Patent GB-812158-A (GB)
Title: Amides of vinyl ethers containing hydroxyl groups and polymers thereof
IPC: C07C233/16
Filed: 1955-12-07
Abstract: In examples: (1) the copolymer of ethyl acrylate and N-(2-vinyloxyethyl)-lactamide (see Groups IV (a) and IV (b), may be mixed with a butylated urea-formaldehyde condensate and butyl phosphoric acid, the mixture filmed on wood, glass or metal panels and baked to give coatings; (2) the copolymers from N-methylN - (21 - vinyloxyethyl) - 4 - hydroxy - butyramide and (a) methyl methacrylate, or (b) methyl methacrylate and ethyl acrylate or acrylonitrile, are mixed with N : N1-di-(methoxymethyl) - N : N1 - ethyleneurea and p - toluenesulphonic acid and the mixtures, which may be pigmented with a mixture of titanium dioxide and zinc oxide, are filmed on steel panels and baked to give hard films.ALSO:Monomeric compounds of the formula CH2 = CHOANRCOR1 I wherein A is a straight- or branch-chain alkylene group having 2-18 carbon atoms, of which at least two in a chain separate the adjoining nitrogen and ether oxygen atoms, R is hydrogen, phenyl, tolyl, benzyl, cyclohexyl or an alkyl group having from 1-18 carbon atoms and R1 is a mono- or poly-hydroxy aliphatic or cycloaliphatic group having 1-17 carbon atoms, which may be substituted by aryl groups (see Group IV(b)), may be converted into polymers or copolymers in the presence of catalysts, e.g. of the acyclic azo type.  Specified catalysts are azodiisobutyronitrile, azodiisobutyramide, dimethyl (or diethyl or dibutyl) azodiisobutyrate, azobis (a :g -dimethylvaleronitrile), azobis (a -methylbutyronitrile) and dimethyl azobismethylvalerate.  The polymerization may be effected in bulk, in solution, or in emulsion systems.  Specified solvents are methanol, ethanol, isopropanol, butanol, dimethylformamide, dimethylacetamide, benzene, toluene and xylene.  When the polymerization is carried out in an aqueous emulsion, suitable emulsifying agents are the alkaryl polyethoxyethanols.  The polymerization is preferably carried out in an inert atmosphere, such as nitrogen gas.  Specified monomers which may be copolymerized with the compounds of formula I are the vinyl halides, 1:1-difluoro- or dichloro-ethylene, isobutylene, 1:3-butadiene, styrene, 2-fluoro- or chloro - 1:3 - butadiene, 2:3 - dichloro - 1:3-butadiene, methyl or ethyl or butyl or methoxymethyl or chloroethyl or betadiethylaminoethyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl formate or acetate or chloroacetate or butyrate or laurate, acrolein, methacrolein, methyl vinyl ketone, N - vinyl - phthalimide or succinimide, 2-carbamidoethyl or aminoethyl or formamidoethyl vinyl ether, vinyl pyridine, N-vinyl caprolactam, tetrafluoroethylene, diethyl fumarate, dimethyl maleate, N - vinyl - N:N1-ethyleneurea, p-divinylbenzene, ethylene-bisacrylate, divinyl ether of ethylene glycol, N:N-bis-vinyloxyethylurea and diallyl phthalate.  The polymers may be modified by reaction with alkylene oxides such as ethylene, propylene and trimethylene oxides.  The monomers of formula I and polymers and copolymers thereof are capable of reacting with aldehydes such as formaldehyde or acetaldehyde and acids such as phthalic and maleic acids and thus may be employed as modifying components in aminoplasts, e.g. urea-formaldehyde, melamine-formaldehyde and mixed melamine-urea-formaldehyde condensates, in alkyd resins, e.g. in glycerol-phthalates, in styrene-maleic anhydride copolymers, in epoxy resins and in phenol-aldehyde resins.  The monomers of formula I may be copolymerized in small proportions, e.g. up to 10 per cent, with monomers lacking an amide group, e.g. methyl methacrylate, to render the copolymer reactive and thus suitable as a modifier for aminoplasts, alkyd resins and epoxy resins.  The water-soluble polymers may be used in paints such as those based on emulsions of polyvinyl acetate or polyacrylates.  The monomers of formula I and polymers thereof may be used as softening agents in "Cellophane" (Registered Trade Mark).  In examples: (1) a mixture of N-(2-vinyloxyethyl) lactamide and glycerine is used to soften "Cellophane"; (2) N-(21vinyloxyethyl) 4-hydroxy-butyramide is used to soften "Cellophane"; (3) N-(2-vinyloxyethyl lactamide or N - methyl - N - (21 - vinyloxyethyl) 4-hydroxy-butyramide is polymerized in the presence of dimethylazoisobutyrate; (4) polymeric N - (2 - vinyloxyethyl) lactamide is treated with ethylene oxide in the presence of sodium hydroxide; (5) N - (2 - vinyloxyethyl)-d-gluconamide is polymerized as in aqueous solution using dimethylazoisobutyrate as catalyst and is used as a softener in regenerated cellulose films or as an additive to polyvinyl acetate emulsion paints; (6) a mixture of N-(21-vinyl-oxyethyl) - 4 - hydroxy - butyramide and butyl methacrylate is emulsified in water using tert.-octyl-phenoxypolyethoxyethanol and the emulsion is heated with sodium persulphate and triethylene tetramine to give a copolymer dispersion which is mixed with kaolin and titanium dioxide to give a coating composition; (7) N-(2-vinyloxyethyl) lactamide and ethyl acrylate are copolymerized in dimethylformamide solution using dimethylazoisobutyrate as catalyst and the copolymer may be mixed with a butylated urea-formaldehyde condensate to give a film-forming composition (see Group III); (8) N-(2-vinyloxyethyl) lactamide and butyl acrylate are copolymerized as in (6) but using ammonium persulphate and diethylene triamine; (9) N-(21 - vinyloxyethyl) - 4 - hydroxybutyramide and N-vinylpyrrolidone are copolymerized in aqueous solution using dimethylazoisobutyrate as catalyst and the resultant copolymer is mixed with an aqueous resin-forming ureaformaldehyde condensate containing an acid catalyst to give a thermosetting adhesive composition; (10) N - (21 - vinyloxyethyl) 4 - hydroxy - butyramide, acrylonitrile and ethyl acrylate are copolymerized as in (8) to give a copolymer which may be formed into films or fibres and in the spinning of which N:N1-di-(n-butoxymethyl) N:N1-ethyleneurea may be added to give thermoset fibres; (11) N-methyl-N-(21-vinyloxyethyl) 4 - hydroxy - butyramide is copolymerized in solution in 2-ethoxyethyl acetate and in the presence of azodiisobutyronitrile with (a) methyl methacrylate, (b) methyl methacrylate and ethyl acrylate, and (c) methyl methacrylate and acrylonitrile and the resulting copolymers are mixed with N:N1-di-(methoxymethyl) N:N1-ethyleneurea and p-toluenesulphonic acid to give film-forming compositions.ALSO:The invention comprises N-vinyloxyalkyl amides of formula: CH2=CHOANRCOR1 (I) wherein A is a straight- or branched-chain alkylene group having 2-18 carbon atoms of which at least two in a chain separate the adjoining nitrogen and ether oxygen atoms, R is hydrogen, phenyl, tolyl, benzyl, cyclohexyl or an alkyl group having from 1-18 carbon atoms and R1 is a mono- or polyhydroxy aliphatic or cycloaliphatic group having 1-17 carbon atoms which may be substituted by aryl groups.  The amides are prepared by reacting a chloride, ester or lactone of an hydroxy acid R1COOH with an amine of formula: CH2=CHOANHR (II) Specified amines of formula (II) are: CH2= CHOCH2CH2NH2, CH2=CHOCH2CH2NHCH3, CH2=CHOCH2CH2CH2NH2, CH2=CHOCH2 CH(CH3)NH2, CH2=CHOCH(CH3)CH2NH2, CH2=CHOCH2C(CH3)2NH2, CH2=CHOC (CH3)2CH2NH2, CH2=CHOCH2CH2CH2CH2 NH2, CH2=CHOC(CH3)2CH2CH(CH3)NH2, CH2 = CHOCH2CH2CH(CH3) (CH2)3 C(CH3)2 NH2, CH2=CHOCH2C(CH3)2CH2NH2, CH2= CHOCH2CH(CH3)NHCH3, CH2=CHOCH(C16 H33)CH2NH2, CH2=CHOCH2CH2NHC6H5, CH2=CHOCH2CH2NHC4H9, CH2=CHOCH (CH3)CH2NHC2H5, CH2=CHOCH2CH2NH CH2C6H5 and CH2=CHOCH2CH2NHC6H11. Specified acids (R1COOH) are glycollic, lactic, alpha- or beta- or gamma-hydroxybutyric, alpha- or beta-hydroxyisobutyric, alpha- or alpha- or beta- or gamma-hydroxy-n-valeric, alpha- or beta-hydroxyisovaleric, hydracrylic, delta - hydroxyvaleric, eta - hydroxycaproic, omega - hydroxy - nonanoic, or - decanoic or -undecanoic or -dodecanoic or -tridecanoic, juniperic, 11-hydroxyhexadecanoic, 9- or 10- or 11- or 12-hydroxystearic, glyceric, 9 : 10-dihydroxystearic, 3 : 12 - dihydroxypalmitic, 2 : 3 : 4 - trihydroxy - n - butyric, trihydroxyisobutyric, aleuritic, sativic, arabonic, xylonic, ribonic, lyxonic, glyconic, mannonic, galactonic, guloric, taloric, idonic, altronic, allonic, alpha-d - glucoheptonic, alpha - hydroxyvinylacetic, ricinoleic, 3-hydroxy-pelargonic, tropic, atrolactic, 4- or 2-hydroxy-cyclohexane-1-carboxylic, shikimic and quinic.  The monomers of formula (I) may be polymerized and copolymerized (see Group IV (a)).  The compounds of formula (I) may be modified by reaction with an alkylene oxide such as ethylene, propylene or trimethylene oxide.  In examples: (1) 2-aminoethyl vinyl ether and methyl lactate are reacted to give N-(2-vinyloxyethyl)-lactamide; (2) glycollic acid chloride (1 mol.) and 3-methylaminapropyl vinyl ether (2 mols.) are reacted in chloroform solution to give N-methyl - N - (3 - vinyloxypropyl) - glycollamide, and similarly glyceric acid chloride and 3-phenylaminopropyl vinyl ether give N-phenyl-N - (3 - vinyloxypropyl) - glyceramide, and ricinoleic acid chloride and 2-(benzylamino)-ethyl vinyl ether give N-benzyl-N-(2-vinyloxyethyl)-ricinoleamide; (3) d-glucono-delta-lactone and 2-aminoethyl vinyl ether are reacted in methanol to give N-(2-vinyloxyethyl)-d-gluconamide and alpha-d-glucoheptona-delta-lactone and 2 - amino - 1 - hexadecylethyl vinyl ether are reacted similarly; (4) butyrol-acetone and 2-aminoethyl vinyl ether or N-methyl-2-aminoethyl vinyl ether are reacted to give N-(21-vinyloxyethyl)-4-hydroxybutyramide or its N-methyl derivative; (5) 4-hydroxy cyclohexane - 1 - carboxylic acid chloride, 2-aminoethyl vinyl ether and potassium carbonate are reacted in a mixture of benzene and water to give N-(21-vinyloxyethyl)-4-hydroxy - cyclohexane - 1 - carboxamide and quinic acid chloride and 2-aminoethyl vinyl ether are reacted similarly.ALSO:A copolymer of butyl acrylate and N-(2-vinyloxyethyl)-lactamide is applied in an aqueous emulsion to a botany wo