Patent GB-838007-A (GB)
Title: Improvements in the production of copolymers from unsaturated polyester resins
Inventor: WILLERSINN HERBERT
IPC: C08F283/01
Filed: 1958-04-25
Abstract: Ethers of methylol-glyoxal-ureines of the formul  <FORM:0838007/IV (b)/1> or <FORM:0838007/IV (b)/2> where R is hydrogen or an aliphatic, cycloaliphatic or aromatic radical, R1 is hydrogen or the radical of a beta, gamma-ethylenically unsaturated alcohol or of a saturated alcohol and R11 is methyl or methylol etherified with a beta, gamma-ethylenically unsaturated alcohol or a saturated, heterocyclic, or aromaticaliphatic alcohol, or an aliphatic, cycloaliphatic, heterocyclic, aromatic or aliphatic aromatic group, are prepared by condensing vicinal dioxo compounds with urea or its derivatives to form the ureines which are reacted with formaldehyde and an alcohol to form the methylol-ether derivative. The desired compounds for use as copolymers (see Group IV (a)) should contain at least two methylol groups etherified with a beta, gamma unsaturated alcohol which may be allyl, methallyl, chlorallyl, crotyl, cyclohexenyl or cyclopentenyl alcohol. Specified compounds are tetraallyl ether of tetramethylol-glyoxal diureine, diallyl ether of dimethylol-glyoxal diureine, trially trimethylol-glyoxal diureine and monobutyldiallyl ether of trimethylol-glyoxal di-ureine.ALSO:Unsaturated polyester resins are copolymerized with a methylol-glyoxal-monoureine which has been etherified with at least 2 mols. of a beta, gamma-ethylenically unsaturated alcohol and, if desired, another copolymerizable monomer.  The etherified methylol-glyoxal-monoureines have the formula <FORM:0838007/IV (a)/1> and the diureines the formula <FORM:0838007/IV (a)/2> where R is hydrogen, alkyl, cycloalkyl or aryl, R1 is hydrogen or the radical of a beta, gammaunsaturated alcohol or of a saturated alcohol and R11 is hydrogen, aliphatic, cycloaliphatic, heterocyclic, aromatic or aliphatic-aromatic groups or a beta-gamma ethylenically unsaturated group attached to the nitrogen by an oxymethylene group, provided that at least two of the R11 groups are derived from a beta, gamma unsaturated alcohol.  The unsaturated radical may be allyl, methallyl, chlorallyl, crotyl cyclopentenyl or cyclohexenyl. Suitable compounds are tetra-allyl ether of tetramethylol-glyoxal-diureine, diallyl ether of dimethylol-glyoxal-diureine, triallyl ether or monobutyl-diallyl ether of trimethylol-glyoxal-diureine.  The polyesters can be formed from ethylene glycol, 1,2- or 1,3-propylene glycol, 2,2-dimethyl-1,3-propanediol, the butylene glycols, 1,6 - hexanediol, 1,8 - octanediol or 1,4 - cyclohexanediol, to which may be added glycerine, trimethylol-propane, pentaerythritol or butanetriol and maleic, fumaric, itaconic, citraconic, aconitic or chlormaleic acid to which may be added up to 70% with reference to unsaturated acid of succinic, glutaric, adipic, pimelic, sebacic, suberic, alpha-methylglutaric, oxadibutyric, sulphone - dibutyric, phthalic, endomethylenetetrahydrophthalic, hexachlorendomethylenetetrahydrophthalic, tetrachlor- or tetrabromphthalic or phenyldibutyric acid.  The third, optional, monomer may be styrene, an alkyl or halogenostyrene, divinylbenzene, vinylnaphthalene, vinyl acetate, propionate or succinate, diallyl phthalate or maleate, triallyl phosphate, vinyl methyl ketone, isobutyl vinyl ether, butane-1,4-diol-divinyl ether, glycol diallyl ether, pentaerythritol tetra-allyl ether, ethyl acrylate or methacrylate, glycol dimethacrylate, ethyl alphachloracrylate, acrylo- or methacrylonitrile, acrylamide or methacrylamide, vinyl pyridine, N-vinylcarbazole, N-vinylpyrrolidone, N-vinylcaprolactam, triallyl cyanurate, methyl vinyl sulphone or divinyl sulphone.  The polymerizable mixture may contain 5-70% of the ether and 10-70% of the optional monomer.  Polymerization may be effected by ultraviolet light or catalysts such as methyl ethyl ketone peroxide, benzoyl peroxide, cyclohexanone peroxide, tertiary butyl hydroperoxide, lauroyl peroxide, azo-bis-isobutyronitrile, azo-bis-isobutyric acid methyl ester or redox systems such as benzoyl peroxide and dimethylaniline or cyclohexanone peroxide and lauryl mercaptan in amounts of 0.5-3%.  Temperatures up to 160 DEG  C. and pressures up to 10 atmospheres are used.  The mixtures can be used to form castings or as lacquers in which latter case metal driers are preferably added e.g. naphthenates, resinates, octoates or linoleates of iron, cobalt, nickel, manganese, chromium, lead, zinc, cerium, aluminium or calcium.  Solvents can also be added e.g. toluene, xylene, ethylene glycol monomethyl ether monoacetate, acetone, methyl ethyl ketone, cyclohexanone, methanol, ethanol, propanol, butanol or tetrahydrofuran.  A phenol, aminophenol or quinone can also be added in amounts of 0.005-0.1% as inhibitor.