Patent GB-911808-A (GB)
Title: New polymerisation products containing epoxy groups and process for their preparation
IPC: C08F2/22
Filed: 1961-05-31
Abstract: New products are obtained by polymerizing, with or without another monomer, a monoepoxide of formula <FORM:0911808/IV(a)/1> where R1 to R8 each represents a monovalent substituent such as a halogen or hydrogen atom, or an alkoxy group or an aliphatic, cycloaliphatic, araliphatic or aromatic hydrocarbon residue, preferably an alkyl group with 1 to 4 carbon atoms, and R1 and R5 together may also represent an alkylene such as a methylene group; X1 and X2 each represents a hydrogen atom or methyl group and X3 a hydrogen atom or an alkyl group with 1 to 4 carbon atoms. Specified are the epoxidized acetal [3-vinyl-2:4-dioxospiro-(5,5)-9:10-epoxy-undecane] called product (1), the epoxidized acetal [3-vinyl-7-methyl-2:4-dioxospiro-(5:5)-9:10-epoxy-undecane] (product 2) and the epoxidized acetal [3-propenyl-2:4-dioxospiro-(5:5)-9:10-epoxy-undecane] (product 3), while examples detail the preparation of the terpolymer: product 1-ethyl acrylate-acrylonitrile; the terpolymer: product 1-butyl acrylate-acrylonitrile; the terpolymer: product 1-butyl acrylate-styrene; the copolymers: product 1 (70)-butyl acrylate (30); product 1 (80)-ethyl acrylate (20); the terpolymer: product 1-ethyl acrylate-vinyl acetate; the homopolymer of product 1; the terpolymer product 2-ethyl acrylate-acrylonitrile; the terpolymer: product 3-ethyl acrylate-acrylonitrile; the terpolymer: product 1-2-ethylhexyl acrylate-acrylonitrile; the copolymers: product 1-acrylonitrile and product 1-styrene; the tetrapolymer: product 1-n-butyl acrylatevinylidene chloride-acrylonitrile; the tetrapolymer: product 1-n-butyl acrylate-vinylidene chloride-acrylic acid; the terpolymer: product 1-n-butyl acrylate-acrylic acid; the tetrapolymer: product 1-2-ethylhexylacrylate-acrylic acid-methylolacrylamide and the tetrapolymer product 1-2-ethylhexyl acrylate-acrylic acid and acrylamide.  Other monomers are given.  The polymerization may take place as block, solvent or emulsion, using peroxy catalysts, emulsifiers, protective colloids, and modifiers. The products may be cross-linked with basic or acidic compounds, e.g. amines, formaldehyde resins, isocyanates and many other well-known curing agents.ALSO:Monoepoxides of formula:-<FORM:0911808/IV (b)/1> where R1 to R8 each represents a monovalent substituent such as a halogen or hydrogen atom, or an alkoxy group or an aliphatic, cycloaliphatic, araliphatic or aromatic hydrocarbon residue and R1 and R5 together may represent an alkylene group; X1 and X2 each represents a hydrogen atom or methyl group and X3 a hydrogen atom or an alkyl group with one to four carbon atoms, are prepared by acetalising an aldehyde or ketone of formula:- <FORM:0911808/IV (b)/2> with a dialcohol of formula <FORM:0911808/IV (b)/3> and then epoxidising the product.  Specified aldehydes and ketones are acrolein, methacrolein, crotonaldehyde, methyl vinyl ketone and ethyl vinyl ketone while specified dialcohols are the 1:1 - bis - [hydroxymethyl]] derivatives of cyclohexene-3, of 6-methylcyclohexene-3, of 2:4:6 - trimethyl - cyclohexene-3, of 2:5-endomethylen-cyclohexene-3 and of -4-chloro-cyclohexene-3. The acetalisation and ketalisation follow the usual pattern of heating the aldehyde or ketone with the dialcohol in the presence of an acidic catalyst such as sulphuric, phosphoric or p-toluene sulphonic acid.  The epoxidisation conditions must be such that only the carbon to carbon double bond in the cyclohexene ring is epoxidised e.g. by using an organic peracid e.g. peracetic, perbenzoic, peradipic, and monoperphthalic acids.  In Examples (1) acrolein and 1:1-bis-[hydroxymethyl]-cyclohexene-3 are heated to 80 DEG C. in the presence of sulphuric acid and the product epoxidised p  with peracetic acid in sodium acetate-benzene, (2) a zinc chloride-phosphoric acid catalyst is used to produce the acetal from acrolein and 1:1 - bis - [hydroxymethyl] - 6 - methylcyclohexene-3 which is then epoxidised and (3) the acetal from crotonaldehyde and 1:1-bis-[hydroxymethyl]-cyclohexene-3 is prepared and epoxidised.