Patent GB-975367-A (GB)
Title: Process for the production of foamed materials
IPC: C08J9/08
Filed: 1962-04-11
Abstract: Carboxylic acid-carbonic acid mixed anhydrides are obtained by the reaction of the corresponding carboxylic acid salts with halogenocarbonic acid esters, particularly at pH 5.5 to 8.5, in the presence of water and possibly of amines, quaternary ammonium bases or their salts. They are used as blowing agents for synthetic resins (see Divisions C3). The anhydrides may be derived from alkyl, cycloalkyl, aralkyl or alkylaryl alcohols and carboxylic acids. Some 20 specific compounds are listed. In them the carboxylic acid portion is derived variously from acetic, propionic, sebacic, acrylic, methacrylic, crotonic, sorbic, benzoic, p-nitrobenzoic, 3-chlorobenzoic, isophthalic, fumaric and terephalic acids; the radicals from which the ester portion of the carbonic acid ester is derived are variously ethyl, methyl, butyl, phenyl, p-tert butylphenyl. Also specified are anhydrides of butane-1, 4-diol, hexane-1, 6-diol and diethylene glycol bis carbonic acid acid esters with carboxylic acids.ALSO:In a process for the production of foamed materials thermoplastic synthetic resins are heated which contain compounds having carboxylic acid-carbonic acid ester groups, or thermoplastic synthetic resins are heated which contain in the molecule carboxylic acid-carbonic acid ester anhydride groups and optionally a content of compounds containing carboxylic acid-carbonic acid ester groups.  The heating causes conversion of the mixed anhydride groups to ester groups, carbon dioxide being liberated. The synthetic resins may contain the mixed anhydride groups as side chains and/or end groups or as part of the main chain. They may also contain residues of polymerizable unsaturated dicarboxylic acids, and may then optionally be used in admixture with monomeric polymerizable compounds and polymerisation catalysts.  There are listed a large number of mono-bis- and polymeric mixed anhydrides. They can contain hydrocarbon groups or may have further substituents such as halogen, nitro, methoxy or ester radicals. They can be obtained by the reaction of the corresponding carboxylic acid salts with halogeno-carbonic acid esters. By analogous methods polymers bearing hydroxyl or carboxyl groups in side chains or end groups can be converted to the corresponding macro-molecular mixed anhydrides. Suitable polymers for this reaction are polyvinyl alcohol, polyacrylic acids, cellulose or partially acylated or alkylated cellulose, and polyethers or polyesters with free hydroxyl and/or carboxyl groups. Polymers containing carboxylic acid-carbonic acid ester groups as side chains can be obtained from the polymerization of unsaturated mixed anhydrides, for example, methacrylic acid carbonic acid ethyl ester anhydride, alone or with other monomers. Polymers having the mixed anhydride group as part of the main chain can be obtained by the reaction of dicarboxylic acid with bis-chlorocarbonic acid esters of diols; or of bis-phenol-bis chlorocarbonic acid ester, a bisphenol and a dicarboxylic acid, with or without a dicarboxylic acid dichloride. Also suitable is a reaction product of hexane-1, 6-diol bis chlorocarbonic acid ester, isophthalic acid and excess hexane diol, which has been further reacted with a diisocyanate. The polymeric compounds containing the mixed anhydride groups can be used in admixture with thermoplastic polymers. A polymer containing mixed anhydride groups and polymerisable bonds can be mixed with a monomer and the peroxide and be simultaneously cross-linked and foamed. Of this type is a bis-chlorocarbonic acid ester of bis-phenol A with fumaric acid or a fumaric acid ester with a diol. In example (1) a mixture of styrene and benzoic acid-carbonic acid methyl ester anhydride is polymerized in the presence of methyl ethyl ketone peroxide and benzoyl peroxide. The product is chopped into granules which are heated to cause melting and foaming. In other examples the material foamed comprises (2) a copolymer of methacrylic acid-carbonic acid anhydride and styrene; (3) a mixture of a poly carbonate from bisphenol A and isophthalic acid-bis-carbonic acid methyl ester anhydride; (4) a polymeric mixed anhydride of isophthalic acid and 2,2-(4,41-dihydroxyphenyl)-propanebis carbonic acid, mixed with a polycarbonate; (5) a polymer prepared by reacting phosgenated bisphenol A with isophthalic acid in the presence of N,N-dimethylcyclohexylamine; (6) a mixture of a bisphenol A polycarbonate with a polymeric mixed anhydride from sebacic acid and 2,2-(4,41-dihydroxy-diphenyl)-propane-bis-carbonic acid.