Patent GB-831635-A (GB)
Title: Monomeric polymerizable ureido and thioureido compounds, methods for producing them and polymers thereof
IPC: C08B11/15
Filed: 1956-04-12
Abstract: Divided out of 822,267, addition to 761,901 Homopolymers and copolymers of compounds having the formula <FORM:0831635/III/1> in which R is H or CH2; A is a phenylene group or an alkylene group having 2-4 carbon atoms, of which a chain of at least 2 extends between the adjoining O and N atoms; R1 is a C4-C12 alkyl group containing a tertiary carbon atom attached to the adjoining N atom; X is O or S; and R2 is an alkyl group, are dissolved in a suitable solvent containing an acid catalyst and may then be applied to paper, leather, textiles, wood, metal, glass or plastics as coatings, adhesives or impregnants which can be dried and directly converted to insoluble and infusible condition by heating.  The polymers may be dissolved or suspended in water or organic solvents, provided with extenders or fillers and then applied to various substrates such as porcelain or metals.  On heating the composition is converted to a baked enamel finish.  If desired, pigments such as titanium dioxide, lithopone, barium sulphate, and ultramarine blue may be added.  In the examples: (a) a solution of CH2=C(CH3) COOCH2CH2-N(C4H9-t) -CONHCH2OCH3 in methanol, ethanol or butanol, containing 5% of butyl acid phthalate (or butyl phosphoric acid) is applied to a substrate such as leather, glass, wood, cotton, nylon, and rayon, and the material is dried at 220 DEG  F.; the surface is receptive to further reaction with amines, such as laurylamine, or with resins, such as maleic polyesters in styrene solution; (b) CH2=C(CH3)COOCH2-CH2N(t-C4H9) CSNHCH2OCH3 is applied from a 5-15% solution containing an acid catalyst such as butyl phosphoric acid or ammonium chloride to such materials as textiles, wood, and the like and the treated material is heated to 150-250 DEG  F.; the treated materials are much less hydrophilic and may be further reacted with amines such as laurylamine to render the surface basic and hydrophobic; (c) a polymer prepared by heating CH2=C(CH3) COOCH2-CH2-N(C4H9-t) CONHCH2OCH3 in butanol solution in the presence of benzoyl peroxide is used for preparing coatings for leather, ceramic tile, metal and fabrics; and (d) a polymer prepared from CH2=C(CH3)COOCH2CH2N(t-C4-H9) CSNHCH2OCH3 is used as a coating for metals or plastics.ALSO:The invention comprises compounds of formula <FORM:0831635/IV (b)/1> in which R is H or CH3; A is a phenylene group or an alkylene group having 2-4 carbon atoms of which a chain of at least two extends between the adjoining O and N atoms; R1 is a C4-C12 alkyl group containing a tertiary carbon atom attached to the adjoining N atom; X is O or S; and R2 is an alkyl group.  They may be prepared by reacting compounds of formula CH2=C(R)COOANHR1 with a compound of formula R2OCH2NCX.  The reaction may be effected in bulk or in solution in an inert organic solvent, such as ether, benzene, acetonitrile, dioxane or t-butanol.  The reaction is carried out at temperatures between 0 DEG  and 50 DEG  C., preferably with cooling. The isocyanates and thioisocyanates used as starting material may be prepared by reacting compounds of formula R2OCH2Cl with silver cyanates or alkali metal thiocyanates.  In the examples (a) methoxymethyl isocyanate is reacted with t-butylaminoethyl methacrylate to give N1-t-butyl-N1-methacrylatoethylurea, CH2=C(CH3)COOCH2CH2-N(C4H9-t.) -CONHCH2OCH3; and (b) methoxymethyl isothiocyanate is reacted with t-butylaminoethyl methacrylate to give N-t-butyl-N-methacrylatoethyl - N1 - methoxymethylthiourea, CH2=C(CH3)COOCH2CH2N(t-C4H9) CSNHCH2OCH3.ALSO:Homopolymers and copolymers of compounds of the formula <FORM:0831635/IV(c)/1> in which R is H or CH3; A is a phenylene group or an alkylene group having 2-4 carbon atoms, of which a chain of at least 2 extends between the adjoining O and N atoms; R1 is a C4-C12 alkyl group containing a tertiary carbon atom attached to the adjoining N atom; X is O or S; and R2 is an alkyl group; are dissolved in a suitable solvent containing an acidic catalyst and are then applied to textiles as coatings, adhesives or impregnants which can be dried and directly converted to an insoluble and infusible condition by heating.  The polymers may be applied to wool, rayon or cotton fabrics to reduce water-sensitivity and to stabilize them against shrinkage.  They may also be applied to cotton and rayon fabrics for crushproofing and crease-proofing and they may be used to impart water-repellency to textile fabrics, especially cotton and rayon, when R1 has 8-12 carbon atoms or there are hydrophobic groups present in the comonomer.  In the examples: (a) N-methoxymethyl-N1-t-butyl-N1 - methacrylatoethylurea, CH2=C(CH3) COOCH2CH2-N(C4H9-t) -CONHCH2OCH3, is dissolved in a lower alcohol containing 5% butyl acid phthalate (or butyl phosphoric acid) and is applied to a substrate such as cotton, nylon or rayon, and the material is dried at 220 DEG  F. for 10 minutes; the surface may now react with an amine such as laurylamine or with a resin such as a maleic polyester in styrene solution; (b) N-t-butyl-N-methacrylato-ethyl - N1 - methoxymethylthiourea, CH2=C (CH3)COOCH2CH2N(t-C4H9) CSNHCH2OCH3, is applied from a 5 to 15% solution containing an acid catalyst, such as butyl phosphoric acid or ammonium chloride, textiles or wool, and the treated material is dried and cured at 150-250 DEG  F.; the treated materials may be further treated with an amine such as lauryl-amine; and (c) a polymer prepared by heating N - methoxymethyl - N1 - t - butyl - N1 - methacrylatoethylurea in butanol in the presence of benzoyl peroxide is used for the treatment of fabrics, preferably butyl phosphoric acid is included and the material is baked.ALSO:Compounds of formula <FORM:0831635/IV (a)/1> in which R is H or CH3; A is a phenylene group or an alkylene group having 2-4 carbon atoms of which a chain of at least 2 extends between the adjoining O and N atoms; R1 is a C4-C12 alkyl group containing a tertiary carbon atom attached to the adjoining N atom; X is O or S; and R2 is an alkyl group; may be polymerized or copolymerized with other p  polymerizable olefinically unsaturated compounds in the presence of an acyclic azo compound or other free radical type of initiator.  Typical azo catalysts are azodiisobutyronitrile, azodiisobutyramide; dimethyl, diethyl and dibutyl azodiisobutyrate; azobis-(a ,g -dimethylvaleronitrile); and dimethyl azobismethylvalerate.  Other free radical types of initiators which may be used are butyl perbenzoate, benzoyl peroxide, lauroyl peroxide, acetyl peroxide and alkali metal persulphates, optionally in conjunction with reducing agents such as sodium hydrosulphite.  To effect polymerization with an azo catalyst the monomer and catalyst are mixed directly or in the presence of an inert solvent, e.g. water, methanol, ethanol, isopropanol, butanol, dimethylformamide, benzene, toluene and ethyl acetate.  Unsaturated compounds which may be used for forming the copolymers are, for example, acrylic, methacrylic, itaconic, maleic, fumaric and citraconic acids with monohydric alcohols such as methyl, dodecyl, cyclohexyl, allyl, cyanoethyl and dimethylaminoethyl alcohols; vinyl esters of carboxylic acid; vinyloxyalkyl esters; vinyl ethers such as ethyl vinyl ether, butyl vinyl ether, octyl vinyl ether, allyl vinyl ether, hydroxyethyl vinyl ether, aminoethyl vinyl ether, aminopropyl vinyl ether, dimethylamino ethyl vinyl ether, vinyloxyethoxyethanol, and vinyloxypropoxyethanol; methacrylonitrile and acrylonitrile; acrylamide, methacrylamide and N-substituted amides of these types; vinyl chloride, vinyl bromide, vinylidine chloride; 1-chloro-1-fluoroethylene, and ethylene; 1-acetoxy-1,3-butadiene; styrene, 2-vinyl-pyridine, 4-vinylpyridine, N-vinylpyrrolidone, formamidoethyl vinyl ether and divinyl benzene; and ethylene diacrylate, ethylene dimethacrylate, bis - (vinoxyethyl) - urea, vinoxyethyl acrylate and vinoxypropyl acrylate.  Copolymerization may be effected in bulk, in solution or in dispersion.  Suitable solvents are, for example, water, benzene, toluene, methanol, ethanol, butanol, acetone, methyl ethyl ketone, dimethylformamide, ethyl acetate and ethylene dichloride.  The compounds to be copolymerized may be dispersed in water and an emulsion and/or dispersing agent may be added in addition to the catalyst.  If desired, modifiers such as buffers, metal ions and mercaptans may be added.  The polymers obtained may be dissolved in a solvent containing an acidic catalyst and then applied to various materials as coatings, adhesives or impregnants which can be dried and directly converted to insoluble and infusible condition by heating.  Suitable acid catalysts are ammonium phosphate, ammonium thiocyanate, the hydrochloride or other acid salt of a hydroxy aliphatic amine, ammonium chloride, pyridine hydrochloride and benzyldimethylamine oxalate.  Compositions containing the homopolymers and copolymers dissolved or suspended in water or organic solvents may be dyed, pigmented or provided with extenders or fillers, and may be combined with other film-forming or coating resins, such as aminoplasts, including urea-formaldehyde and melamine-formaldehyde resins, alkyds and vinyl polymers.  These compositions may be applied to various substrates and subsequently converted by heating to a baked enamel finish. Pigments such as titanium dioxide, lithopone, barium sulphate, and ultramarine blue may be added to the compositions.  In the examples: (a) N-methoxymethyl-N1-t-butyl - N1 - methacrylatoethylurea, CH2= C(CH3)COOCH2CH2 - N(C4H9 - t) - CONH CH2OCH3, dissolved in methanol, ethanol, or butanol containing 5% of butyl acid phthalate or butyl phosphoric acid, is applied to leather, glass, wood, cotton, nylon or rayon and the material is dried at 220 DEG  F.; the resulting surface is receptive to further reaction with amines such as lauryl amine or with resins such maleic polyesters in styrene solution; (b) CH2 = CCCH3)