Patent GB-747184-A (GB)
Title: Improvements in or relating to a process for preparing ureido derivatives of vinyl ethers and their polymers
IPC: C08F20/36
Filed: 1953-04-08
Abstract: New ureido compounds of formula CH2 = CHOAN(R)CONH2 in which A represents either (a) a hydrocarbon group containing at least two carbon atoms between the ether oxygen and the nitrogen atom shown; or (b) a hydrocarbon group having a chain between the oxygen and nitrogen atom which contains one or more of the hetero atoms, oxygen, nitrogen and sulphur, provided that each hetero atom in the group -OAN- is separated from a neighbouring hetero atom by at least 2 carbon atoms; and in which R represents hydrogen, a thenyl group, a hydrocarbon group or a hydrocarbon group containing etherlinked oxygen, can be polymerized alone, or copolymerized with each other or with other unsaturated compounds, in a solvent, an aqueous medium or in bulk, preferably in the presence of an azo-type catalyst.  The polymers may be after-treated with formaldehyde or with a solvent-soluble butylated urea-formaldehyde resin.  In the examples details are given of the polymerization of ureidoethyl vinyl ether (CH2= CHOCH2CH2NHCONH2), b  - ureidoisobutyl vinyl ether, 1 - ureido - 2 - vinoxyoctadecane, 8 - vinoxy - 2.6 - dimethyl - 2 - ureido-octane, N - benzyl - N - vinoxyethyl urea, 4 - ureido - 4 - methyl - 2 - pentyl vinyl ether, 3 - ureido - 3 - phenylbutyl - vinyl ether, 1 - phenyl - 2 - ureido - ethyl - vinyl ether, 5 - ureidopentyl - vinyl ether, 2 - ureidopropyl - vinyl ether, N - cyclohexyl - N - vinyloxy - ethyl urea, N - methyl - N - vinyloxyethyl urea, N - C18H33-Nvinyl oxyethyl urea, N-allyl-N-vinyloxyethyl urea, N - crotonyl - N - vinyl oxyethyl urea and N - cyclohexenyl, oleyl or methylethynylN-vinyloxy ethylurea. Example are also given of the copolymerization of the new ureido compounds with each other and with one or two unsaturated compounds such as vinoxyethanol, vinyl acetate, methyl acrylate, acrylonitrile, acrylic acid, vinyl pyridine, aminoethyl vinyl ether, ethyl acrylate, bis(vinyloxy ethyl)urea, butyl acrylate, methyl methacrylate, butyl methacrylate, vinyl chloride, isobutyl acrylate, vinyl acetate and ethoxyethoxyethyl acrylate.  The polymers and copolymers can be used in coatings, sheetings, mouldings, castings, impregnating compositions, sizings and binders.  The new ureido compounds also react with polyvinyl alcohols to give urea-modified materials which can be further reacted with formaldehyde.  Polymers of the ureidovinyl ethers may be formed within cellular materials.  For instance ureidoethyl vinyl ether may be applied to cellulose from a water solution and the polymer formed in situ.  The ureido compounds may also be added to an aqueous spinning medium, such as viscose, to yield fibres which become crease-proof when heated to 100-150 DEG C.ALSO:The invention comprises compounds of formula CH2=CHOAN(R)CONH2 in which A represents either (a) a hydrocarbon group containing at least 2 carbon atoms between the ether oxygen and the nitrogen atom shown in the formula or (b) a hydrocarbon group having a chain between the ether oxygen and nitrogen atom which contains one or more of the hetero atoms, oxygen, sulphur or nitrogen, with the proviso that each hetero atom in the group -OAN- is separated from a neighbouring hetero atom by at least 2 carbon atoms; and wherein R represents hydrogen, a thenyl group, a hydrocarbon group or a hydrocarbon group containing ether linked oxygen.  They are prepared from amino-organo vinyl ethers of formula RHN-A-O-CH=CH2 by treating them with a water-soluble inorganic cyanate, preferably an alkali metal cyanate, in the presence of an acid.  The preferred acids are sulphuric, phosphoric and hydrochloric acid. Strong organic acids, for example, acetic and formic acids, may also be used.  The preferred starting materials are those of formula CH2=CHOCnH2nNHR, in which n is 2-18, and in their case the reaction can be represented as follows: - -CH2=CHOCnH2nNHR + MCNO + HX-->CH2=CHOCnH2nN(R)COHN2 + MX, where M is a salt-forming group or metal, X is the anion of a strong non-oxidizing acid and R is a hydrogen or a hydrocarbon group, especially an alkyl group containing not more than 4 carbon atoms, or a benzyl, phenyl, cycloalkyl or alkenyl group.  The reaction takes place conveniently in solution at temperatures between 0 DEG  and 50 DEG  C.  Alternatively the new ureido compounds may be prepared by heating urea with a vinyl ether starting compound, as defined above, to a temperature between 100 DEG  and 150 DEG  C., with evolution of ammonia.  A long list of starting materials in which A may be various aliphatic, aromatic and cycloaliphatic groups or aliphatic chains interrupted by hetero atoms and in which R may be hydrogen saturated or unsaturated hydrocarbon groups or a thenyl group, is given.  The examples describe the preparation of, among other compounds:  (a) CH2=CHOCH2CH2NH.CONH2 <FORM:0747184/IV(a)/1> <FORM:0747184/IV(a)/2> <FORM:0747184/IV(a)/3> <FORM:0747184/IV(a)/4> <FORM:0747184/IV(a)/5> <FORM:0747184/IV(a)/6> (h) (CH2=CHOCH2CH2)2NCONH2 <FORM:0747184/IV(a)/7> <FORM:0747184/IV(a)/8> <FORM:0747184/IV(a)/9> <FORM:0747184/IV(a)/100> (m) CH2=CHO(CH2)5NHCONH2 and <FORM:0747184/IV(a)/111>ALSO:Polymers obtained by condensing ureidovinyl ethers with other materials may be used for treating textiles.  In the examples (21) a cotton fabric is immersed in a 50 per cent aqueous solution of ureidovinyl ether containing 1.5 per cent by weight of dimethyl azodi-isobutyrate; the fabric is then heated, dried and treated with formaldehyde and an acid catalyst to yield a fabric having an increased crease recovery; (47) polymers prepared from 2-20 per cent ureido isobutyl vinyl ether, or 5 per cent of N-a-methylbenzyl-N-vinoxy ethyl urea, and ethyl, butyl or ethoxyethoxyethyl acrylate are applied to wool fabrics in the presence of oxalic acid to give shrinkage resistance.ALSO:Certain polymers obtained by condensing ureidovinyl ethers with other materials may be used as additives for lubricating oils.  In the examples, (a) a polymer obtained by condensing <FORM:0747184/III/1> with dimethyl azodiisobutyrate in amounts of 0.1-1 per cent depresses the pour-point of Pennsylvania Bright Stock (Examples 23) and (b) a polymer obtained by condensing isobutyl acrylate with <FORM:0747184/III/2> may be used as a thickener and stabilizer for oils and greases; if dodecyl acrylate is substituted for isobutyl acrylate the product may be used for depressing the pour-point and improving the viscosity-temperature relationship of lubricating oils (Example 54).