Patent GB-822266-A (GB)
Title: Unsaturated ureido ethers and polymers thereof
IPC: C08F16/30
Filed: 1955-09-07
Abstract: Polymers of vinyloxyureas of the formul  CH2 : CHO-A-NRCONHR1 CH2 : CHO-A-NR2CONR1R3 CH2 : CHO-Y-C(R4)(R5)NHCONR1R3 and CH2 : CHO-Z-NHCONR1R3 wherein A is a C2-18 divalent hydrocarbon group with at least 2 carbon atoms between the adjoining ether oxygen and nitrogen atoms or uch a group in which the chain is interrupted by O, N and/or S atoms, provided that in the group -OAN- there are at least 2 carbon atoms between hetero atoms, Z is the same as A except that at least 4 carbon atoms are interposed between the oxygen and nitrogen atoms in the group -OZN-, Y is C1-2 alkylene, R4 and R5 are C1-4 alkyl groups, R is H or a C1-18 hydrocarbon group, R2 is a C1-18 hydrocarbon group, R1 and R3 are C1-24 hydrocarbon groups or are combined with the ureido nitrogen atom to form a morpholino or piperidino group and the hydrocarbon radicals R, R1, R2 and R3 may be optionally substituted by halogens or hydroxy, amino, cyano or nitro groups, or interrupted in the carbon skeleton by O,N and/or S atoms, copolymers of the above vinyloxyureas with other ethylenically unsaturated monomers and methylol and alkoxymethyl derivatives of such polymers and copolymers, are used to impart whiteness - building and whiteness - retention characteristics to built detergent systems, such as those containing alkyl aryl sulphonates (e.g. sodium isopropyl naphthalene sulphonate and sodium octyl phenyl sulphonate); for preventing surface moving and the build-up of static charges on plastic coatings, such as poly-(methylmethacrylate), by application of films thereof from methanol solution; and for forming water, soap, alkali and solvent resistant, hard, glossy films on panels of glass, wood, fibreboard, steel, phosphated steel and other metals or on refrigerators, washers, air-conditioners and other metal appliances, which films are cast from solutions of the above compounds in acetone, dioxane, dimethylformamide, dimethylacetamide, acetonitrile, nitromethane, xylene, 2-ethoxyethylacetate, butanol or water, optionally containing further ingredients such as formaldehyde, N : N1-bis-methoxymethylethylene urea, methoxymethylated diethylene glycol dicarbamates, butyl acid phthalate, para-toluenesulphonic acid, alkyd resins, gums, rosin-ester, linseed-oil and/or titanium dioxide, followed by baking or curing at 60 DEG  to 150 DEG  C. Specification 763,635, [Group IV (a)], also is referred to.ALSO:Vinyloxyurea compounds of the formulae <FORM:0822266/IV(c)/1> wherein A is a C2-18 divalent hydrocarbon group with at least 2 carbon atoms between the adjoining ether oxygen and nitrogen atoms or such a group in which the chain is interrupted by O, N and/or S atoms, provided that in the group -OAN- there are at least 2 carbon atoms between hetero atoms, Z is the same as A except that at least 4 carbon atoms are interposed between the oxygen and nitrogen atoms in the group -OZN-, Y is C1-2 alkylene, R4 and R5 are C1-4 alkyl groups, R is H or a C1-18 hydrocarbon group, R2 is a C1-18 hydrocarbon group, R1 and R3 are C1-24 hydrocarbon groups or are combined with the ureido nitrogen atom to form a morpholino or piperidino group and the hydrocarbon radicals R, R1, R2 and R3 may be optionally substituted by halogens or hydroxy, amino, cyano or nitro groups, or interrupted in the carbon skeleton by O, N and/or S atoms, and their methylol derivatives, polymers, copolymers with other ethylenically unsaturated monomers, and methylolated and alkoxymethylated polymers and copolymers are (1) used in aqueous methanol or acetone solution as a warp-size for nylon, polyacrylonitrile, polyethyleneterephthalate and other synthetic filaments and staple yarns to increase weaving time between yarn breaks and to reduce filling and fuzz-balling; (2) padded on to wool or rayon fabric or nylon net from aqueous or alcoholic solution in presence of triethylamine phosphate or ethanolamine hydrochloride and cured at 250 DEG  to 300 DEG  F. to impart shrink resistance and a crisp bond; (3) applied to wool fabric from aqueous solution to impart a soft bond; and (4) emulsified in water with octyl polyoxyethylene phenol and exhausted on to cotton gabardine and cured at 300 DEG  F. to impart a soft bond. Specification 763,635 also is referred to.ALSO:One or more vinyloxyurea monomers of the formul  CH2 : CHO-A-NRCONHR1, CH2 : CHO-A-NR2CONR1R3, CH2 : CHO-Y-C(R4)(R5)NHCONR1R3 and CH2 : CHO-Z-NHCONR1R3, wherein A is a C2-18 divalent hydrocarbon group with at least 2 carbon atoms between the adjoining ether oxygen and nitrogen atoms or such a group in which the chain is interrupted by O, N and/or S atoms, provided that in the group -OAN- there are at least 2 carbon atoms between hetero atoms, Z is the same as A except that at least 4 carbon atoms are interposed between the oxygen and nitrogen atoms in the group -OZN-, Y is C1-2 alkylene, R4 and R5 are C1-4 alkyl groups, R is H or a C1-18 hydrocarbon group, R2 is a C1-18 hydrocarbon group, R1 and R3 are C1-24 hydrocarbon groups or are combined with the ureido nitrogen atom to form morpholino or piperidino groups and the hydrocarbon radicals R, R1, R2 and R3 may be optionally substituted by halogens or hydroxy, amino, cyano or nitro groups, or interrupted in the carbon skeleton by O, N and/or S atoms, alone or in admixture with one or more other copolymerizable olefinically unsaturated comonomers, are polymerized in bulk, aqueous or organic solution or dispersion in presence of a polymerization catalyst.  The catalyst may be used in presence of diethylenetriamine, buffers, metal ions, mercaptans, dispersing agents and emulsifiers such as tert.-octylpolyethylene oxyethylphenol.  Specified solvents are water, methanol, ethanol, isopropanol, butanol, dimethylformamide, benzene, toluene, ethyl acetate, acetone, methyl ethyl ketone and ethylene dichloride.  Specified polymerization catalysts include azo compounds, butyl perbenzoate, benzoyl peroxide and ammonium persulphate.  A large number of vinyloxyurea monomers is specified and their polymerization and copolymerization illustrated in examples. Specified comonomers are acrylic and methacrylic acids and their esters, amides and nitriles, including vinyloxyalkylacrylates; itaconic, maleic, fumaric and citraconic acids; vinyl, including vinyloxyethyl esters; ethyl, butyl, octyl, allyl, hydroxyethyl, aminoethyl, aminopropyl and dimethylaminoethyl vinylethers; vinyloxyethoxyethanol and vinyloxypropoxyethanol; vinyl chloride and bromide; vinylidene chloride; 1-chloro-1-fluoroethylene; ethylene; 1-acetoxy-1 : 3-butadiene; styrene; 2- and 4-vinylpyridines; divinylbenzene; and bis-(vinoxyethyl) urea.  The polymers may be further reacted with aldehydes, ketones, isocyanates and isothiocyanates.  Methylolated and alkoxymethyl derivatives are prepared by reacting the polymers with formaldehyde or a mixture of formaldehyde with an appropriate alcohol, respectively. Alkoxymethylated polymers are also prepared by reacting the corresponding methylolated polymers with an appropriate alcohol.  The polymers may be cured or insolubilized with polyvalent metal ions (e.g. Ca or Al), butyl acid phthalate, N : N1-bismethoxymethylene urea, para-toluenesulphonic acid or diethylene glycol dicarbamate. The vinyloxyurea monomers defined above may be incorporated in polyvinyl chloride resins to provide plasticisation and actinic light stabilization.  The monomers may be further reacted with cellulosic materials (e.g. hydroxyethylcellulose) or with polyhydric substances (e.g. polyvinyl alcohol), such materials being, if desired, in the form of films, fibres or fabrics and subjected to further reaction with formaldehyde.  The monomers and their methylol derivatives may also be used as components of urea-formaldehyde or melamine-formaldehyde resins.  Uses.-The polymers and their methylol and alkoxymethyl derivatives may be formed into filaments or fibres or cast as films on panels of wood, glass, metal or fibre-board; they may be used to form coatings, impregnations, adhesives and castings, to impart wet-strength to paper, to bond tyre fabric to rubber, as corrosion inhibitors in oils, as soil suspending or redispersing agents, as ingredients of detergent compositions, to impart water-repellency to cellulose, wool and silk, for shrink-proofing and imparting a soft hand to nylon, wool and rayon, as a warp-size for nylon and staple yarns providing reduction of pilling and fuzz-balling, as additives to pigments, alkyd resins, gums, rosin-esters and linseed oil esters, for incorporation into spinning dopes such as cuprammonium cellulose, cellulose acetate, nylon, P.V.C. and polyacrylonitrile dopes from which films and fibres having improved dyeability and insolubility are formed. Methanol solutions of the polymers may be applied to plastic coatings (e.g. of polymerized methyl methacrylate) to prevent surface-marring and static charge accumulation.  Specification 763,635 also is referred to.ALSO:The invention comprises compounds of the formul CH2:CHO-A-NRCONHR1, CH2:CHO-A-NR2CONR1R3, CH2:CHO-Y-C(R4)(R5)NHCONR1R3 and CH2:CHO-Z-NHCONR1R3, wherein A is a C2-18 divalent hydrocarbon group with at least 2 carbon atoms between the adjoining ether oxygen and nitrogen atoms or such a group in which the chain is interrupted by O, N and/or S atoms, provided that in the group -OAN- there are at least 2 carbon atoms between hetero atoms, Z is the same as A except that at least 4 carbon atoms are interposed between the oxygen and nitrogen atoms in the group -OZN-, Y is C1-2 alkylene, R4 and R5 are C1-4 alkyl groups, R is H or a C1-18 hydrocarbon group, R2 is a C1-18 hydrocarbon group, R1 and R3 are C1-24 hydrocarbon groups or are combined with the ureido nitrogen atom to form a morpholino or piperidino group, and the hydrocarbon radicals R, R1, R2 and R3 may be optionally substituted by halogens or hydroxy, amino, cyano or nitro groups, or interrupted in the carbon skeleton by