GB1130308A - Process for manufacturing polymers - Google Patents

Abstract

1,130,308. Halogen-containing polyesters. UNIVERSAL OIL PRODUCTS CO. 10 Feb., 1966, No. 5837/66. Headings C3P and C3R. A cured polyester is produced by copolymerizing (a) an unsaturated monomer with (b) an unsaturated polyester obtained by the reaction of (1) a polyhydric alcohol, (2) a polybasic acid or an ester or anhydride thereof, (3) a polyhalopolyhydromethanonaphthalenedicarboxylic acid or an anhydride or ester thereof and (4) a phosphoric acid. Compound (3) is preferably a 5,6,7,8,9,9-hexahalo-1,2,3,4,4a,5- 8,8a - octahydro - 5,8-methano - 2,3 - naphthalenedicarboxylic acid or anhydride or a dialkyl ester thereof, e.g. the hexachloro-, hexabromo- and dibromo, tetrachlorocompounds. Any phosphoric acid or a precursor thereof, e.g. P 2 O 5 is used. Suitable polyhydric or polybasic compounds (1) and (2) include 2- butene-diol-1,4- pentaerythritol, butanediol-1,4, alkylene and dialkylene glycols, glycerol, isopropylidene bis (p-phenyleneoxypropylene- 2), maleic acid or anhydride, citraconic, itaconic, phthalic, isophthalic tetrachlorophthalic, and saturated dicarboxylic acids, e.g. succinic acid, phthalic and succinic anhydrides, and dialkyl ester of these acids. The phosphoric acid is incorporated during preparation of the unsaturated polyester, in which esterification catalysts and chain stoppers may be employed. The preferred polyester comonomer (a) is styrene, others specified being substituted styrenes, alkyl esters of saturated and unsaturated mono- and dicarboxylic acids, alkyl alcohol, vinyl phenol, vinyl acetate and alkyl (meth) acrylates. The polyester-monomer mixture may include an inhibitor, e.g. a quinone, hydroquinone, phenol, catechol, cresol or aromatic amine, tannic acid or butylated hydroxy anisole. The polymerization is initiated thermally, photo-chemically or catalytically with e.g. an organic peroxide, hydroperoxide, peracid or ozonide. Promoters such as SnCl 2 , FeCl 2 , cobalt naphthenate, dimethyl aniline, dibutylamine and mercaptans can be used. Glass fibres may be included in the polyester-monomer mixture. In examples poyesters are prepared from 5,6,7,8,9,9-hexachloro-1,2,3,4,4a,5,8,8aoctahydro - 5,8 - metharo - 2,3 - naphthalenedicarboxylic anhydride, maleic anhydride, orthophosphoric acid and (I) ethylene glycol and diethylene glycol, (II) diethylene glycol, (III) ethylene glycol or (IV) propylene glycol. The resulting polyesters are copolymerized, in bulk and in a mould, with styrene, using in Examples I to III tertiary butyl anisole as inhibitor and in Example IV, hydroquinone. In each example the catalyst is methyl ethyl ketone peroxide and the promoter is cobalt naphthenate.