Patent GB-1087854-A (GB)
Title: Polymerisation products from monomeric esters of ªú¼ª-unsaturated carboxylic acids containing a cycloaliphatic ring in the alcohol residue and a method for their preparation
IPC: D06M14/00
Filed: 1964-12-01
Abstract: Polymers are made from novel monomeric esters of any of the following formulae <FORM:1087854/C3/1> <FORM:1087854/C3/2> <FORM:1087854/C3/3> in which R1 and R2 denote hydrogen atoms or methyl groups, A and the vicinal carbon atoms to which the hydroxy group and the ester group are attached together form a saturated cycloaliphatic ring with 5-10 carbon atoms, which may be substituted with aliphatic hydrocarbon radicals, Y1 denotes (1) a hydroxy group, (2) a group of the formula -CH2OZ, in which Z denotes a hydrogen atom or aliphatic, cycloaliphatic or aromatic radical linked to the -CH2- group by an ether or ester linkage, (3) an aldehyde group or (4) a radical of the formula -CH(OZ1)(OZ2), in which Z1 and Z2 denote monovalent aliphatic or cycloaliphatic radicals or together denote a bivalent aliphatic or cycloaliphatic radical, and Y2 denotes a hydrogen atom or a group of the formula -CH2OZ, in which Z is as defined above and may be common to Y1 and Y2 in an acetal linkage (see Division C2).  The esters may be derived for example, from acrylic, methacrylic, crotonic, maleic, fumaric, citraconic and itaconic acids. Specific esters described include those of the formulae <FORM:1087854/C3/4> <FORM:1087854/C3/5> <FORM:1087854/C3/6> <FORM:1087854/C3/7> <FORM:1087854/C3/8> <FORM:1087854/C3/9> The esters may be polymerized in solution or emulsion or by bulk or bead polymerization methods, alone or with other polymer-forming compounds, many of which are specified. Polymerization may also be effected on a substrate, e.g. glass fibre fabric or textile material. Suitable catalysts for polymerization include ionic catalysts and free radical catalysts such as azoisobutyrodinitrile, benzoyl peroxide, lauroyl peroxide, potassium persulphate and potassium persulphate/sodium bisulphite. Since the polymers contain free hydroxy groups, they may be further reacted (cross-linked) with appropriate reagents, many of which are specified.  Examples 1-13 illustrate the homopolymerization and copolymerization of the novel ester monomers; comonomers used are one or more of ethyl acrylate, butyl acrylate, t.-butyl acrylamide, acrylonitrile, calcium acrylate, vinyl acetate, dimethyl itaconate, styrene, vinyl butyl ether, vinylidene chloride, N-vinyl-pyrrolidone, and the acetal formed from acrolein and 1,1-bis-(hydroxymethyl) - 3,4 - epoxycyclohexane. Examples 14-16 illustrate compositions for treating fabrics comprising emulsions or ethyl acetate solution of certain of the novel copolymers and additionally containing (a) hexamethylolmelamine-methanol reaction product, sodium alginate, gas soot, non-ionic emulsifier, dioctyl phthalate blue pigment (organic), caseinurea mixture and diammonium phosphate; (b) butanol solution of melamine methylol butyl ether and acetic acid; (c) methylolmelamine methyl ether, dimethylol ethylene urea dimethyl ether, polyethylene, magnesium chloride and citric acid.ALSO:The invention comprises esters of any of the formulae <FORM:1087854/C2/1> <FORM:1087854/C2/2> <FORM:1087854/C2/3> in which R1 and R2 denote hydrogen atoms or methyl groups, A and the vicinal carbon atoms to which the hydroxy group and the ester group are attached together form a saturated cyclo-aliphatic ring or ring system with 5-10 carbon atoms, which may be substituted with aliphatic hydrocarbon radicals, Y1 denotes (1) a hydroxy group; (2) a group of the formula -CH2OZ, in which Z denotes a hydrogen atom or an aliphatic, cycloaliphatic or aromatic radical linked to the -CH2- group by an ether or ester linkage, (3) an aldehyde group; or (4) a radical of the formula -CH(OZ1)(OZ2), in which Z1 and Z2 denote monovalent aliphatic or cycloaliphatic radicals or together denote a bivalent aliphatic or cycloaliphatic radical, and Y2 denotes a hydrogen atom or a group of the formula -CH2OZ, in which Z is as defined above and may be common to Y1 and Y2 in an acetal linkage.  The esters are obtainable by reacting an unsaturated acid of 3-5 carbon atoms or its anhydride (1) with an appropriately substituted cycloaliphatic 1,2-mono-epoxide; or (2) with a mono-unsaturated compound of the formula <FORM:1087854/C2/4> in the presence of an epoxidizing agent, as described in Specification 956,180.  Esters of acrylic, methacrylic, crotonic, maleic, fumaric, citraconic and itaconic acids may be so prepared, and the preparation of esters of the following formulae is described <FORM:1087854/C2/5> <FORM:1087854/C2/6> <FORM:1087854/C2/7> <FORM:1087854/C2/8> <FORM:1087854/C2/9> <FORM:1087854/C2/100> Other specified esters includ those of the following formulae <FORM:1087854/C2/111> <FORM:1087854/C2/122> <FORM:1087854/C2/133> <FORM:1087854/C2/144> <FORM:1087854/C2/155> The products are polymerizable (see Division C3).ALSO:Polymers are made from monomeric esters of any of the following formul  <FORM:1087854/D1-D2/1> in which R1 and R2 denote hydrogen atoms or methyl groups, A and the vicinal carbon atoms to which the hydroxy group and the ester group are attached together form a saturated cycloaliphatic ring with 5-10 carbon atoms, which may be substituted with aliphatic hydrocarbon radicals, Y1 denotes (1) a hydroxy group, (2) a group of the formula -CH2OZ, in which Z denotes a hydrogen atom or an aliphatic, cycloaliphatic or aromatic radical linked to the -CH2- group by an ether or ester linkage, (3) an aldehyde group or (4) a radical of the formula -CH(OZ1) (OZ2), in which Z1 and Z2 denote monovalent aliphatic or cycloaliphatic radicals or together denote a bivalent aliphatic or cycloaliphatic radical, and Y2 denotes a hydrogen atom or a group of the formula -CH2OZ, in which Z is as defined above and may be common to Y1 and Y2 in an acetal linkage (see Division C2). Specific esters described include those of the formul <FORM:1087854/D1-D2/2> fibre fabric or textile material.  Since the polymers contain free hydroxy groups, they may be further reacted with appropriate reagents, many of which are specified.  The polymers or their further reaction products may be used in the treatment of textiles materials, e.g. cotton, linen, acetyl cellulose, dacron, Terylene, Orlon.  Thermovyl, Perlon and nylon.  They are useful to for the impregnation of paper or cardboard.  In Example 14, a cotton, nylon, terylene or terylene-cotton fabric is impregnated with a composition containing a product of Formula V and a blue anthraquinone pigment.  In Example 15, a nylon fabric is coated with a composition containing a product of Formula V.  In Example 16, cotton is given an improved crease-resistance by padding with a composition containing a product of Formula V followed by washing with a condensation product from p-nonylphenol and ethylene oxide.ALSO:Polymers are made from monomeric esters of any of the following formul  <FORM:1087854/B1-B2/1> in which R1 and R2 denote hydrogen atoms or methyl groups, A and the vicinal carbon atoms to which the hydroxy group and the ester group are attached together form a saturated cycloaliphatic ring with 5-10 carbon atoms, which may be substituted with aliphatic hydrocarbon radicals, Y1 denotes (1) a hydroxy group, (2) a group of the formula -CH2OZ, in which Z denotes a hydrogen atom or an aliphatic, cycloaliphatic or aromatic radical linked to the -CH2- group by an ether or ester linkage, (3) an aldehyde group or (4) a radical of the formula -CH(OZ1) (OZ2), in which Z1 and Z2 denote monovalent aliphatic or cycloaliphatic radicals or together denote a bivalent aliphatic or cycloaliphatic radical, and Y2 denotes a hydrogen atom or a group of the formula -CH2OZ, in which Z is as defined above and may be common to Y1 and Y2 in an acetal linkage (see Division C2). Specific esters described include those of the formul  <FORM:1087854/B1-B2/2> Since the polymers contain free hydroxy groups, they may be further reacted with appropriate reagents, many of which are specified.  The polymers or their further reaction products may be used in the treatment of textiles materials, e.g. cotton, linen, acetyl cellulose, dacron, Terylene, Orlon, Thermovyl, Perlon and nylon.  In Example 15, a nylon fabric is coated with a composition containing a product of Formula V.