Patent ES-318376-A1 (ES)
Title: Olefinically unsaturated cyanic acid aryl esters and polymers thereof
IPC: D06M15/267
Filed: 1965-10-09
Abstract: Aryl esters of cyanic acid containing an olefinically unsaturated group, e.g. esters of formula <FORM:1047859/C2/1> wherein R1 is H, CH3 or Cl, R2 is H, an alkyl group of 1 to 4 carbon atoms or Cl and X is -O- or -NH- are prepared according to the method of Specification 1,007,790 by reaction of the corresponding phenol with a cyanohalide and are subsequently polymerized. The esters prepared are 4-methacrylaminophenyl cyanate, 4-methacrylyloxy phenyl cyanate, 4-acryl-aminophenyl cyanate, 2,6-dichloro-4-methacryl-aminophenyl cyanate, 2-methyl-5-methacry-aminophenyl cyanate and 2-methyl-4-metl-acrylaminophenyl cyanate.ALSO:Cross-linked polymers are obtained by preparing homopolymers of mono-olefinically unsaturated aryl esters of cyanic acid, or copolymers thereof with 99.5 to 80% by weight, based on the total monomer weight, of other olefinically unsaturated compounds, and subjecting the polymers to heating at 70 DEG to 200 DEG C. and/or treatment with alkaline-reacting substances. The preferred esters are of formula <FORM:1047859/C3/1> wherein R1 is H, CH3 or Cl, R2 is H, an alkyl group of 1 to 4 carbon atoms or Cl and X is O or NH. A list is given of substituents which may be present in the aryl radical of other suitable esters, in which the olefinically unsaturated group may be attached directly to the aryl nucleus or by a thiolcarboxylic acid, thiocarboxylic acid, dithiocarboxylic acid or thioamidecarboxylic acid group, or as in Formula 1. Specified comonomers are a ,b -unsaturated carboxylic acids, e.g. (meth)acrylic acid, and esters thereof with alcohols containing 1 to 20 carbon atoms or cycloaliphatic alcohols containing 5 to 20 carbon atoms, amides or nitriles of said acids, vinyl ethers, esters, ketones or halides, e.g. vinyl ethyl ether, vinyl acetate, and vinyl chloride, conjugated diolefins of 4 to 6 carbon atoms, e.g. butadiene, isoprene, 2,3-dimethyl butadiene and chloroprene and aromatic vinyl compounds, e.g. styrene and a -methyl styrene. Polyunsaturated monomers may also be incorporated, e.g. glycol di(meth)acrylates, allyl(meth)acrylates, divinyl benzene, triallyl cyanurate, bis-(4-methacrylaminophenyl)-imino carbonic ester, and bis-(4-methacrylaminophenyl)-4-methacrylhydroxyphenylimino carbonic ester. Preferred copolymers are "soft" ones containing (a) 0.5 to 20% of cyanic acid ester 1, (b) 99.5 to 40% of a plasticizing monomer such as esters of acrylic acid and C1 to C8 alcohols, butadiene or isoprene and (c) 0 to 40% of a hardening monomer, e.g. styrene, a -methyl styrene, acrylonitrile, vinyl chloride, vinylidene chloride or esters of methacrylic acid and C1 to C4 alcohols and " hard " copolymers in which the amount of (b) is 0 to 40% and that of (c) is 99.5 to 40%. The homopolymers are prepared by solution or precipitation polymerization in e.g. benzene, toluene or CHCl3, using organic peroxides, peroxycarbonates or azo compounds as catalysts. The copolymers are prepared by bulk, solution, suspension or emulsion polymerization using conventional stabilizers, emulsifiers, catalysts and solvents (examples are listed). Graft polymers may be prepared by polymerizing the monomers in the presence of preformed polymers, e.g. polybutadiene. Modifiers such as alkyl mercaptans and diisopropyl xanthogenate may be used during polymerization. Aqueous emulsion polymerization is preferred, in which case the polymer is cross-linked by adjusting the pH of the dispersion to an alkaline value with NaOH, KOH, Na2CO3, K2CO3 or KHCO3, applying the dispersion to a substrate and evaporating the water at room or elevated temperature or, alternatively, merely by heating the neutral dispersion to 70 DEG to 200 DEG C. In Example 1 copolymers of 4-(acrylaminophenyl)-cyanate or 4-(acryloxyphenyl)-cyanate, or the corresponding methacrylylesters, and n-butyl acrylate are produced in aqueous emulsion, using an oleyl alcohol/ethylene oxide reaction product and a sodium salt of a naphthalene sulphonic acid/formaldehyde condensation product as emulsifiers and potassium persulphate and sodium pyrosulphate as catalyst, and cross-linked by adjusting the pH to 10 with aqueous NaOH and drying at room temperature. In Example 2 copolymers of 4-(methacrylaminophenyl)-cyanate, or the corresponding acryl ester, and ethyl acrylate are produced using a p-nonyl phenol/ethylene oxide reaction product as emulsifier and crosslinked at pH9. The copolymer produced in Example 3 is of 4-(methacrylaminophenyl)-cyanate or 4-(methacrylyloxyphenyl)-cyanate and n-butyl acrylate, acrylonitrile and acrylic acid, the emulsifier being the sodium salt used in Example 1 and an o-benzyl phenol/ethylene oxide product. Copolymers of 4-(methacrylaminophenyl)-cyanate or 4-(acrylyl or methacrylyloxyphenyl)-cyanate and n-butyl acrylate are produced in Example 4 by solution polymerization in toluene, with azoisobutyronitrile as catalyst. In Example 5, 4-(methacrylaminophenyl)-cyanate is homopolymerized in benzene, with azodiisobutyronitrile as catalyst.