Patent GB-842091-A (GB)
Title: Vinyl sulfides of substituted ureas and thioureas and polymers and copolymers thereof
IPC: C07C323/25
Filed: 1956-07-03
Abstract: The invention comprises polymers and copolymers of compounds of the following formulae:-I: CH2=CH,S,#j(NHCX)nNR1R2; II: CH2=CH,S,A,NR3,CX,NR1R2; III:(CH2=CH.S.#j.NH.CX.NH)mR4; IV: (CH2=CH,S,A,NR3,CX,NH)mR4, where A is C2-C6 alkylene, #j is o- or p-phenylene optionally mono- or disubstituted by C1-C4 alkyl, R1 is H, C1-C18 alkyl, alkenyl, cycloalkyl, aralkyl, aryl or chloroaryl, R2 is H, methyl or ethyl (or NR1R2 is a morpholino, piperidino or pyrrolidino residue), R3 is H or C1-C4 alkyl, R4 is C4-C10 alkylene, phenylene, tolylene, methylene-bis-phenylene, methylidyne-tris-phenylene or dias nisylene, X is O or S, m is 2 or 3, and n is 1, or is 2 if R1=R2=H and X=O.  Polymerization can be effected in bulk, solution, emulsion or suspension using as catalysts organic peroxides, azo compounds, boron trifluoride, sulphur dioxide, stannic chloride or aluminium chloride.  The compounds may be copolymerised with acrylic and methacrylic acids, esters, amides and nitriles; esters of maleic, fumaric, itaconic and citraconic acids; vinyl and vinyloxyalkyl carboxylates; vinyl alkyl and hydroxyalkyl ethers; vinyl and vinylidene halides; acetoxybutadiene; ethylene, styrene and divinylbenzene; ethylene diacrylate and dimethacrylate; vinyloxyalkyl acrylates; bis-(vinyloxyethyl)-urea.  The monomers or polymers which contain an -NH,CX,NH-grouping form methylol derivatives by treatment with formaldehyde and these can be acid-condensed to methylene-bis-compounds.  Infusible products are also obtained by further heating the methylol-free polymers.  The sulphide group in the monomers can be oxidised to a sulphoxide or sulphone group, in which case polymerization is carried out with an anionic or basic catalyst, e.g. sodamide, potassamide or a lithium alkyl.  Examples show the polymerization of N-ethyl-N1-methyl-N1-2-(vinylthio)-ethyl-urea, N1-methyl-N1-2-(vinylthio) -ethyl-morpholine-N-carboxamide and N-octadecyl-N1-2-(vinylthio)-propyl-urea, and the preparation of the following copolymers:- (1) N-ethyl-N1-methyl-N1-2-(vinylthio)-ethyl-urea or N1-methyl-N1-2-(vinylthio) -ethyl-morpholine-N-carboxamide with methyl methacrylate or acrylonitrile, the latter giving spinnable fibres; and (2) N-octadecyl-N1-methyl-N1-2-(vinylthio)-ethyl-thiourea with butyl acrylate.  It is also stated that hexamethylene-bis-(N1methyl-N1-2-(vinylthio) -ethyl-urea) can be copolymerised with formamidoethyl vinyl ether, ureidoethyl vinyl ether, vinyloxyethyl-ethylene-urea, allyl carbamate, styrene, vinyl acetate, acrylonitrile, acrylates and methacrylates.  The polymers and copolymers (including methylolated derivatives) are useful additives to cellulose acetate or cellulose acetate-butyrate spinning dopes, the polymer of N-ethyl-N1-methyl-N1-2-(vinylthio)-ethyl-urea being mentioned for this purpose.ALSO:The invention comprises compounds of the following formulae:-I : CH2 = CH.S.#j(NHCX)n NR1R2; II: CH2 = CH.S.A.NR3.CX.NR1R2; III;(CH2 = CH.S.#j.NH.CX.NH)mR4;IV:(CH2 = CH.S.A.NR3.CX.NH)mR4, where A is C2-C6 alkylene, #j is o- or p-phenylene optionally monoor disubstituted by C1-C4 alkyl, R1 is H, C1-C18 alkyl, alkenyl, cycloalkyl, aralkyl, aryl or chloroaryl, R2 is H, methyl or ethyl (or NR1R2 is a morpholino, piperidino or pyrrolidino residue), R3 is H or C1-C4 alkyl, R4 is C4-C10 alkylene, phenylene, tolylene, methylene-bis-phenylene, methylidyne-tris-phenylene or dianisylene, X is O or S, m is 2 or 3, and n is 1, or 2 if R1 = R2 = H and X = O. Compounds I where n is 2 and X is O are made by treating amines CH2 = CH.S.#j.NH2 with an alkali metal cyanate and a mineral acid. Compounds I and II where R1 but not R2 is H are made from the corresponding amines and R2NCO or R2NCS.  Compounds I and II where both R1 and R2 are other than H are obtained from the amines and R1R2 NCX.halogen.  Compounds II where R1 and R2 are both H are prepared from the amines and an alkali metal cyanate or thiocyanate with a mineral acid, or by fusing the amines with urea or thiourea, this latter method also serving for compounds I where n is I, X is S and R1 and R2 are both H. Compounds III and IV are made from the amines and the appropriate di- or tri-isocyanate or -isothiocyanate.  The sulphide group in the products can be oxidised to the corresponding sulphoxides and sulphones and can add mercaptans in the b -position to give di-sulphides.  Those which have a -NH.CX.NH- grouping also react with aldehydes, especially formaldehyde to give methylol derivatives which can be further condensed to methylene-bis-compounds.  Examples show the preparation of the following: (1) 2-ureidoethyl vinyl sulphide from 2-aminoethyl vinyl sulphide with potassium cyanate and acid or by heating with urea; (2) the N-methyl derivative of (1) by the cyanate method; (3) N : N1-disubstituted ureas from 2-(N-methylamino)-ethyl vinyl sulphide with ethyl and octadecyl isocyanates respectively; (4) 2-(vinylthio)-phenyl-biuret from 2-aminophenyl vinyl sulphide with potassium cyanate and acid; (5) a disubstituted urea from 2-aminophenyl vinyl sulphide and ethyl isocyanate; (6) a disubstituted urea from 3-aminopropyl vinyl sulphide and dimethylcarbamyl chloride; (7) an amide from 2-(N-methylamino)-ethyl vinyl sulphide and morpholine-N-carboxylic chloride; (7) a disubstituted thiourea from 2-aminoethyl vinyl sulphide and phenyl isothiocyanate; (8) a disubstituted thiourea from 2-(N-methylamino)-ethyl vinyl sulphide and t-octyl isothiocyanate; (a) bis-ureas from 2-(N-methylamino)-ethyl sulphide and hexamethylene di-isocyanate and diphenylmethane-4 : 41-di-isocyanate respective; (10) 2-thioureidoethyl vinyl sulphide by heating 2-aminoethyl vinyl sulphide with thiourea.  Other suitable starting materials are mentioned in which A may also be propylene or isobutylene, #j may be p-phenylene, tolylene or xylylene, R1 may be propyl, isopropyl, butyl, isobutyl, t-butyl, amyl, isoamyl, hexyl, decyl, dodecyl, hexadecyl, oleyl, cyclohexyl, chlorophenyl, naphthyl or benzyl, R2 may be ethyl, R3 may be butyl and R4 may be tetramethylene, decamethylene, tolylene, dianisylene and methylidyne-tris-phenylene. N : N1-bis-(2-vinylthioethyl)-urea is obtained by heating 2-aminoethyl vinyl sulphide with urea.  Aminoalkyl and aminoaryl vinyl sulphides unsubstituted on the N-atom are made from the corresponding mercaptans and acetylene with a basic catalyst. Alkylaminoalkyl vinyl sulphides are obtained by reacting thiourea with an alkylaminoalkyl halide and treating the resulting isothiouronium salt with acetylene.  Specification 747,184 is referred to.ALSO:A compound of one of the formulae specified below is applied to wool from aqueous or alcoholic solution to react with the SH groups of the wool; the wool is then heated with formaldehyde and an acid catalyst, whereby the hand and stiffness are modified and shrinkage is reduced.  Also, one of the compounds can be N-methylolated and applied to textiles (especially cellulosic or glass fibre) to provide anchoring sites for subsequent reagents. Polymers and copolymers of these compounds also give reduced shrinkage on woollen and cellulosic fabrics.  The four types of compounds are CH2=CH,S,#j(NHCXn) NR1R2, CH2=CH,S,A,NR3,CX,NR1R2, (CH2=CH,S,#j,NH,CX,NH)mR4 and (CH2=CH,S,A,NR3,CX,NH)mR4, where A is C2-C6 alkylene, #j is o- or p-phenylene optionally mono- or disubstituted by C1-C4 alkyl, R1 is H,C1-C18 alkyl, alkenyl, cycloalkyl, aralkyl, aryl or chloroaryl, R2 is H, methyl or ethyl (or NR1R2 is a morpholino, piperidino or pyrrolidino residue), R3 is H or C1-C4 alkyl, R4 is C4-C10 alkylene, phenylene, tolylene, methylene-bis-phenylene, methylidyne-tris-phenylene or dianisylene, X is O or S, m is 2 or 3, and n is 1, or is 2 if R1=R2=H and X=0.  It is stated in particular that the polymer of N-octadecyl-N1-2-(vinylthio)-propyl-urea imparts a soft hand to fabrics.ALSO:Materials for coating comprise polymers and copolymers of compounds of one of the following formulae, including N - methylol derivatives which become cross-linked on heating: CH2=CH.S.#f(NHCX)nNR1R2, CH2=CH.S.A.NR3.CX.NR1R2, (CH2=CH.S.#f.NH.CX.NH)mR4 and (CH2=CH.S.A.NR3.CX.NH)mR4, where A is C2-C6 alkylene, #f is o- or p-phenylene optionally mono- or disubstituted by C1-C4 alkyl, R1 is H, C1-C18 alkyl, alkenyl, cycloalkyl, aralkyl, aryl or chloroaryl, R2 is H, methyl or ethyl (or NR1R2 is a morpholino, piperidino or pyrrolidino residue), R3 is H or C1-C4 alkyl, R4 is C4-C10 alkylene, phenylene, tolylene, methylene-bis-phenylene, methylidynetris-phenylene or dianisylene, X is O or S m is 2 or 3, and n is 1, or is 2 if R1=R2=H and X is O.  In an example, metal panels are treated with a solution of a copolymer of methyl methacrylate and N-ethyl-N1-methyl-N1-2vinylthio)-ethyl-urea in ethoxyethyl acetate with the addition of titanium dioxide, and then baked; there may also be present ureaformaldehyde-butanol condensates and acids such as butyl acid phthalate; the panels can also be glass or ceramic.  A polymer of N1methyl - N1 - 2 - (vinylthio) - ethyl - morpholineN-carboxamide is also stated to be useful as a coating material.ALSO:Fungicidal compositions for plants comprise solutions in high-flash naphtha of compounds of one of the following formulae = CH2 = CH,S,#F (NHCX)n NR1R2, CH2 = CH,S,NR3,CX, NR1R2, (CH2 = CH,S,#F,NH,CX,NH)m R4 and (CH2 = CH,S,A,NR3,CX,NH)m R4, where A is C2-C6 alkylene, #F is o- or p-phenylene optionally mono- or di-substituted by C1-C4 alkyl, R1 is H, C1-C18 alkyl, alkenyl, cycloalkyl, aralkyl, aryl or chloroaryl, R2 is H, methyl or ethyl (or NR1R2 is a morpholino, piperidino or pyrrolidino residue), R3 is H or C1-C4 alkyl, R4 is C4-C1 alkylene, phenylene, tolylene, methylene-bis-phenylene, methylidyne-tris-phenylene or dianisylene, X is O or S m is 2 or 3, and n is 1 or 2 if R1 R2 = H and X = O. Particular compounds mentioned are N-phenyl-N1-2-(vinylthio)-ethyl thiourea and N-t-octyl-N1-methyl-N1-(2-vinylthio)-ethyl thiou