Patent GB-1109493-A (GB)
Title: Esters of unsaturated carboxylic acids
IPC: D04H1/64
Filed: 1965-05-12
Abstract: Polymers or copolymers of the unsaturated carboxylic esters of formula <FORM:1109493/C3/1> in which R is a hydrogen atom or methyl group, m is 1, 2 or 3, p is 1, 2, 3 or 4, x is 1, 2, 3 or 4, A is an alkylene group (2-4C) and Z is a substituted morpholinone group <FORM:1109493/C3/2> or a substituted glycine group <FORM:1109493/C3/3> in which Y is an alkylene group (2 or 3C); either R1 is a hydrogen atom, an alkyl group (1-8C), or a phenyl group and R2 is hydrogen, an alkyl group (1-8C) or R1 and R2 are joined in a ring of 5 to 7 C atoms with the proviso that when p is greater than 1 then m is 1, and when m is greater than 1 then R is hydrogen (see Division C2) are prepared by vinyl addition processes. Hydrolysis of the cyclic radical to form the glycine radical during the polymerization in aqueous media varies with the temperature and acidity or alkalinity of the medium, or the hydrolysis may be brought about after polymerization by heating in aqueous medium. Conventional free-radical catalysts may be used and copolymers with H2C=C< group containing compounds such as vinyl esters; the nitriles, amides and esters of a ,b -monoethylenically unsaturated acids; monovinyl aromatic compounds; vinyl or vinylidine chloride; and polyethylenically unsaturated monomers are mentioned.  Heat curing of the polymer or copolymer compositions cyclize the substituted glycine type esters to the more insoluble and heat resistant form.  The copolymers are used as coating or impregnating agents, and oil-soluble types are used as lubricating additives. Examples describe the polymerization of the hydrolysis product of N-(b -methacryloxyethyl)-2 - morpholinone; the copolymerization of methyl methacrylate, ethyl acrylate and N-(b -methacryloxyethyl) - 2 - morpholinone; methyl methacrylate, butyl methacrylate and N-[b -(4-pentenoyloxyethyl] - 2 - morpholinone; butyl and methyl methacrylate and N-(b -methacryloxyethyl) - 2 - morpholinone; ethyl acrylate, methyl methacrylate, di - isobutylphenoxypoly (40) ethoxyethanol and N-(b -methacryloxyethyl) - 2 - morpholine; methyl and 2 - ethyl hexyl methacrylate, vinyl toluene and N-[3-(crotonoxy) propyl] - 5 - methyl - morpholinone; vinyl acetate, vinyl chloride, styrene, butyl acrylate and N - [b  - (3 - pentenoyloxy) propyl]-3,3 - dimethyl - 2 - morpholinone; ethylacrylate, N - methylolacrylamide, acrylamide, and N-(5 - hexenoyloxyethoxyethoxy ethoxyethyl)-2-morpholinone; and vinyl toluene, vinylidene chloride, ethyl acrylate and N-(b -methacryloxyethyl) - 3,3 - pentamethylene - 2 - morpholinone, and the use of these copolymers as coatings, for metal, paper, fibres, chipboard, electrical conductors, steel; as bonding for non-woven fabrics, sizes and as paint media.ALSO:The invention comprises unsaturated carboxylic acid esters of formula <FORM:1109493/C2/1> in which R is a hydrogen atom or a methyl group, m is 1,2, or 3; p is 1,2,3 or 4; #c is 1,2,3 or 4; A is an alkylene group (2-4 C); and Z is a substituted morpholinone group <FORM:1109493/C2/2> or a substituted glycine group <FORM:1109493/C2/3> in which Y is an alkylene group (2-3 C); R1 is hydrogen, alkyl (1-8 C), or phenyl group; R2 is hydrogen, alkyl (1-8 C) or R1 and R2 may be joined to form a 5-7 C ring; providing that when p is greater than 1 then m is 1, and when m is greater than 1 R is hydrogen, specifically N - (b  - methacryloxyethyl) - 2 - morpholinone, N - (b  - acyloxyethyl) - 2 - morpholinone, N - [b  - (4 - pentenoyloxy)ethyl] - 2 - morpholinone or mixtures thereof.  The esters are prepared by reacting <FORM:1109493/C2/4> in which R0 is an alkyl group with an N-substituted morpholinone-2 <FORM:1109493/C2/5> under transesterifying conditions e.g. in presence of tetra alkyl titanate or an alkali metal (C1-C4)-alkoxide. Alternatively, an acyl halide may be reacted with the N-substituted morpholinone-2, e.g. in the presence of a hydrogen halide acceptor.  The ester may be hydrolysed to form a compound with Z a substituted glycine group. The N-substituted-morpholinone-2 may be prepared by reacting an alkylene oxide (2-4 C) with a compound <FORM:1109493/C2/6> where M is an alkali metal and acidifying and dehydrating the intermediate formed, or by reacting the alkylene oxide with a hydroxy-(poly)-alkoxyamine H(OA)#c-NH2 (#c=2-4), followed by reaction with an alkali metal a -chloro-acetate.  The ester products are normally stable, colourless liquids which may form addition linear polymers, or copolymers with vinyl monomers. Examples describe the preparation of the compounds specified above and N - [b  - (3 - pentenoyloxy)propyl] - 3,3 - dimethyl - 2 - morpholinone, N - [3 - (crotonoxypropyl] - 5 - methyl - 2 morpholinone, N - (acyloxyethoxyethyl) - 2 - morpholinone, N - (methacryloxypropoxypropyl) - 3 - phenyl - 2 - morpholinone, and N-(5-hexenoyloxyethoxyethoxyethoxyethyl) -2-morpholinone and their hydrolysis to the corresponding glycines.ALSO:Polymers or copolymers of the unsaturated carboxylic esters of formula <FORM:1109493/B1-B2/1> in which R is a hydrogen atom or a methyl group; m is 1, 2 or 3; p is 1, 2, 3 or 4; x is 1, 2, 3 or 4; A is an alkylene group (2-4C) and Z is a substituted morpholinone group <FORM:1109493/B1-B2/2> or a substituted glycine group <FORM:1109493/B1-B2/3> which Y is an alkylene group (2 or 3C); either R1 is a hydrogen atom, an alkyl group (1-8c) or a phenyl group and R2 is hydrogen-an alkyl group (1-8C) or R1 and R2 are joined in a ring of 5 to 7C atoms with the proviso that when p is greater than 1 then m is 1, and when m is greater than 1 then R is a hydrogen atom (see Divns C2 and C3) may be used to coat substrates much as wood or metal, e.g. steel plate, a copper wire or glass.  Conventional comonomers are specified together with usual additives and the coatings which may be on either bare or primed surfaces (with alkyd, epoxy or aminoplast primers) may be cured by heating with or without a catalyst. Examples describe the coating of steel with a copolymer of methyl methacrylate, ethyl acrylate and N-(B-methacryloxyethyl)-2-morpholinone; methyl methacrylate, butyl methacrylate, N-[B-(4-pentenoyl-oxy) ethyl]-2-morpholinone; methyl methacrylate, vinyl toluene, 2-ethylhexyl methacrylate and N-[3-(crolonoxy) propyl]-5-methyl-2-morpholinone; and vinyl acetate, vinyl chloride, styrene, butyl acrylate and N-[B-(3-pentenoyloxy)propyl]-3, 3-di-methyl-2-morpholinone; aluminium or wood with a copolymer of methyl and butyl methacrylate and N-(B-methacryloxyethyl)-2-morpholinone; and the enamelling of copper wire by passing through a latex prepared by polymerising a solution of the hydrolysis product of N-(diglycol)-2-morpholinone with N-methoxymethyl-methacrylamide, acrylonitrile and butyl acrylate, to which is added dimethyl formamide.ALSO:Polymers or copolymers of the unsaturated carboxylic esters of formula:  <FORM:1109493/D1-D2/1> in which R is a hydrogen atom or a methyl group; m is 1, 2 or 3; p is 1, 2, 3 or 4; x is 1, 2, 3 or 4; A is an alkylene group (2-4C) and Z is a substituted morpholine group:  <FORM:1109493/D1-D2/2> or a substituted glycine group:  <FORM:1109493/D1-D2/3> in which Y is an alkylene group (2 or 3C); either R1 is a hydrogen atom, an alkyl group (1-8c) or a phenyl group and R2 is hydrogen, an alkyl group (1-8c) or R1 and R2 are joined in a ring of 5 to 7C atoms with the proviso that when p is greater than 1 then m is 1, and when m is greater than 1 then R is a hydrogen atom (see Divisions C2 and C3) may be used to treat textiles, (e.g. bonding non-woven fabrics, shrink proofing wool and crease-proofing cotton and rayon), paper (e.g. p  to increase wet strength or as a binder in mineral coating. Conventional comonomers are specified together with usual additives and the compositions may be cured in situ with heat and with or without a catalyst.  Examples describe the bonding of non-woven fabric of carded viscose fibres with an aqueous dispersion of a copolymer from N-(5-hexenoyloxyethoxy ethoxyethoxyethyl) - 2 - morpholinone, ethyl acrylate, acrylamide and N-methylolacrylamide which is cured thereon; the sizing of yarns of cotton, rayon, wool, nylon and cellulose acetate with aqueous solutions of hydrolysis products of N-(B-methacryloxyethyl)2-morpholinone, N-(B-acryloxyethyl)-2-morpholinone, N-[B-(3-pentenoyloxy) propyl]-3, 3-di-methyl-2-morpholinone, N-[3-(crotonxy) propyl]-5-methyl-2-morpholinone, N-(acyloxyethoxyethyl)-2-morpholinone, N-(methacryloxypro poxypropyl))-3-phenyl-2-morpholinone, and N-(5-hexenoyloxyethoxyethoxyethoxyethyl) - 2 - morpholinone which are directly polymerised without isolation of the hydrolysed monomer. The size is water-soluble, and may be removed by normal scouring.