Patent GB-840891-A (GB)
Title: Unsaturated carbamato ethers and thioethers, polymers thereof and methods of making them
IPC: C07D295/205
Filed: 1956-07-06
Abstract: Carbamato-ethers and -thioethers of the formula <FORM:0840891/IV(a)/1> (where Y is oxygen or sulphur; A is cyclohexylene, a C2-C10 alkylene group providing a chain of at least 2 C atoms between adjacent O and Y atoms, or an alkylene group the chain of which is interrupted by one or more O atoms such that in -YAO- every two adjacent hetero atoms are separated by a C2-C4 alkylene group, of which at least two C atoms extend in a chain between the hetero atoms; R and R1 either collectively represent a single tetra-, penta- or 3-oxapenta-methylene group, or individually represent separate groups, R being hydrogen, phenyl, or C1-C6 alkyl, and R1 being hydrogen, cyclohexyl, phenyl, chlorophenyl, naphthyl, benzyl, oleyl, or C1-C22 alkyl) and the N-methylol and N-(C1-C4 alkoxy) methyl derivatives of those compounds where one or both of R and R1 are hydrogen, are employed as plasticizers or modifiers of synthetic resins or cellulose or cellulose derivatives, or are subjected to polymerization or copolymerization.  Cellulosic materials such as cotton, paper, or rayon fabrics may be reacted with the monomers and modified by the introduction of groups which are capable of reacting with other unsaturated compounds such as styrene, acrylates, acrylamides, and acrylonitrile.  Copolymers of the carbamatoethers with acrylonitrile may be used for the production of filaments and films, e.g. by extrusion of a solution in dimethyl formamide, or by casting and curing by heat.  A cotton fabric may be impregnated with a solution of 2-(vinylthio) ethyl N-methylol carbamate, dried and heatcured to form a reactive material which may be reacted with carbon bisulphide to form a xanthate suitable for extrusion to form filaments after solution in caustic soda.  A suspension of 2 - vinyloxyethyl - N,N - dimethylcarbamate in petroleum ether is heated in presence of azo-di-isobutyronitrile to form a polymer which may be used as a plasticizer for cellulose acetate or butyrate.  The carbamatoethers may be used for modifying urea-, triazine-, and thiourea-formaldehyde resins which may be used for moulding, casting, or coating.  The monomers may be polymerized in the presence of BF3, SO2 or other cationic or acidic catalyst, or if they are first converted to sulphoxides or sulphones there may be used a basic catalyst such as sodamide. Azo catalysts may be used and polymerization may take place in bulk, solution, emulsion, or suspension under neutral or slightly alkaline conditions.  Catalysts employed for co-polymerization include organic peroxides, and persulphates.  Specified compounds which may be copolymerized with the carbamato-ethers include methacrylic acid, esters of saturated and unsaturated alcohols with methacrylic acid, vinyl esters, vinyl ethers, vinyloxypropoxyethanol, methacrylamide, vinyl halides, chloro-fluoro ethylene, acetoxy butadiene, ethylene diacrylate, and bis (vinoxyethyl) urea.  Hompolymers from carbamato ethers, in which both R and R1 of the formula are hydrogen, are water-soluble, and those from monomers, in which only one or neither of R and R1 is hydrogen, are water-insoluble but are soluble in organic solvents. The solutions or emulsions may be used for sizing, coating, or impregnating textiles, e.g. cotton, rayon, nylon and wool, or for coating paper, wood, leather, or metals.  The polymers may be treated with formaldehyde before or after application to a substratum to provide groups which may be condensed on heating.  Examples describe the preparation of copolymers of methyl methacrylate with 2-(vinylthio) ethyl-N-tthyl carbamate and the modification of these by the admixture of N.N1-bis-methoxymethyl ethyleneurea so as to obtain products which on heating become resistant to organic solvents.  The polymerization of vinyl-thiopentyl N - p - chlorophenylcarbamate by heating a solution thereof in presence of dimethyl azo - di - isobutyrate is described.  The polymer so obtained is used for plasticizing polyvinyl chloride resins.ALSO:The invention comprises compounds of the general formula <FORM:0840891/IV(b)/1> where Y is oxygen or sulphur, A is cyclohexylene, a C2-C10 alkylene group which provides a chain of at least 2 carbon atoms between adjacent O and Y atoms, or an alkylene group the chain of which is interrupted by one or more oxygen atoms and which is such that, in the group -YAO- every two adjacent hetero atoms are separated by a C2-C4 alkylene group of which at least two carbon atoms extend in a chain between them.  R and R1 are either collectively a tetramethylene, pentamethylene, or 3 oxapentamethylene group, or separate groups, in which case R is hydrogen, phenyl or C1-C6 alkyl, and R1 is hydrogen, cyclohexyl, phenyl, chlorophenyl, naphthyl, benzyl, a C1-C22 alkyl group or an oleyl group, or R2OCH2, where R2 is hydrogen or C1-C4 alkyl.  Compounds of the general formula <FORM:0840891/IV(b)/2> are used as a starting material together with another suitable compound, depending upon the nature of R and R1.  When both R and R1 are hydrogen, preferably equal quantities of urea and the compound of formula II are mixed and heated between 100 DEG  C. and 160 DEG  C., preferably in the presence of a basic catalyst, e.g. sodium, potassium or lithium carbonates or cyanates or zinc oxide, and in the presence of vacuum or an inert gas e.g. nitrogen to assist the removal of ammonia.  It is preferable to use anhydrous reaction conditions, and the product may be recovered by distillation or recrystallization from e.g. water or ethyl acetate.  For compounds where R is hydrogen and R1 is one of the other groups defined above, an organic isocyanate of general formula R1NCO is reacted with the compound of formula II in equimolar amounts generally in the presence of e.g. benzene, ether or carbon tetrachloride preferably with a small amount of basic catalyst e.g. triethylamine benzyl dimethylamine, sodium and potassium methoxides, at a temperature 20-100 DEG  C. for 4-16 hours.  In the case where R1 is CH2OR2 an alkoxymethyl isocyanate of general formula R2OCH2NCO is used under similar conditions, or formaldehyde with or without a C1-C4 alkanol is reacted with a compound of general formula I where at least one of R and R1 are hydrogen.  When neither R nor R1 are hydrogen but are radicals as defined above the required compounds are obtained by reacting a carbamyl chloride of formula RR1NC11Cl with the compound of formula II in the presence of a tertiary amine e.g. triethylamine, pyridine, benzyl dimethylamine, or sodium or potassium hydroxides or carbonates.  An organic solvent e.g. acetonitrile, ether, benzene or carbon tetrachloride, or water may be present.  The reaction is carried out at 0-100 DEG  C. for 2-12 hours.  Many examples are given.ALSO:Carbamato-ethers and thioethers containing a vinyl group (see Group IV(b)), their N-methylol and N-(C1-C4 alkoxy) methyl derivatives, and their polymerization or co-polymerization products are used for treating textile materials so as to produce such effects as crease-resistance, shrink-resistance and stiffening, improving handle and modifying water absorption. Specified compounds with which the ethers or thio ethers, may be co-polymerized include methacrylic acid, esters of saturated and unsaturated alcohols with methacrylic acid, vinyl esters, vinyl ethers, vinyloxypropoxyethanol, acrylonitrile, acrylamide, vinylhalides, chlorofluoroethylene, acetoxybutadiene, ethylene, styrene, ethylene diacrylate and bis(vinoxyethyl) urea.  Specified textile materials are cotton, wool, nylon and viscose rayon. Homopolymers of the ethers may be used as dye strippers to remove substantive dyes from dyed fabrics.  In Examples (18) a cotton fabric is treated with 2-(vinylthio) ethyl N-methylol carbamate to give a water-repellent fabric when dried and cured and reacted with such compounds as acrylonitrile, and a rubbery fabric when reacted with butyl methacrylate; (32) wool is treated with the copolymer of butyl acrylate and 2(vinylthio) ethyl-N-ethylcarbamate to produce a shrink-resistant fabric.ALSO:Carbamato-ethers and thio ethers containing a vinyl group (see Group IV (b)), their N-methylol and N-(C1-C4 alkoxy) methyl derivatives, and their polymers, copolymers and condensation products are used for coating surfaces such as wood, glass, masonry, brick, cement, plaster and metal.  The monomers and polymers may be used as anti-oxidants in lubricating oils and in drying-oil paints.  The monomers and their methylol compounds may be incorporated in aminoplast resins such as urea-, melamine-, and thiourea-formaldehyde resins and these may be used as coating or adhesive resins for wood or glass e.g. in the production of plywood and safety glass. Homopolymers and copolymers may be applied to substrata from solutions or emulsions to provide protective coatings.  After application the coatings may be cured by heating or other means.  In examples: (1) vinylthioethyl carbamate is converted with aqueous formaldehyde into a methylol derivative and applied by brushing or dipping to cellulose, nylon, wood, glass, or other substratum, and the coating is dried and heated; the treated article may then be firmly bonded to polyester-vinyl type resin coatings applied thereon in the form of solutions and then dried and cured; (4) 2-(vinylthio ethyl N-ethylcarbamate is added to the extent of 0.25-2.0% to a drying-oil paint as an anti-oxidant and anti-skinning agent; (7) a copolymer of methyl methacrylate and 2-(vinylthio) ethyl N-ethylcarbamate is mixed with N.N1-bis-methoxymethyl ethylene urea and a catalyst, the solution is formed into film-coatings on glass and metal plates, and the coatings are cured by heating; (9) vinyl-thiopentyl N-p-chlorophenyl-carbamate is incorporated to the extent of 0.25-1.0% as an antioxidant in a cutting oil; (15) a mixed vinylthioethyl N-tert. alkyl carbamate in which the alkyl groups have an average of 13 carbon