Patent GB-849823-A (GB)
Title: Preparation of polymers
IPC: C08F22/04
Filed: 1956-12-19
Abstract: Polymers containing in the main polymer chain a plurality of units of the formula:  <FORM:0849823/IV(a)/1> where R is hydrogen, a-CN group, an alkyl group of 1 to 10 carbon atoms, an aryl group, an aralkyl group, or chlorine, bromine, or fluorine, and R1 is hydrogen, chlorine, bromine, or fluorine, are made by polymerising in the presence of an inert diluent and a polymerisation catalyst a mixed anhydride of an alpha-betaunsaturated carboxylic acid of the formula, <FORM:0849823/IV(a)/2> and a saturated carboxylic acid having at least 2 carbon atoms and of the general formula R2-(COOH)n where n is an integer from 1 to 4, R and R1 have the meanings designated above and R2 is a hydrocarbon or halogenated hydrocarbon radical.  The polymerisation may also be effected in the presence of other monomers and polyunsaturated cross-linking agent containing a plurality of terminal CH2 = C< groups.  The mixed anhydrides may be made (1) reacting together acetylene carbon monoxide, and a monocarboxylic acid containing at least two carbon atoms in the presence of a metal carbonyl, or (2) reacting a ketene with an alpha-betaunsaturated monocarboxylic acid of the above formula, or (3) reacting the salt of an alpha-beta unsaturated monocarboxylic acid and an acid halide having the general formula:  <FORM:0849823/IV(a)/3> where X is a halogen, and R2 as previous, or (4) reacting an acid halide of the said alpha-betaunsaturated monocarboxylic acids and a salt of an acid of the formula R2(COOH)n. The Specification includes long lists of alpha-beta unsaturated monocarboxylic acids and saturated carboxylic acids and also cross-linking agents and other monomers.  The preferred mixed anhydrides are those of acetic and acrylic or methacrylic acids. In Example (1) polyacrylic anhydride is made by polymerising an acrylicacetic anhydride in the presence of caprylyl peroxide, in Example (2) polymethacrylic anhydride is made by polymerising methacrylic-acetic anhydride in the presence of benzoyl peroxide and benzene, in Example (3) polyacrylic anhydride is made by polymerising an acrylic-acetic anhydride in the presence of azodiisobutyronitrile, in Example (4) a mixed anhydride of acrylic and propionic acids are polymerised in a manner similar to Example (3), in Example V a mixed anhydride of phthalic acid and acrylic acid is polymerised in the presence of benzoyl peroxide, and in Example VI a mixed anhydride is made from sodium acrylate and adipoyl chloride. The polymers may be used for coating glass and metals and may also function as an adhesive in laminates. Specification 849,669 is referred to.ALSO:Mixed anhydrides of an alpha-beta unsaturated carboxylic acid of the formula:  <FORM:0849823/IV(b)/1> and a saturated carboxylic acid containing at least 2 carbon atoms and of the general formula R2-(COOH)n where n is an integer from 1 to 4 and R represents hydrogen, a-CN group, an alkyl group of 1 to 10 carbon atoms, an aryl group, an aralkyl group, or chlorine, bromine, or fluorine, R1 represents hydrogen, chlorine, bromine, or fluorine, and R2 a hydrocarbon or halogenated hydrocarbon radical are made by (1) reacting together acetylene, carbon monoxide, and a monocarboxylic acid containing at least two carbon atoms in the presence of a metal carbonyl, or (2) reacting a ketene with an alpha-beta unsaturated monocarboxylic acid of the above formula or (3) reacting the salt of an alpha-beta unsaturated monocarboxylic acid and an acid halide having the general formula <FORM:0849823/IV(b)/2> where X is halogen, or (4) reacting an acid halide of an alpha-beta unsaturated monocarboxylic acid and a salt of an acid of the formula R2(COOH)n. The unsaturated acid may be acrylic or methacrylic acid, alpha-chloro, bromo, fluoro, ethyl, propyl, butyl, amyl, hexyl, heptyl, nonyl, or decyl acrylic acid, alpha-phenyl acrylic acid, alpha-cyano acrylic acid, or alpha-benzyl acrylic acid.  The other carboxylic acid may be acetic, propionic, butyric, pentanoic, hexanoic, octanoic, benzoic, toluic, xylidinic, ethyl benzoic, trimethyl benzoic, alkyl and halogen-substituted benzoic acids, cyclohexane monocarboxylic acid, cyclopentane monocarboxylic acid, phenyl acetic, phenyl propionic, naphthyl acetic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, phthalic, isophthalic, terephthalic, naphthalic, biphenyl-o, o'-dicarboxylic, trimellitic, trimesic, cyclobutane-1, 3-dicarboxylic, cyclopentane dicarboxylic, or cyclohexane dicarboxylic acid.  In Example 1 an acrylic-acetic anhydride is made by bubbling gaseous ketene through acrylic acid, in Example 2 a methacrylic-acetic anhydride is made by passing ketene into a benzene-methacrylic acid solution, in Example 3 an acrylic-acetic anhydride is made by mixing acetic acid and acetic anhydride with acetylene and adding nickel carbonyl portionwise, in Example 4 an acrylic propionic anhydride is made by mixing acrylyl chloride and sodium propionate in dry benzene, in Example 5 a mixed anhydride of phthalic acid and acrylic acid is made by mixing sodium acrylate and phthalyl dichloride in dry benzene, whilst in Example 6 a mixed anhydride is made by reacting adipoyl chloride and sodium acrylate in dry benzene.  The mixed anhydrides polymerize in the presence of initiators to high molecular weight polymers. Specification 849,669 is referred to.