Patent GB-838817-A (GB)
Title: New vinyl heterocyclic nitrogen compounds and polymers thereof
IPC: C08F226/06
Filed: 1956-09-05
Abstract: The invention comprises compounds of the formula <FORM:0838817/IV (b)/1> where A is C2-C3 alkylene, R and R1 are H C1-C18 alkyl, C2-C18 alkenyl, phenyl, benzyl or cyclohexyl, or with the N atom form a morpholine, piperidine or pyrrolidine ring (not further substituted) and Z is C2-C18 alkylene (optionally substituted by phenyl or vinyl) or cycloalkylene; also quaternary salts of the above.  The compounds are prepared by reacting acetylene with compounds <FORM:0838817/IV (b)/2> at 90-160 DEG  C. and 300-500 p.s.i.g. in the presence of sodium or potassium, and, if desired, quaternating the product (if R and R1 are not H).  Examples show the preparation of compounds where A is ethylene or trimethylene, Z is ethylene or propylene, and NRR1 is amino, methylamino, dimethylamino, didodecylamino, octadecylamino, methylbenzylamino, dicyclohexylamino or morpholino.  Other specified groups are: A, propylene; Z, trimethylene, tetramethylene, pentamethylene, octylene, decylene, decamethylene, octadecylene, butenylene, phenylethylene and cyclohexylene; R and/or R1, isopropyl, n-butyl, s-butyl, amyl, hexyl, octyl, decyl, dodecenyl, hexadecyl and phenyl.  Quaternary salts are made by quaternating the compounds, after progressive alkylation, if necessary. Quaternating agents that may be used are methyl chloride, ethyl chloride, benzyl chloride, allyl chloride, dodecenyl chloride, pentadecenyl chloride, octylbenzyl chloride, chlorobenzyl chloride, chloromethylthiophene, -furan or -naphthalene, phenoxyethyl bromide, methyl iodide, dimethyl sulphate, sulphite or phosphite, ethylene oxide, propylene oxide, butylene oxide or styrene oxide.  The compounds in which R is hydrogen can be reacted with formaldehyde.  Starting materials of the formula <FORM:0838817/IV (b)/3> are made by reacting primary or secondary amines with halogen compounds <FORM:0838817/IV (b)/4> The latter (X=chlorine or bromine) are obtained by the action of thionyl halides on hydroxy compounds <FORM:0838817/IV (b)/5> which are described in Specification 772,666.  Suitable reactants for these steps are mentioned, containing groups A, R, R1 and Z as specified above.ALSO:Compounds of the formula <FORM:0838817/IV(c)/1> are applied to textiles (a) of dyed cellulose esters, to inhibit gas-fading of the dye, and (b) of cellulosic materials, to function as a lubricant when a long-chain group is present in R, R1 and/or Z (see below).  The compounds (or polymers thereof) can also be incorporated in urea- or melamine-formaldehyde resins to give products which are applied to fibres of cellulose, wool, casein, rayon or cotton as shrink-proof or crease-proof treatments or to provide anchorage for other resins to be applied thereto.  In the formula A is C2-C3 alkylene, R and R1 are H, C1-C18 alkyl, C2-C18 alkenyl, phenyl, benzyl or cyclohexyl, or with the N atom form a morpholine, piperidine or pyrrolidine ring (not further substituted), and Z is C2-C18 alkylene (optionally substituted by phenyl or vinyl) or cycloalkylene.  Polymerized 1 - (b  - octadecylaminoethyl) - 3 - vinyl - imidazolidin - 2 - one after-quaternated with benzyl chloride gives an antistatic finish on fibres, filaments and yarns of cellulose acetate, polyacrylonitrile and vinyl chloride-acetate copolymers.ALSO:The invention comprises polymers and copolymers of compounds of the formula <FORM:0838817/IV (a)/1> where A is C2-C3 alkylene, R and R1 are H C1-C18 alkyl, C2-C18 alkenyl, phenyl, benzyl or cyclohexyl, or with the N atom form a morpholine, piperidine or pyrrolidine ring (not further substituted) and Z is C2-C18 alkylene (optionally substituted by phenyl or vinyl) or cycloalkylene; also quaternary salts of the above. Polymerization may be carried out in bulk, solution (e.g. in water, dioxane, ethanol or isopropanol), emulsion or suspension (in brine if the monomer is water-soluble). The catalyst may be an organic or inorganic peroxide, a persulphate (e.g. in a redox system) or an azo compound, a number being specified; a mercaptan regulator can also be present.  The usual non-ionic, anionic or cationic emulsifiers are suitable.  If R or R1 is hydrogen the compounds may be copolymerized with ethylene, isobutylene, vinyl chloride and vinyl ethers.  Such polymers or copolymers can be aftertreated with formaldehyde or can be cured to an insoluble state by after-heating.  If neither R nor R1 is hydrogen other comonomers can be used, e.g. acrylic and methacrylic acids, salts, amides, esters and nitriles; itaconic, maleic and fumaric acids and esters; maleic anhydride; vinyl esters and sulphides; styrene and its derivatives; vinyl-pyridine and -carbazole; allyl esters.  Compounds of these types are listed, and also diethyl citraconate, diethyl chloromaleate, dialkylaminoalkyl acrylamides and esters (and methacryl-), uredialkyl vinyl ethers and vinyl-naphthalene.  Insoluble interpolymers result from using di-unsaturated compounds, e.g. alkenyl or alkylene esters of unsaturated acids, di- and tri-vinylbenzene, bis-(vinyloxyethyl)-urea, and vinyloxyethyl acrylate and methacrylate.  The monomers or polymers, where R or R1 is hydrogen, can be incorporated in aminoplasts (e.g. urea- or melamine-formaldehyde) to provide a resin which can be made infusible and insoluble by baking.  When quaternary salts are desired the quaternization can be carried out before or after polymerization, a number of suitable agents being specified. Examples show the production of polymers of 1-(b -aminoethyl)-3-vinyl-imidazolidin-2-one (after-treated with formaldehyde); 1 - (b  - dimethylaminoethyl) - 3 - vinyl - imidazolidin - 2 - one; 1 - (b  - aminoethyl) - 3 - vinyl - hexahydropyrimidin - 2 - one; 1 - (b  - octadecylaminoethyl) - 3 - vinyl - imidazolidin - 2 - one (after-quaternated with benzyl chloride); and 1 - (b  - dicyclohexylaminoethyl) - 3 - vinyl - hexahydropyrimidin - 2 - one.  Copolymers are obtained from (1) 1-(b -dimethylaminoethyl)-3-vinyl-imidazolidin-2-one and methyl methacrylate (or any acrylic, methacrylic or itaconic ester); (2) 1 - (b  - methylaminoethyl) - 3 - vinylimidazolidin-2-one and isobutylene; (3) 1-(b -didodecylaminoethyl) - 3 - vinyl - hexahydropyrimidin - 2 - one, methyl methacrylate and butyl acrylate; (4) 1-(b -morpholinoethyl)-3-vinyl-imidazolidin-2-one, acrylonitrile and vinyl acetate; (5) 1-(b -dicyclohexylaminoethyl)-3-vinyl-hexahydropyrimidin-2-one and styrene; and (6) 1-(b -dimethylaminoethyl)-3-vinylimidazolidin-2-one and ethyl acrylate.  These copolymers give fungicides on quaternation with methyl or benzyl chloride.