Patent GB-853619-A (GB)
Title: New unsaturated glycidyl ethers, polymers thereof and methods for producing them
IPC: C08F16/12
Filed: 1957-01-31
Abstract: The mixture comprises polymers containing <PICT:0853619/IV(a)/1> units derived by polymerizing a compound of the general formula <FORM:0853619/IV(a)/1> through the vinyl group and/or the epoxy group, X representing oxygen or sulphur and A representing a C2-C12 alkylene group providing at least two carbon atoms between the adjacent O and X atoms and which may contain cycloalkyl, aryl or aralkyl substitutents or, alternatively, A representing the group -(CnH2nX1)x CnH2n-wherein X1 is oxygen or sulphur, n is an integer from 2 to 12 and x an integer from 1-5, there being at least two carbon atoms between each adjacent pair of hetero atoms in the group -XAO-.  The above monomeric vinyl compounds may be polymerized alone via the epoxy group with the aid of a boron trifluoride catalyst. The monomers may also be subjected to addition polymerization alone or with other ethylenically unsaturated compounds by the usual techniques employing free radical catalysts to give thermo plastic polymers containing glycidyl groups which may be cured to cross-link the polymer through the epoxy linkage, suitably by treatment with an acid catalyst.  The monomeric vinyl compounds and their thermoplastic addition polymers may be incorporated in amino-plast resin-forming condensates such as those of the urea- or triazineformaldehyde type or in products derived therefrom such as moulded articles or textile finishes, and then be subjected to curing.  The vinyl monomers and the epoxy group-containing polymers thereof may be used as stabilizing or platicising agents in halogencontaining polymers including inter alia polyvinyl chloride and vinyl or vinylidene chloridevinyl acetate or acrylonitrile copolymers.  Various of the polymers may be used as coating materials (see Group VIII).  In typical Examples: (10) 2-vinyloxyethyl glycidyl ether is treated with BF3 in diethyl ether yielding inter alia a polymer free from oxirane oxygen; (11) 2-(vinyl thio) ethyl glycidyl ether is treated with azo-bisisobutyronitrile yielding an addition polymer containing epoxy groups; (12) the monomer of (11) is addition polymerized with styrene, vinyl acetate, acrylonitrile, diethyl maleate and ethyl acrylate respectively; (15) 5-vinyloxypentyl glycidyl ether is copolymerized with vinyl chloride; (16) the monomer of (11) is copolymerized with a mixture of butyl methacrylate and methyl methacrylate and the polymers cured by heating with cumyl succinic acid.  Numerous other vinyl monomers and unsaturated comonomers and amino plast condensates are mentioned.ALSO:The invention comprises vinyl ethers of the general formula :  <FORM:0853619/IV(b)/1> in which X represents oxygen or sulphur and A represents either a C2-12 alkylene group providing at least two carbon atoms between the adjacent O and X atoms and which may be straight or branched and may or may not be substituted with a cycloalkyl aryl or aralkyl group, or A represents a group of the formula -(Cn H2n X1)x Cn H2n-wherein X1 represents oxygen or sulphur, n is an integer from 2 to 12 and x is an integer from 1 to 5, there being at least two carbon atoms between each adjacent pair of hetero atoms in the group-XAO-.  The ethers may be prepared by reacting an epihalohydrin of the formula <FORM:0853619/IV(b)/2> wherein Y is chlorine or bromine with an alcoholate of the formula CH2=CHXAOZ wherein Z represents an alkali metal, suitably at a temperature of 20-100 DEG  C.  The epihalohydrin is preferably used in excess and the alcoholate is desirably added gradually to the epihalohydrin.  The alcoholate may be prepared by reacting an alkali metal or hydroxide or alkoxide thereof with the alcohol CH2=CHXAOH and may be used in solution, for example in an alcohol, or in the form of a slurry in an inert non-solvent ; alternatively, the vinyl ether alcohol CH2 CHXAOH may be dissolved in a solution of an alcohol to be used as reaction solvent and containing an alkoxide thereof, the solution them being added to the epihalohydrin, and in this method, the alkali metal alkoxide of the vinyl ether alcohol is formed in situ through an equilibrium interchange.  The alcoholic solvents e.g. isopropanol or sec butanol, which may be used should not give rise to a competing reaction with the epihalohydrin to a significant extent.  The epoxy ether products may be isolated by filtering or extracting with water to remove solid salts followed by distillation.  The epoxy compounds are useful as stabilisers for halogen containing polymers and may be polymerised (see Group IV(a)).  Examples describe the preparation of (1) 2-(vinyl thio) ethyl glycidyl ether and 3-(vinyl oxy) propyl glycidyl ether, (2) 2- (vinyl oxy) ethyl glycidyl ether, (4) 2-(vinyl oxy) isopropyl glycidyl ether, (5) 5-(vinyl oxy) pentyl glycidyl ether and 12-(vinyl oxy) lauryl glycidyl ether, (6) 2-(vinyl oxy) ethyl thio ethyl glycidyl ether and 1-(vinyl oxy hexa-ethenoxy)-2:3. epoxypropane, (7) 2-[2-(vinyl thio) ethyl thio] ethyl glycidyl ether, (8) 2- (vinyl thio) propyl glycidyl ether and (9) 2-phenyl-2-(vinyl thio) ethyl glycidyl ether.  Numerous other alcoholic vinyl ethers are specified as reagents, including some wherein the alkylene radical A is substituted by cyclohexyl, chlorphenyl or benzyl.ALSO:Textiles, such as cotton, wool and rayon fabrics, are rendered crease-resistant and shrinkproof by treatment with thermoplastic ethylenic addition polymers or co-polymers of vinyl compounds of the general formula: <FORM:0853619/IV (c)/1> or with amino-plast resin forming condensates, such as urea or melamine formaldehyde condensates, having incorporated therein a monomeric vinyl compound of the given formula or a thermoplastic addition polymer thereof, X representing oxygen or sulphur and A representing a C2-C12 alkylene group which may or may not contain cycloalkyl, aryl or aralkyl substituents and which provides at least two carbon atoms between the adjacent O and X atoms or, alternatively, A represents the group: -(CnH2nX1)x CnH2n-wherein X1 is oxygen or sulphur, n is an integer from 2 to 12 and x an integer from 1-5, there being at least two carbon atoms between each adjacent pair of hetero atoms in the group -XAO-.  The treated material is subjected to curing or baking, suitably with the aid of an acid catalyst, to effect a cross-linking via the epoxy groups.  In Examples 17 and 18: wool flannel is treated with an aqueous dispersion of a copolymer obtained from 2-(vinyl thio) ethyl glycidyl ether and butyl acrylate and the flannel is thereafter dried and baked and so rendered shrinkproof. Numerous other similar resins are mentioned.ALSO:Glass, wood, metal and other substrates are treated, to render them water-repellant, with thermoplastic ethylenic addition polymers or copolymers of vinyl compounds of the general formula <FORM:0853619/III/1> or with amino-plast resin-forming condensates, such as urea or melamine-formaldehyde condensates, in which are incorporated a monomeric vinyl compound of the given formula, or a thermoplastic addition polymer thereof, X representing oxygen or sulphur, and A denoting a C2-C12 alkylene group which may or may not be substituted by a cycloalkyl, aryl or aralkyl group, and which provides at least two carbon atoms between the O and X atoms, or, alternatively, A denoting a group -(CnH2nX1)xCnH2n wherein X1 represents oxygen or sulphur, n is an integer from 2-12 and x is an integer from 1 to 5, there being at least two carbon atoms between each adjacent pair of hetero atoms in the group -XAO-.  The treated materials may be cured or baked, suitably in the presence of an acid catalyst to effect cross-linking via the epoxy groups.  In Example 16, glass plates are coated with a co-polymer derived from 2-(vinyl thio) ethyl glycidyl ether and methyl and butyl methacrylates and containing cumyl succinic acid, and baked.