Patent GB-759860-A (GB)
Title: Improvements in or relating to polymerizable isocyanato esters
IPC: C08F20/18
Filed: 1953-10-19
Abstract: Iso-cyanato esters having the general formula Z-COO-A-NCO, in which A represents a saturated aliphatic, a saturated cycloaliphatic or aryl substituted saturated aliphatic, divalent hydrocarbon group having up to 14 carbon atoms, there being at least 2 carbon atoms between the oxygen and nitrogen atoms shown, and in which ZCO represents acryl, methacryl, a -chloracryl or crotonyl, may be polymerized alone or in mixtures with each other or in copolymerizable mixtures with other compounds containing at least one vinylidene group, e.g. N-dialkyl acrylamides, alkyl esters of acrylic, a -chloroacrylic and methacrylic acids, styrene, a -methyl styrene, vinyl naphthalene, vinyl and vinylidene chlorides, allyl and methallyl esters of saturated aliphatic carboxylic acids, acrylonitrile and vinyl pyridine. The polymers, and also the copolymers with vinylidene compounds free from reactive hydroxyl, amino and carboxylic groups, are generally oil-soluble, thermoplastic resins.  These resins contain a plurality of isocyanate groups and are reactive with organic compounds containing reactive hydrogen, e.g. in amino, hydroxyl, carboxyl and mercapto groups.  Thus, they may be reacted per se with cellulosic compounds and proteins, e.g. glue.  The thermoplastic resins may be cross-linked and rendered infusible and insoluble by reaction with, e.g., ethylene and polyethylene poly-amines and glycols, glycerol, pentaerythritol, sorbitol, mannitol, oxalic acid, adipic acid, ethanolamines and propanolamine and also alkyd resins.  The polymerization or copolymerization of the iso-cyanato esters may be carried out in bulk or in solution; those esters having a tertiary carbon atom attached to -NCO may be polymerized in aqueous emulsion.  Heat, ultra-violet light or free-radical catalysts may be used, especially the azo-type catalysts such as azoisobutyronitrile, a  : a 1-bis-azoisobutyronitrile and methyl azoisobutyrate. In examples (3) beta-iso-cyanato ethyl methacrylate is polymerized; (4) the same ester is copolymerized with methyl methacrylate at 60 DEG  C. yielding a toluene soluble resin which, on further heating at 180 DEG  C., is rendered thermoset; (5) the same ester is copolymerized with stenyl acrylate in refluxing benzene; (6) as in (4) using "Cellosolve" (Registered Trade Mark) acetate as solvent, yielding a film-forming solution; (7) the solution of (6) is gelled by reaction with hexamethylene diamine, ethylene diamine or 1,8-diamino-p-menthane; numerous amino alcohols and polyols are mentioned as alternatives; (8) 7-isocyanato-3,7-dimethyl-1-octyl methacrylate and butyl acrylate are copolymerized in an aqueous emulsion containing ammonium persulphate and sodium hydrosulphite, yielding a soluble rubber which becomes cross-linked on heating at 100 DEG  C.  The preparation of the esters is described (see Group IV (b)).ALSO:The invention comprises polymerizable isocyanato esters of acrylic, methacrylic, a -chloracrylic and crotonic acids having the general formula Z-COO-A-NCO in which A represents a saturated aliphatic, a saturated cycloaliphatic or aryl substituted saturated aliphatic, divalent hydrocarbon group having up to 14 carbon atoms, there being at least 2 carbon atoms between the oxygen and nitrogen atoms shown, and in which Z represents CH2=CH-, CH2 = C(CH3)-, CH2 = C(Cl)- or CH3CH= CH-.  The compounds may be prepared by the thermal decomposition of urethano esters of the general formula Z-COO-A-NHCOOC2H5 where Z and A are as above defined, at a temperature at which ethyl alcohol is split off but below the temperature of decomposition of the desired isocyanato ester.  Suitably, the thermal decomposition may be carried out in the presence of phosphorus pentachloride or thionyl chloride when the carbon atom in group A which is attached to the urethane group of the urethano ester is a primary or secondary carbon atom; also when the carbon atom is secondary decomposition may be effected in the presence of an inorganic basic compound such as a salt of a carboxylic acid and an alkali metal, a water-soluble hydroxide of an alkaline earth metal or a water-insoluble oxide or hydroxide of an alkaline earth metal or heavy metal.  When the carbon atom in question is tertiary, decomposition is preferably effected by the last above mentioned method at from about 170 DEG  C. upwards, preferably under reduced pressure.  Specific basic inorganic compounds mentioned in this connection are sodium acetate, potassion butyrate, lime, barium oxide, cerium oxide, cadmium oxide and basic lead carbonate.  The isocyanato esters may be polymerized or copolymerized (see Group IV (a)).  The urethano esters may be prepared by reacting ethyl chloroformate with an amino alcohol HO-A-NH2 generally at a temperature not above 80 DEG  C., in the presence of an acid-acceptor and a solvent and reacting the product HO-A-NHCOOC2H5 with an acid halide Z-CO-X, desirably in the presence of an acid-acceptor especially acrylonitrile, or with the corresponding acid anhydride thereby forming the desired urethano ester.  An alternative method comprises reacting an ester Z-COO- alkyl with a chloralcohol HO-A-Cl to form the compound Z-COO-A-Cl which is then reacted with a metallic isocyanate and ethanol to give the urethano ester. In examples (1) ethanolamine is reacted with ethyl chloroformate yielding N-hydroxyethyl urethane which is condensed in acrylonitrile solution with methacrylyl chloride; the resulting urethano ester is then added dropwise to a volume of mineral oil containing PCl5 at 70 DEG  C. and 120 mm. pressure and thereafter heated to 170 DEG  C. at 10 mm. and distilled yielding the methacrylyl ester of hydroxy ethyl isocyanate; several other named isocyanate esters are stated to have been prepared similarly; (2) methyl methacrylate is reacted in excess with 3-chloro1-propanol and the resulting gamma-chloro propyl methacrylate is reacted at 85 DEG C. with potassium isocyanate in the presence of KI and in dimethyl formamide solution yielding the methacrylic ester of N-hydroxypropyl urethane which on treatment as in the last step of (1) yields the desired isocyanato ester.  A number of isocyanato esters in which the carbon atom of group A attached to the urethano group is secondary or tertiary are mentioned which are prepared by thermal decomposition aided by one of the above-specified inorganic basic compounds. Numerous additional amino alcohols are listed as starting materials including various hydroxy propylamines, hydroxy butylamines, a hydroxy decyl amine, HOCH2CH (C6H5)CH2NH2, p - hydroxymethyl hexahydrobenzylamine and 4-hydroxy-1-methyl cyclohexylamine.ALSO:Wool is treated with polymers or co-polymers of isocyanate esters having the general formula Z-COO-A-NCO, wherein Z-CO represents the acryl, methacryl, a-chloracryl or crotonyl radical and A represents a saturated aliphatic, saturated cycloaliphatic or aryl-substituted saturated aliphatic, divalent hydrocarbon group having up to 14 carbon atoms, there being at least 2 carbon atoms between the oxygen and nitrogen atoms shown (see Group IV(a)).