Patent GB-934979-A (GB)
Title: Unsaturated n-substituted amic acids, imides and esters, polymers thereof, and methods of preparation
IPC: C08G18/62
Filed: 1959-09-15
Abstract: Polymers of N-[mega-(1,3-cyclodiazolidin-2-oxyl)-alkyl] substituted unsaturated amic acids esters and cyclic imides in which maleamic, chloromalamic, fumaramic, itaconamic, mesaconamic or citraconamic acids are N-substituted by a group <FORM:0934979/IV(a)/1> in which A is an alkylene group having 2 or 3 carbon atoms in a chain between the adjoined N atoms, for example N-substituted maleamic acids and esters <FORM:0934979/IV(a)/2> and the cyclic imide, <FORM:0934979/IV(a)/3> where R is H or an n-alkyl with 1-4 carbon atoms (see Group IV(b)), are prepared using conventional free-radical catalysts and bulk, solution, emulsion or suspension techniques. Homopolymers are only produced from compounds derived from itaconic anhydride but all the monomers are copolymerizable with ethylenically unsaturated compounds such as, vinyl pyridines, acrylo- and methacrylonitriles, acrylic and methacrylic acids, esters (particularly C1 to C18 alkyl esters), amides, salts, itaconic, maleic and fumaric acids and their esters, vinyl ethers and esters, styrene, and substituted styrene, vinyl carbazole, allyl esters of monocarboxylic acids, and compounds containing two or more polymerizable vinylidene groups.  An alternative method of preparation may be by reacting a copolymer of the anhydride, e.g. with ethylenically unsaturated compounds, many listed, or a homopolymer of itaconic anhydride with the amine. <FORM:0934979/IV(a)/4> which is added to a heated organic solution of the polymer. Cross-linking reactions with aldehydes, polyepoxides, polyisocyanates or anhydrides of polycarboxylic acids yield infusible products, and the polymers may also be mixed with other resins, e.g. aminoplasts, phenolics, or unsaturated polyester resin.  Substrates, e.g. steel panels, may be coated, or impregnated with the thermosetting composition which is then heated to cross-link.ALSO:The invention comprises N-[omega-(1,3-cyclodiazolidin-2-onyl)-alkyl] substituted unsaturated amic acids, esters and cyclic imides in which maleamic, chloromaleamic, fumaramic, itaconamic, mesaconamic or citraconamic acids are N-substituted by a group <FORM:0934979/IV(a)/1> in which A is an alkylene group having two or three carbon atoms and at least two carbon atoms in a chain between the adjoined N atoms.  The compounds, for example N substituted maleamic acids and esters <FORM:0934979/IV(a)/2> in which R is H or a 1-4 C alkyl group are prepared by reacting the anhydride with an amine, in an inert solvent, at up to 60 DEG C., with or without a catalyst such as p-toluene sulphonic acid, followed by reaction with alcohol or treatment with a dehydrating agent such as acetic anhydride or a dialkyl or dicyclohexyl carbodiimide, to form esters and cyclic imides, <FORM:0934979/IV(a)/3> respectively. Alternatively half alkyl ester chlorides of the acids are reacted with the amine.  Examples describe the preparation of 1-[2-(b -carboxy acylamido) ethyl]-, 1-[2-(b -carboxychloroacylamido) ethyl]-, and 1-[2-(b -carbomethoxy acylimido) ethyl] imidazolidinone-2, and isomers, 1-[2-(b -carboxy acylamido) propyl] pyrimidinone-2, 1-[2-(N maleimidyl) ethyl] imidazolidinone-2, 1-[3-(N-maleimido) propyl] hexahydropyrimidinone-2, 1-[3-(b -carbobutoxy acylamido) propyl] hexahydropyrimidinone-2, and 1-[2-(N-itaconimidyl) ethyl] imidazolid inone-2.  Homopolymers may be prepared from the itaconic anhydride derivatives and this and the other derivatives may be copolymerised with ethylenically unsaturated compounds such as vinyl and acrylic monomers (see Group IV(a)).