is obtained; for the preparation of a solutioll, a larger amount of neutralizing agent is used than for the preparation of a dispersion.
For preparing an acidic solution of a hydrolyzed sty-rene/maleic anhydride copolymer it is recommended to carry out the alkaline treatme!lt in the presence of an emulsi ~ 5 - HOE 79/F_253 fier, preferably an aniorlic emulsifier. Suitable emulsi-fiers are especially alkali metal salts or ammonium salts of alkylsulfonic, arylsulfonic or alkylarylsulfonic acids or the corresponding sulfuric, phosphoric or phosphonic acids, the cited compounds possibly containing ethylene oxide units between the hydrocarbon radical in question (having preferably from 10 to 18 carbon atoms) and the an-ionic group, the oxethylated compounds contain preferably from 5 to 30 ethylene oxide units. Examples of suitable emulsifiers are sodium laurylsulfate, sodium octylphenol-glycol ether sulfate, sodium dodecylbenzene sulfonate, sodium lauryldiglycol sulfate, and the ammonium salts of oxethylated and sulfated tri-t.-butylphenol, t.-butylphenol and nonylphenol.
The emulsifier is used in an amount of from 3 to 100, preferably 5 to ~5, % by weight (relative to the styrene/
maleic anhydride copolymer).
The copolymer dispersion may be converted to a solu-tion by heating it to a temperature within the abovemen-tioned range of treatment temperature after having addedan emulsifier of the cited kind.
The aqueous solution or dispersion of a hydrolyzed co-polymer of styrene and maleic anhydride according to the invention has an acidic reaction. Its pH is below 7, pre-ferably below 6; especially advantageous is a solution ordispersion having a pH of from 2.0 to 5.7. The copolymer content of the solution or dispersion is in the range of from 5 to 50, preferably 10 to 30, % by weight, and its viscosity is from 20 to 20,000, preferably 50 to 3,000 mPa.s (measured according to Epprecht).
The copolymer solution or dispersion of the invention is applied as emulsifying, dispersing, sizing, gluing, thickening, flocculating or hydrophobizing agent, and as coating or binder in the fields of textile, paint and varnish, adhesives and paper manufacture. The dissolved or disperseà copolymer is fixed to materials such as wood, paper, ceramics, metals or plasti.cs by applying the ~6 ~
solution or dispersion thereto and removing the water, o, by electrochemical deposition.
The solution or dispersion is excellently suitable for stabilizing aqueous dispersions of natural or synthe-tie, i.norganie or organie substances, for example cellu-lose, plasties, pigments or fi.llers. It is furthermore a~pplied for the suspension or emulsion polymerization of vinyl compounds, especially vinyl esters and aerylic esters.
The plastics dispersions so stabiliæed have an inereased stability to shearing forces and pigments. The moment of adding the stabilizer solution or dispersion is irrelevant;
it may be added with similar results during or after the preparation of the dispersion to be stabilized.
The eopolymer solution or dispersion of the invention is applied above all in the polymerization of vinyl com-poutlds in an aqueous medium under aeidie eondition3. Espe-eially suitable monomers are olefinieally unsaturated com-pounds of the formula H2C = C - R1 in whieh R1 is a hydrogen atom or a methyl radical, and R2 is a) an alkylcarboxyl radical having from 2 to 1~, preferably 2 to 12, carbon atoms, b) an alkoxy radical having from 1 to 4 earbon atoms, e) a nitrile group, d) a halogen atom, preferably chlorine, e) a carboxyl or sulfo group, ~) an alkoxyearbonyl radieal having from 2 to 12, prefer-ably 2 to 9, carbon atoms, g) an aminocarbonyl radical, h) a hydrogen atom, i~ a phenyl radical, or k) a vinyl radleal.
B~.
- 7 - ~OE 79/F ~53 E~amples of such olefinically unsaturated compounds are a) vinyl esters of aliphatic carboxylic acids having ~rom 2 to 18, preferably 2 to 12, carbon atoms, such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl piva-late, vinyl isononate, vinyl laurate or vinyl decanates,furthermore vinyl esters of a mixture of monocarboxylic acids having from 9 to 11 carbon atoms;
b) vinyl ethers, such as vinylmethyl ether, vinylethyl ether or vinyl-n-butyl ether;
c) acrylonitrile or methacrylonitrile;
d) vinyl halides, such as vinyl chloride or allyl chloride;
e) unsaturated monocarbGxylic acids such as acrylic, meth-acrylic or vinylsulfonic acid;
f) acrylic esters or methacrylic esters of monohydric alka-nols having from 1 to 11, prefrably 1 to 8, carbon atoms, such as ~ethyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methylmethacrylate, ethylmeth-acrylate, butylmethacrylate, hexylmethacrylate, octyl-methacrylate or 2-ethylhexylmethacrylate;
g) acrylic or methacrylic acid amides such as acrylic, N
methylolacrylic, methacrylic or N-methylolmethacrylic acid amide;
h) ethyletle;
i) styrene or methylstyrene; or k) butadiene or isoprene.
Especially suitable monomers are the vinyl esters a), the vinyl ethers b), the vinyl halides d) and the acrylic and methacrylic esters f). ~he monomers are used per se or as mixtures with one another; monomer combinations are for e~ample obtained from an acrylic ester and a methacry-lic ester, an acrylic or methacrylic ester and a vinyl ester, a mixture of different vinyl esters, especially vinyl acetate and vinyl esters of a mixture of monocarboxy-lic acids having from 9 to t1 carbon atoms, furthermore from vinyl acetate and ethylene, or from vinyl acetate, ethylene and vinyl chloride.
The polymerization is usually carried out in the pre.-- 8 ~ _HOE 79/F 253 sence of a free radical-forming initiator, prefer~bly a peroxide compound or an aliphatic azo compoundO The ini~
tiator is oil-soluble or, preferably, water-soluble, and used in an amount of from 0.05 to 2, prefer~bly 0.1 to 1, % by weight (relative to the total amount Or monomers).
Suitable are especially hydrogen peroxide, alkali metal or ammonium salts of persulfuric, peroxydisulfuric or peroxy-diphosphoria acid, for example sodium persulfate, potassium peroxydisulfate or ammonium peroxydisulfate; furthermore alkylhydroperoxides such as t.-butyl hydroperoxide; dialkyl peroxides such as di-t.-butyl peroxide; diacyl peroxides such as diacetyl peroxide, dilauroyl peroxide or dibenzoyl peroxide; furthermore azo-di-isobutyric acid nitrile, azo-dicarbonamide or azo-~ ~ bis(4~cyanovaleric acid). The initiator i5 optionally used in combination with a reducing agent, especially an ammonium salt, alkali metal salt or alkaline earth metal salt of a sulfur-containing acid hav-i.ng a reducing action; suitable are preferably sulfites, ~isulfites, pyrosulfites, dithionites, thiosulfates or formaldehyde sulfoxylates. The amount of reducing agent is from 0.05 to 20, preferably 0.5 to 10, % by weight (relative to the styrene/maleic anhydride copolymer).
For increasing the polymerization speed, it is advan-tageous to use a solution or dispersion of a hydrolyzed styrene/maleic anhydride copolymer which has been prepared in the presence of a sulfite. Suitable sulfites are neu-tral or acidic salts of sulfurous or pyrosulfurous acid, especially ammonium t alkali metal or alkaline earth metal salts, and the amounts to be used are from 0.05 to 20, pre-ferably 0.5 to 10, ~ by weight (relative to the styrene/ma-leic anhydride copolymers).
In emulsion polymerization, the solution or dispersion of the hydrolyzed styrene/maleic anhydride copolymer is used in such an amount that the copolymer is present in a ~uantity`of from 0.1 to 10, preferably 0.5 to 5, ~ by weight ~relative to the total amount of monomers). In suspension polymerization, from 0.01 to 2 and preferably 0.05 to 1, ~
by weight ~relative to the total amoutlt of monomers) are sufricie!lt. Polymerization is carried out at a tempera-ture of from 25 to 90C, preferably 40 to 75C. Depending on the kind and amount of the monomers in question the po-lymerization time is in the range of from 2 to 8, p~efer-ably 2.5 to 5, hours.
The resulting polymer dispersions are excellently stable to shearing forces and have a very good pigment-birding capacity. Therefore, they are applied above all as binder dispersions in paints, especially dispersion paints, and paper coating compositions. The paper so coated is distinguished by high wet pick resistance and water re-sistence of crating (determined be measuring the wet rub in a so called Taber-Abraser).
The following examples illustrate the invention, the percentages beillg by ~leight in all cases.
X _ M P L E 1:
In a vessel provided with agitator and reflux conden-ser, 150 g of a copolymer of styrene and maleic anhydride(molar ratio 2:1) having an average molecular weight of 1,700 are heated for 2 hours at a temperature of 95 -100C together with 790 g of water and 7.05 g of caustic soda, and then cooled to room temperature. A clear solu-tion having a pH of 4.7 and a polymer content of 16.5 p isobtained. lhe carboxyl groups of the hydrolyzed copolymer are neutraliæed to an extent of 18 ~.
E X A M P L E` 2;
___ 30 a) Example 1 is repeated; ho~ever, instea~ of 7.05 g of caustic soda, 3.52 g only are used and the water amount is 720 g instead of 790 g. Moreover, the reac-tion mixture is filtered after cooling to room tempera-ture, thus obtaining a residue of 30.9 g (after drying).
hs filtrate, a dispersion having a pH of 4.1 and a poly-mer content of 14.9 % is obtained.
b) 8 g of the dispersion obtained according to a) are - 10 - H0~ 79/F 253 heated to 70C toge'her with 2 g of a 15 ~ aqueous solu-tion of sodium laurylsulfate, thus causing the copolymer to be dissolved.
c) 8 g of the dispersion obtained according to a) are heated to 80C together with 2 g of a l5 ~ aqueous solu-tion of the ammonium salt of a nony'phenol oxethylated with 25 mol of ethylene oxide and then sulfated as emul-sifier, thus dissolvlng the copolymer.
10 E X A M P L E 3:
In a vessel provided with agitator and reflux conden-ser, 300 g of a copolymer of styrene and maleic anhydride (molar ratio 3:1) having an average mo1ecular weight of 1,900 are heated for 2 hours at a temperature of 96C to-gether with 1,680 g of water and 29.3 g of caustic soda,and then cooled to room temperature. A solution having a pH of 6.8 and a polymer content of 16.7 % is obtained. 50 %
of the carboxyl groups of the hydrolyzed copolymer are neu-tralized.
E X A M P L E 4:
In a vessel provided with agitator and reflux conden-ser, 150 g of a copolymer of styrene and maleic anhydride (molar ratio 3:1) having an average molecular weight of 1,900 are heated for 2 hours at a temperature of 100C to-gether with 790 g of water and 25 g of a 25 % aqueous ammo-nia solution, and then cooled to room temperature. A solu-tion having a pH of 6.8 and a polymer content of 16.1 ~ is obtained. 50 ~ of the carboxyl groups of the hydrolyzed copolymer are neutralized.
E X A M P L E 5:
a) In a vessel provided with agitator and reflux con-denser, 150 ~ of a copolymer of styrene and maleic an~
hydride (molar ratio 3:1) havirg an average molecular weight of 1,900 are heated f`or 3 hours at a temperature of 97C toget'ner with 720 g of water and 7.3 g of caustic ~ HOE 79/F 253 soda, and then cooled to room temperature. A dispersion having a pH of 5.6 and a polymer content of 17.6 ~ i9 obtained. 25 % of the carboxyl grcups of the hydrolyzed copolymers are neutralized. The mean diameter of the dispersed polymer particles is 0.038 /um.
b) 8 g of the dispersion obtained according to a) are heated to 85C together with 2 g of a 15 % aqueous solu-tion of sodium laurylsulfate, thus dissolving the copo-lymer.
c) 8 g of the dispersion obtained according to a) are heated to 90C together with 2 g of the 15 % aqueous so-lution of the emulsifier of Example 2c), thus dissolving the copolymer.
~5 E X A M P L_E S 6 to 8:
In a vessel provided with agitator and reflux conden-ser, 150 g each of a copolymer of styrene and maleic anhy-dride (molar ratio 3:1) having an average molecular weight of 1,900 are heated for varying periods of time to a tem-perature of 97C together with 720 g each of water anddifferent amounts of lithium hydroxide, and then cooled to room temperature. Details and properties of the solution or dispersion in question are listed in Table 1.
Table 1 Example 6 7 8 amount LiOH (g) 4.4 3.3 2.2 time of treatment (h) 2 2 3 result solution dispersion dispersion pH 5.3 5.1 11.7 polyrner content (%) 17.6 17.3 16.9 neutralized 25 18.7 12.5 carboxyl groups (%) __ ~ 12 - 0 _79/~ 253 E X A ~5 P L E J-In a vessel provided with agitator anà reflux conden~
ser, 150 g of a copolymer of styrene and maleic anhydride (molar ratio 3:1) having an average molecular weight of 1,900 are heated under a nitrogen blanket for 2 hours at a temperature of 96C iogether with 1,300 g of water~ 7.3 g of caustic soda, ,25 g of a 30 ~ solution of the emulsifier of Example 2c) and 12 g of sodium pyrosulfite, and then oooled to room temperatur~. A solution having a pH of 5.3 and a polymer content of 13.3 % is obtained. 25 % of the carboxyl groups of the hydrolyzed copolymer are neutralized.
The solution is adjusted with water to a concentration of 7.8 ~, for application in the polymerization of viny1 acetate.
E X A M P L E 10:
In a vessel provided with agitator and reflux conden-ser, 150 g of a copolymer of styrene and maleic anhydride (molar ratio 2:1) having an average molecular weight of 1,700 are heated for 2 hours under a nitrogen blanket to a temperature of 96C together with 1,300 g of water, 7.3 g of caustic soda, 12~ g of a 30 ~ aqueous solution of the emulsifier of Example 2c) and 12 ~ of sodium pyrosulfite, and then cooled to room temperature. A solution having a pH of 4.3 and a polymer content of 13 % is obtained. 18.6 ~
of the car~oxyl groups of the hydrolyzed copolymer are neu-tralized.
The solution is adiusted with water to a concentration o~ 7.8 % for use in the polymerization of vinyl acetate.
3o EXAMPLE OF APPLICATION 1:
510 g ¢f water, 1.77 g of a 6 % aqueous sodiu~ alkyl-sulfonate solution (mean chain leng~h of the alkyl group:
12 to 14 carbon atoms), and 2 g of a 30 % aqueous solution of the ammonium salt of nonylphenol oxethylated with 25 mols of ethylene oxide and then sulfatQd are intr-oduced into a vessel provlded with agitator t and then flushed with nitro~-- l3 ~ HOE 79/F 253 gen. After having added a solution of 2.25 g of ammoniurn persulfate in 20 g of water, the mixture is heated to a tem~erature of 50C. While rnaintaining this temperature, 750 g of vinyl acetate and a solution of 0.39 g of sodium formaldehyde-sulfoxylate in 50 g of water are added sepa-rately and uniformly within 3 hours to the mixture. With-in the 1st hourj the same amount of the emulsifier combi-nation is added again to t,he batch; withln the following 2 hours, 100 g of the copolymer solution obtained according to Example 9 and 1.87 g of the above alkylsulfonate solu-tion and 21.2 g of the above 30 % ammonium sa;t solution are added in corresponding doses. Subsequently 9 a solution of 0.75 g of ammonium persulfate in 30 g of water is added to the mixture, and the batch is heated for 30 minutes to 75C and then cooled to room temperature.
A coagulate-free polyvinyl acetate dispersion is ob-tailled whicn is adjusted to pH 6 with 3.2 g of 12.5 %
ammonia solution. The solids content of the dispersion is 50.8 ~, and the polymer particles have a mean diameter of 0.22 /um. The dispersion is stable to shearing;after a 2 minutes' agitation by means of a high-speed agitator (5000 rpm) no coagulate formation can be observed, and the mean particle size of the polymer has not changed.
EXAMPLE OF APPLICATION 2:
Example of application 1 is repeated; however, the co-pol.ymer solution of Example 10 is used instead of that of Example 9. The polyvinyl acetate dispersion obtained is coagulate-free. The solids content of the dispersion is 50.~ ~, and the polymer particles have a mean diameter of 0.18 /um. The dispersion is stable to shearing (test ac-cording to Example of application 1).
0MPARATIVE EXAMPI,E 1:
1,620 g oF the styrene/maleic anhydride copolymer used in Example 3 are a~itated for 6 hours 3/4 at a temperature of ~0C in 8,024 g of water with addition of 316 g of 14 - _OE ~9/F 253 caustic soda. Tne suspension obtained after coolinx to room temperature is filtered, thus obtaining a solid resi-due of 47 g. The filtrate has a pH of 10.0 and a polymer content of 18.7 %. 100 ~ of the carboxyl groups of the hydrolyzed copolymer are neutralized.
COMPARATIVE EXAMPLE 2:
Example 4 is repeated; however, the temperature of heating is 70C only. 50 ~ only of the styrene/maleic anhydride copolymer are dissolved; the solution has a pH
of 5.2.
COMPARATIVE EXAMPLE 3:
Example 4 is repeated, the temperature of heating be-ing only 70C, and the double amount of ammonia solutionis used. The solution obtained has a pH of 9.3.
COMPA~ATIVE EXAMPLE 4:
Example of application 1 is repeated while replacing the copolymer solution obtained in Example g by water.
The polyvinyl acetate dispersion obtained coagulates in the test for stability to shearing, COMPARATIVE EXAMPLE 5~
_ Example of application 1 is repeated while replacing the copolymer solution obtained in Example 9 by a corres-pondingly prepared solution of a styrene~maleic anhydride copolymer (molar ratio 1:1) having an average molecular weight of 1,600, the carboxyl groups of which being neu-tralized to an extent of 12.3 % after hydrolysis. The polyvinyl acetate dispersion obtained coagulates in the test for stability to shearing.
Claims (7)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Aqueous solution or dispersion of a hydrolyzed copolymer of styrene and maleic anhydride wherein the molar ratio of styrene to maleic anhydride is in the range of from 1.5:1 to 6;1, the molecular weight (number average) is from 500 to 80,000, 1 to 60 percent of the carboxyl groups of the copolymer are neutralized, and the pH of the solution or dispersion is below 7.
2. The solution or dispersion of claim 1, wherein the copolymer has a molar ratio of styrene to maleic anhydride of from 1.6:1 to 4:1.
3. The solution or dispersion of claim 1, wherein the copolymer has a molecular weight of from 800 to 30,000 (number average).
4. The solution or dispersion of claim 1, wherein from 6 to 50 percent of the carboxyl groups of the copolymer are neutralized.
5. A process for the preparation of an aqueous solution or dispersion of a hydrolyzed copolymer of styrene and maleic anhydride by hydrolysis of a styrene/maleic anhydride copolymer and partial neutralization with an inorganic neutralizing agent, which comprises heating a copolymer having a molar ratio of styrene to maleic anhydride of from 1.5:1 to 6:1 and a molecular weight (number average) of from 500 to 80,000 to a temperature of from 75 to 250°C in the presence of water and in the presence of an amount of ammonia, an alkali metal hydroxide or alkaline earth metal hydroxide, or zinc oxide that is sufficient to neutralize 1 to 60 percent of the carboxyl groups of the copolymer.
6. The process of claim 5, which comprises using the copo-lymer in a concentration of from 5 to 50 % by weight (relative to the total amount of copolymer and water).
7. The process of claim 5, which comprises heating in the presence of an anionic emulsifier.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP2938429.0 | 1979-09-22 | ||
| DE19792938429 DE2938429A1 (en) | 1979-09-22 | 1979-09-22 | AQUEOUS SOLUTION OR DISPERSION OF A STYRENE / MALEIC ACID ANHYDRIDE COPOLYMER, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1161581A true CA1161581A (en) | 1984-01-31 |
Family
ID=6081599
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000360619A Expired CA1161581A (en) | 1979-09-22 | 1980-09-19 | Aqueous solution or dispersion of a styrene/maleic anhydride copolymer and process for the preparation thereof |
Country Status (16)
| Country | Link |
|---|---|
| EP (1) | EP0025979B1 (en) |
| JP (1) | JPS5647412A (en) |
| AR (1) | AR222101A1 (en) |
| AT (1) | ATE3555T1 (en) |
| AU (1) | AU537112B2 (en) |
| BR (1) | BR8005999A (en) |
| CA (1) | CA1161581A (en) |
| DE (2) | DE2938429A1 (en) |
| DK (1) | DK156579C (en) |
| ES (1) | ES495100A0 (en) |
| FI (1) | FI72990C (en) |
| IE (1) | IE50353B1 (en) |
| MX (1) | MX156364A (en) |
| NO (1) | NO802786L (en) |
| PT (1) | PT71820B (en) |
| ZA (1) | ZA805810B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4818794A (en) * | 1986-09-19 | 1989-04-04 | Basf Aktiengesellschaft | Slightly crosslinked, water-soluble polymaleic acid, its preparation and its use |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU5017985A (en) * | 1984-11-05 | 1986-06-03 | Owens-Corning Fiberglas Corporation | Glass fiber size and impregnant compositions |
| CN1048190C (en) * | 1989-06-06 | 2000-01-12 | 普拉斯-斯托弗公司 | Highly concentrated aqeous suspension of minerals and/or fillers and/or pigments |
| IT1236966B (en) * | 1989-10-25 | 1993-05-07 | Ausidet Srl | PROCESS FOR THE PRODUCTION OF AQUEOUS SOLUTIONS OF ANTI-INCRUSTATION AGENTS AND SOLUTIONS SO OBTAINED |
| JPH07157524A (en) * | 1993-11-24 | 1995-06-20 | Union Carbide Chem & Plast Technol Corp | Vinyl copolymer containing macromonomer |
| FI991295A (en) * | 1999-06-07 | 2000-12-08 | Neste Chemicals Oy | A process for preparing styrene-maleic hydride copolymers |
| EP1405865A1 (en) * | 2002-10-04 | 2004-04-07 | DSM IP Assets B.V. | Process for preparing a polymer dispersion |
| JP5207097B2 (en) * | 2006-06-16 | 2013-06-12 | 星光Ｐｍｃ株式会社 | Filler modifier, filler slurry and paper making method |
| JP5515217B2 (en) * | 2008-01-11 | 2014-06-11 | 東洋インキＳｃホールディングス株式会社 | Dispersant, and pigment composition and pigment dispersion using the same |
| JP5614786B2 (en) * | 2013-05-09 | 2014-10-29 | 株式会社Adeka | Novel polymer and non-aqueous electrolyte secondary battery using the polymer |
| JPWO2015099170A1 (en) * | 2013-12-27 | 2017-03-23 | コニカミノルタ株式会社 | Acrylic resin film and method for producing the same, polarizing plate protective film, polarizing plate including the same, and liquid crystal display device |
| KR102440479B1 (en) * | 2018-07-11 | 2022-09-05 | 아라까와 가가꾸 고교 가부시끼가이샤 | Tackifying resin emulsion, water-based adhesive composition, and adhesive sheet |
| KR20240033249A (en) * | 2021-07-15 | 2024-03-12 | 산 노프코 가부시키가이샤 | Dispersants and water-based coating compositions |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2490489A (en) * | 1944-02-03 | 1949-12-06 | Du Pont | Process for copolymerizing maleic anhydride and styrene |
| US3444151A (en) * | 1965-09-07 | 1969-05-13 | Sinclair Research Inc | Styrene-maleic anhydride-amine polymers as emulsifiers in polymerization of vinyl monomers |
| GB1414918A (en) * | 1973-02-14 | 1975-11-19 | Ciba Geigy Uk Ltd | Treatment of water to prevent the deposition of scale |
| US3835122A (en) * | 1973-04-25 | 1974-09-10 | Atomic Energy Commission | Novel polystyrene product having rapid-post-irradiation decay of conductivity and process of making same |
| US3939108A (en) * | 1974-12-16 | 1976-02-17 | National Starch And Chemical Corporation | Cold water resistant starch-based adhesive containing styrene-maleic anhydride resin and fixed alkali |
| JPS5299104A (en) * | 1976-02-17 | 1977-08-19 | Toyo Ink Mfg Co | Composition of water dispersive material |
| JPS54107945A (en) * | 1978-02-14 | 1979-08-24 | Toagosei Chem Ind Co Ltd | Aqueous dispersion of finely granulated polymer |
-
1979
- 1979-09-22 DE DE19792938429 patent/DE2938429A1/en not_active Withdrawn
-
1980
- 1980-09-16 ES ES495100A patent/ES495100A0/en active Granted
- 1980-09-18 FI FI802934A patent/FI72990C/en not_active IP Right Cessation
- 1980-09-18 DE DE8080105591T patent/DE3063516D1/en not_active Expired
- 1980-09-18 AT AT80105591T patent/ATE3555T1/en not_active Application Discontinuation
- 1980-09-18 EP EP80105591A patent/EP0025979B1/en not_active Expired
- 1980-09-19 IE IE1958/80A patent/IE50353B1/en not_active IP Right Cessation
- 1980-09-19 NO NO802786A patent/NO802786L/en unknown
- 1980-09-19 CA CA000360619A patent/CA1161581A/en not_active Expired
- 1980-09-19 ZA ZA00805810A patent/ZA805810B/en unknown
- 1980-09-19 AU AU62551/80A patent/AU537112B2/en not_active Ceased
- 1980-09-19 DK DK399380A patent/DK156579C/en active
- 1980-09-19 BR BR8005999A patent/BR8005999A/en unknown
- 1980-09-19 JP JP12939380A patent/JPS5647412A/en active Granted
- 1980-09-19 PT PT71820A patent/PT71820B/en unknown
- 1980-09-19 AR AR282593A patent/AR222101A1/en active
- 1980-09-22 MX MX184014A patent/MX156364A/en unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4818794A (en) * | 1986-09-19 | 1989-04-04 | Basf Aktiengesellschaft | Slightly crosslinked, water-soluble polymaleic acid, its preparation and its use |
| US4886859A (en) * | 1986-09-19 | 1989-12-12 | Basf Aktiengesellschaft | Slightly crosslinked, water-soluble polymaleic acid, its preparation and its use |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5647412A (en) | 1981-04-30 |
| EP0025979A1 (en) | 1981-04-01 |
| FI72990C (en) | 1987-08-10 |
| AR222101A1 (en) | 1981-04-15 |
| ES8105356A1 (en) | 1981-06-16 |
| PT71820A (en) | 1980-10-01 |
| ES495100A0 (en) | 1981-06-16 |
| FI802934A (en) | 1981-03-23 |
| IE801958L (en) | 1981-03-22 |
| DE3063516D1 (en) | 1983-07-07 |
| JPH0336854B2 (en) | 1991-06-03 |
| AU6255180A (en) | 1981-04-09 |
| EP0025979B1 (en) | 1983-05-25 |
| NO802786L (en) | 1981-03-23 |
| DK156579C (en) | 1990-01-29 |
| MX156364A (en) | 1988-08-15 |
| IE50353B1 (en) | 1986-04-02 |
| DK399380A (en) | 1981-03-23 |
| PT71820B (en) | 1981-10-23 |
| FI72990B (en) | 1987-04-30 |
| ZA805810B (en) | 1981-10-28 |
| BR8005999A (en) | 1981-03-31 |
| AU537112B2 (en) | 1984-06-07 |
| ATE3555T1 (en) | 1983-06-15 |
| DE2938429A1 (en) | 1981-04-09 |
| DK156579B (en) | 1989-09-11 |
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