2,855,387

United States
1.
Patent Office 2
Patented Oct. 7, 1958

is a hard clear mass having a slight yellow tint. The

product may be pulverized to form a molding powder.
2,855,387 The powder is soluble in water and aqueous solutions
TERPOLYMER OF MALEIC ANHYDRIDE, VINYL 5 thereof are useful as textile sizes and in coating compo
ACETATE AND ALKYL ACRYLATE sitions. The viscosity of the 5% aqueous solutions of
the powder ranges from 30-45 centipoises at 25 C.
Gerald R. Barrett, Winchester, Mass, assignor to Mon Example III
Santo Chemical Company, St. Louis, Mo., a corpora
tion of Delaware Mix together 42 parts of vinyl acetate, 48 parts of
No Drawing. Application December 20, 1954 O maleic anhydride, 10 parts of ethyl acrylate, 0.1 part
Serial No. 476,553 of benzoyl peroxide, 0.3 part of tertiary butyl perben
zoate, and 0.06 part of beta nitro styrene. Polymerize
4 Claims. (Cl. 260-78.5) the mixture using the same cycle as shown in Example
II. The product is similar to that of Example II except
This invention relates to modified copolymers of vinyl 15 that the viscosity of a 5% aqueous solution at 25 C.
acetate and maleic anhydride. More particularly the ranges from 7-12 centipoises. .
invention relates to terpolymers of vinyl acetate, maleic Example IV
anhydride and esters of acrylic or methacrylic acids. Mix together 43 parts of vinyl acetate, .50 parts of
Vinyl acetate copolymerizes quite rapidly with maleic
anhydride usually in substantially equimolar proportions. 20 maleic anhydride and about 7 parts of methyl methac
The copolymer is insoluble in eithed monomer and separ rylate and add to the mixture 0.05 part of benzoyl per
ates out as a gel before polymerization is complete. oxide, 0.3 part of tertiary butyl perbenzoate and about
These gels are hard to purify and contribute to the 0.015 part of beta nitro styrene. Initiate polymeriza
production of heterogeneous materials. Furthermore the tion by a short preliminary heating at 50-70 C, con
copolymers of vinyl acetate and maleic anhydride are tinue polymerization with agitation at 40-60 C. for about
quite hard and brittle. 20 hours and finish the polymerization by gradually in
One object of this invention is to provide new terpoly creasing the temperature to 105 C. over a period of about
mers of vinyl acetate, maleic anhydride and alkyl esters 36 hours. The product is a hard clear and nearly color
of acrylic and methacrylic acids. less mass. It may be pulverized to form a molding
A further object is to modify copolymers of vinyl powder. The powder is soluble in water and 5% aqueous
acetate and maleic anhydride to render them softer and solutions thereof have a viscosity of 20-25 centipoises at
less brittle. 25 C. The aqueous solutions are useful as textile sizes
Another object is to modify vinyl acetate-maleic anhy andTheas terpolymers
ingredients of aqueous coating compositions.
dride copolymers so that substantially no gel formation merizing together aofmixture this invention are prepared by poly
of vinyl acetate, maleic an
occurs in the polymerization reaction.
These and other objects are attained by copolymerizing in the presence of a free radicalacrylic
hydride and an alkyl ester of or methacrylic acid
producing catalyst. The
vinyl acetate with maleic anhydride and an alkyl ester polymerization is best carried out in a mass process or
of acrylic or methacrylic acid in a mass polymerization in an organic liquidinert to the reactants which is a solvent
system in the presence of a free radical producing catalyst.
The following examples are given in illustration and 40 for the monomers but not for the polymers. The poly
merization reaction should be initiated by a relatively
are not intended as limitations on the scope of this inven short heating cycle at 50–70° C. Thereafter the tempera
tion. Where parts ade mentioned they are parts by ture should be reduced about 10° C. and the reaction
weight. continued with or without agitation for from 15-25 hours.
Example I 45 Then the temperature should be raised slowly to from
Mix together about 45 parts of vinyl acetate, about 100-120° C. over a period of from 30-40 hours. To
49 parts of maleic anhydride and about 5 parts of ethyl insure completion of the reaction the temperature is held
acrylate. Add to the mixture, about 0.3 part of tertiary at the highest point for about 1-3 hours.
butyl perbenzoate and about 0.05 part of di(tertiary The amount of vinyl acetate should be regulated by the
butyl) peroxide. Remove air from the reaction vessel 50 amount of maleic andydride so that a mol percent ratio
by flushing with nitrogen and heat the mixture at 50-70 of vinyl acetate to maleic anhydride of from 52-48 to
C. until the reaction begins as evidenced by a thicken 50-50 is attained. The amount of alkyl acrylic or meth
ing of the reaction medium. Then reduce the tempera acrylic ester may be varied from 1 to about 30 mol per
ture to 40-60° C. and maintain the reaction mixture at cent of the final product.
this temperature for about 20 hours. Then increase the 55 The esters which are operative in this invention are
temperature slowly and gradually to about 105 C. over alkyl esters of acrylic and methacrylic acids in which the
a period of about 36 hours. The final product is a hard alkyl groups contain from 1-8 carbon atoms including
solid which can be pulverized to form a fine powder. methyl, ethyl, propyl, butyl, isobutyl, 2-ethyl hexyl, octyl
The product is soluble in water, and the aqueous solu etc. groups.
tions thereof are particularly suitable for sizing textile 60 The catalysts which may be used are free radical pro
yarns. It has a viscosity of about 15 centipoises in a 5% ducing catalysts especially the peroxy type catalysts includ
aqueous solution at 25 C. ing the organic and inorganic peroxides and hydro
Example II peroxides, esters of peracids such as peracetic acid and
perbenzoic acid, etc. Other free radical producing cat
Mix together 42 parts of vinyl acetate, 48 parts of 85 alysts such as azonitriles, other organic azo compounds,
maleic anhydride, 10 parts of ethyl acrylate, 0.05 part tetra-alkyl diamino diphenyl methanes, etc., may be used.
of benzoyl peroxide, and 0.3 part of tertiary butyl per For many purposes it is desirable to use two or more cat
benzoate. Heat the mixture for a short time at 50-70 alysts. The total amount of catalyst may vary between
C. to initiate the reaction and then maintain the reaction 0.1 and 0.5 part per 100 parts of total monomer.
mixture at 40-60° C. for about 20 hours. Then raise 70 Using the mass process described above and the pro
the reaction temperature slowly and gradually to about portions of vinyl acetate, maleic anhydride and acrylic or
105 C, over a period of about 36 hours, The product methacrylic ester shown, substantially no gel separation
 3
2,855,887
4
is detected at any stage of the preparation of the ter contain from 1 to 8 carbon atoms, the ratio of vinyl
polymer. If the acrylic or methacrylic ester is omitted acetate to maleic anhydride on a mol percent basis vary
from the reaction, gel separation occurs during the heat ing from 52-48 to 50-50 and the amount of ester varying
sing period at 50-70° C. and the product is a heterogene from 1-30 mol percent of the terpolymer.
ous mixture. 5
The properties of the products vary with the type of 2. A terpolymer as in claim 1 wherein the ester is ethyl
acrylate.
ester and the amount of ester used. Most of the products 3. A terpolymer as in claim 1 wherein the ester is
are completely water-soluble without the use of alkali but methyl methacrylate.
the esters having the longer carbon chains reduce the 4. A process for preparing a terpolymer of vinyl
solubility to the point where a small amount of alkali is 10 acetate. maleic anhydride and an ester taken from the
necessary. The viscosity of the products as measured in group consisting of alkyl esters of acrylic and methacrylic
5% aqueous solutions at 25 C. may vary between 5 and acids in which the alkyl groups contain from 1 to 8 carbon
100 centipoises depending on the reaction conditions and atoms, which comprises mixing the three monomeric com
the particular ester used. .. . .
ponents with a free radical producing catalyst, heating
For some purposes it is desirable to ensure that the the mixture at 50–70° C. to initiate polymerization, then
viscosity of the products will be on the lower part of the heating the mixture at 40-60° C. for 15-25 hours and
range. To effect this lowering of viscosity, a small then gradually raising the temperature to 100-120. C.
amount of a polymerization controlling agent such as the over a period of 30-40 hours, the ratio of vinyl acetate to
beta nitro styrene of the examples may be included. analeic anhydride on a mot percent basis varying from
Other materials may be substituted for the beta nitro 20 52-48 to 50-50 and the amount of ester varying from
styrene such as, for example, various mercaptains. 1-2 mol percent of the terpolymer.
The terpolymers of this invention are particularly use
ful in the form of aqueous solutions as sizing agents for References Cited in the file of this patent
various textiles and especially for nylon yarns. Since UNITED STATES PATENTS
they are tougher than copolymers of vinyl acetate and 25
maleic anhydride, the terpolymers provide a more abra 2,047,398 Voss et al. ------------- July 14, 1936
sion resistant size which eliminates many of the difficulties 2,616,867 Rossin ----------------- Nov. 4, 1952
previously experienced in the weaving of sized nylon 2,640,039 Williams --------------- May 26, 1953
yarns.
What is claimed is: 30 OTHER REFERENCES
1. A terpolymer of vinyl acetate, maleic anhydride and Seymour et al.: "Ind. and Eng. Chem.' vol. 41, No.
an ester taken from the group consisting of alkyl esters 7 (1948), pages 1509-1513.
of acrylic and methacrylic acids in which the alkyl groups