Patent GB-839856-A (GB)
Title: Unsaturated thioureido ethers, polymers thereof and process of making them
IPC: C07C275/10
Filed: 1956-07-03
Abstract: Compounds of general formula <FORM:0839856/III/1> in which A is an alkylene group having 2-10 carbon atoms of which at least 2 extend in a chain between the adjoining N and O atoms; R is hydrogen or a C1-C18 hydrocarbon group; and R1 and R2 either collectively represent a single group which is tetramethylene, -(CH2)4-, pentamethylene, -(CH2)5-, or 3-oxapentamethylene, -(CH2)2O(CH2)2-, an which group forms a heterocycle with the adjoining nitrogen atom; or R1 and R2 represent separate groups or atoms, in which case R1 is H, phenyl, chlorophenyl, naphthyl, benzyl, alkoxybenzyl, cyclohexyl, a C1-C18 alkyl group or a C2-C18 alkenyl group; and R2 is H or a C1-C4 alkyl group; with the proviso that when R1 and R2 are other than H, and A has less than 4 carbon atoms in a chain separating the adjoining O and N atoms, R is other than hydrogen, can be converted to polymers which may be used for coating materials such as metal, concrete, asbestos and glass.  In the examples, (a) a polymer obtained by condensing CH2=CHOCH2CH2NHCSNHC6H5 with methyl methacrylate in the presence of toluene and dimethyl azobisisobutyrate is applied in solution in ethylene dichloride to metal, concrete and asbestos to provide a durable protective coating upon drying; and (b) a polymer obtained by condensing CH2=CHOCH2C(CH3)2NHCSNHC6H5 with methyl methacrylate, and dimethylformamide in the presence of dimethyl azobisisobutyrate is mixed in solution with bis-N,N1-methoxy methyl ethyleneurea and p-toluene sulphonic acid; panels of glass and metal are coated with films of the resultant mixture and baked; the resultant coatings are solvent-resistant and have good adhesion to the substrate panel.ALSO:The invention comprises new thioureidoalkyl vinyl ethers of formula <FORM:0839856/IV (b)/1> in which A is an alkylene group having 2-10 carbon atoms of which at least 2 extend in a chain between the adjoining N and O atoms; R is hydrogen or a C1-C18 hydrocarbon group; and R1 and R2 either collectively represent a single group which is -(CH2)4-, -(CH2)5 or -(CH2)2O(CH2)2 which forms a heterocycle with the adjoining nitrogen atom; or R1 and R2 represent separate groups, R1 being hydrogen, phenyl, chlorophenyl, naphthyl, benzyl, alkoxybenzyl, cyclohexyl, a C1-C18 alkyl group or a C2-C18 alkenyl group and R2 being hydrogen or a C1-C4 alkyl group, with the proviso that when R1 and R2 are other than H and A has less than 4 carbons in a chain separating the adjoining oxygen and nitrogen atoms R is not hydrogen.  Preferred compounds are those in which R is hydrogen or a C1-C18 alkyl group, particularly methyl. The new compounds may be prepared by one of the following methods: (a) the compounds in which R1 and R2 are both H may be obtained by the fusion of molar equivalent quantities of thiourea with an amine of formula H2C = CHOANHR; (b) compounds of the above formula in which R1 is a hydrogen atom may be obtained by the reaction, preferably in an inert solvent, of an amine of formula H2C = CHOANHR with an organic isothiocyanate of formula R3NCS in which R3 represents any of the individual groups specified above for R2 when it is not joined to R1; or (c) compounds of the above formula in which R1 and R2 are other than hydrogen may be obtained by the reaction of an amine of formula H2C = CHOANHR with a thiocarbamyl chloride of formula <FORM:0839856/IV (b)/2> in which R4 and R5 are as previously defined for R1 and R2 except that neither represents hydrogen; preferably an excess of amine is used and the reaction is carried out under substantially anhydrous conditions in an inert organic solvent; alternatively equimolar amounts of amine and chloride may be used with sufficient inorganic base to react with the hydrogen chloride liberated.  All the compounds of the above general formula in which at least one of R, R1 and R2 substituents is hydrogen, form isothiouronium salts in the presence of an alkylating agent, such as methyl chloride, dimethyl sulphate or benzyl chloride.  Those compounds in which at least one of the R1 and R2 substituents is hydrogen also form water-soluble salts with alkali metals in aqueous alkaline solutions.  The new compounds may be converted to homopolymers and copolymers (see Group IV (a)).  The monomers and/or polymers may be used for the treatment of textiles (see Group IV (c)), for proofing of materials to prevent bacterial and fungal attack (see Group VIII), as insecticides and fungicides (see Group VI), and for coating glass wood and other materials (see Group III). Examples are given of the production of compounds in which A is -CH2CH2-, -CH2CH(CH3)-, -CH2C(CH3)2-, -CH (C8H17)CH2-, -(CH2)5- or -(CH2)3-; R is H, CH3, C1 2H2 5 or C18H37; R1 is n-C4H9, CH3, phenyl, p - methoxybenzyl, p - chlorphenyl, cyclohexyl, lauryl or naphthyl; R2 is H or CH3; and R1 and R2 together form pentamethylene or -(CH2)2O(CH2)2; in some case the thiouronium salts are also formed.ALSO:Compounds of the general formula <FORM:0839856/IV(c)/1> in which A is an alkylene group having 2-10 carbon atoms, of which at least 2 extend in a chain between the adjoining N and O atoms; R is hydrogen or a C1-C18 hydrocarbon group; and R1 and R2 either collectively represent a single group which is tetramethylene, -(CH2)4,-, pentamethylene -(CH2)5- or 3-oxapentamethylene, -(CH2)2O(CH2)2-, which group forms a heterocycle with the adjoining nitrogen atom; or R1 and R2 represent separate groups or atoms, in which case R1 is H, phenyl, chlorophenyl, naphthyl, benzyl, alkoxybenzyl, cyclohexyl, a C1-C18 alkyl group or a C2-C18 alkenyl group, and R2 is H or a C1-C4 alkyl group; with the proviso that, when both R1 and R2 are other than H and A has less than 4 carbon atoms in a chain separating the adjoining O and N atoms, R is other than hydrogen; and their copolymers and homopolymers, may be used for the treatment of textiles.  The monomers may be converted into isothiouronium salts which may be used as antistatics for the treatment of textiles comprising hydrophobic fibres, such as cellulose acetate, polymers of vinyl chloride, acrylonitrile or vinylidine chloride, or copolymers of these monomers.  The new monomers may first be converted by addition polymerization into linear fusible or soluble polymers which are adapted for application to fabrics of cellulose, wool, nylon or rayon and then subsequently cured to an infusible and insoluble condition to crease-proof or crush-proof the fabric or to improve the dimensional stability of wool fabrics.  In the examples (a) N-n-butyl-N1-vinyloxyethyl - S - methyl thiouronium monosulphate is used as an antistatic agent for various synthetic fabrics; and (b) a wool fabric is padded with an emulsion of a copolymer obtained by emulsifying a mixture of butyl acrylate and CH2=CHOCH2C(CH3)2NHCSNHC6H5 with t-octylphenoxypolyethoxyethanol in water and adding diethylenetriamine and ammonium persulphate; the fabric is then dried, the resulting material being more resistant to shrinkage and felting.ALSO:The invention comprises new compounds of formula <FORM:0839856/IV (a)/1> in which A is an alkylene group having 2 to 10 carbon atoms, of which at least two extend in a chain between the adjoining N and O atoms, R is hydrogen or a C1-C18 hydrocarbon group, and R1 and R2 either collectively represent a single group which is tetramethylene, -(CH2)4-; pentamethylene, -(CH2)5-; or 3-oxapentamethylene, -(CH2)2O(CH2)2- and which group forms a heterocycle with the adjoining nitrogen atom; or R1 and R2 represent separate groups or atoms in which case R1 is H, phenyl, chlorophenyl, naphthyl, benzyl, alkoxybenzyl, cyclohexyl, a C1-C15 alkyl group or a C2-C18 alkenyl group, and R2 is H or a C1-C4 alkyl group with the proviso that when both R1 and R2 are other than H and A has less than 4 carbons in a chain separating the adjoining O and N atoms, R is other than hydrogen; and their copolymers and homopolymers.  The new thioureido-alkyl vinyl ethers are polymerizable to form homopolymers under the influence of azo catalysts.  The polymerization may be carried out with conventional azo catalysts in bulk, solution, emulsion or suspension under neutral or slightly alkaline conditions. The new compounds may be copolymerized with other monoethylenically and polyethylenically unsaturated polymerizable compounds in the presence of azo catalysts, or organic peroxides.  Suitable unsaturated compounds are, for example, acrylic and methacrylic acids and their esters; esters of itaconic, maleic, fumaric and citraconic acids; vinyl esters of carboxylic acids; vinyloxyalkyl esters of carboxylic acids; vinyl ethers such as ethyl vinyl ether, allyl vinyl ether, hydroxy ethyl and aminoethyl vinyl ether and vinyloxyethoxyethanol; methacrylonitrile and acrylonitrile; acrylamide and methacrylamide, and N-substituted amides; vinyl halides; ethylene and halosubstituted ethylene; styrene and divinyl benzene; bis-(vinoxyethyl) urea; ethylene diacrylate and dimethacrylate; and vinoxyethyl acrylate.  The polymers may be mixed with film-forming materials such as linear polyesters, including polyethylene glycol terephthalate, nitrocellulose and rosin esters. Those of the polymers which contain nitrogen - attached hydrogen form isothiouronium salts.  Copolymers in which the nitrogen atoms are still attached to hydrogen atoms may first be converted by addition polymerization to linear fusible or soluble polymers which may be applied to a substrate and subsequently cured.  To accelerate the 2nd stage cross-linking catalysts such as ammonium phosphate or thiocyanate, acid salts of hydroxy aliphatic amines, ammonium chloride, pyridine hydrochloride or benzyl dimethylamine oxalate may be used.  The linear heat-convertible polymers may also be incorporated into a spinning melt or solution containing a polymer of acrylonitrile and after spinning, the linear polymer may be converted to insoluble and infusible form by spinn