Patent GB-1061022-A (GB)
Title: Salts of esters of sulpho-carboxylic acids and polymers thereof with acrylonitrile
IPC: C07C309/17
Filed: 1963-10-24
Abstract: The invention comprises compounds of the general formula <FORM:1061022/C2/1> where R represents a hydrogen atom or a methyl group, R1 represents a hydrogen atom or a straight or branched chain alkyl group of from 1 to 7 carbon atoms, and M represents an alkali metal atom or an aliphatic tertiary amine of from 3 to 12 carbon atoms or a heterocyclic tertiary amine, n being zero when M is an alkali metal atom and 1 when M is a tertiary amine. The tertiary amine may be trimethylamine or tributylamine or a 5- or 6-membered heterocyclic tertiary amine e.g. pyrrole or pyridine. They may be prepared by esterifying the carboxylic group of a compound of formula HOOC-CH(R1)-SO3-(H)n-M with a compound of formula CH2 = C(R)-CH2-OH using an alkyl sulphonic acid as a catalyst. Compounds in which M is an alkali metal may also be prepared by esterifying a compound of formula Cl.CH(R1)-COOH with a compound of Formula III to form a compound of the formula Cl.CH(R1)-COOCH2-C(R) = CH2 and then reacting this compound with an alkali metal sulphite to give the compound of Formula I.  Examples are given for the preparation of the pyridine salts of allyl sulphoacetate and methallyl sulphoacetate, and of the sodium salt of allyl sulphoacetate.  The compounds of Formula I are useful for the preparation of copolymers and terpolymers with acrylonitrile (see Division C3).ALSO:The invention comprises copolymers containing units of acrylonitrile and units of a compound of the general formula CH2=CR-CH2OCOCH(R1)-SO3(H)nM where R represents a hydrogen atom or a methyl group, R1 represents a hydrogen atom or a straight or branched chain alkyl group of from 1 to 7 carbon atoms, and M represents an alkali metal atom or an aliphatic tertiary amine of from 3 to 12 carbon atoms or heterocyclic tertiary amine, n being zero when M is an alkali metal atom and 1 when M is a tertiary amine (see Division C2).  The polymer may be a binary copolymer containing from 85 to 96% by weight of units derived from acrylonitrile, or a terpolymer containing from 50 to 93% of units derived from acrylonitrile, from 2 to 20% of units derived from the compound of formula I and from 3 to 48% of units derived from a different compound containing a -CH=C< or CH2=C< group.  The preparation of the polymers is accelerated by heat, by actinic light and by polymerization catalysts such as peroxides, persulphates, perborates, the water-soluble salts of percarbonic acid, azo-bis-isobutyronitrile and mixtures of one or more of these catalysts.  An activating agent such as sodium bisulphite or an iron salt can be used in conjunction with the polymerization catalysts in aqueous systems.  Chain regulators such a alkyl mercaptans can also be added to the polymerization mixtures.  The polymerization can be carried out in mass, in solution, or in a non-solvent for the monomers or polymers, e.g. water.  In aqueous systems a surfactant can be used in amount not exceeding about 5% of the starting monomers.  Suitable copolymerizable monomers containing a -CH=C< or CH2=C< group include styrenes, vinyl and isopropenyl esters of saturated aliphatic or aromatic carboxylic acids containing from 2 to 17 carbon atoms, vinyl alkyl ethers and vinyl alkyl ketones wherein the alkyl group contains from 1 to 4 carbon atoms, vinyl sulphonamides, vinyl halides, vinylidene halides, vinylidene cyanide, acrylic acid and its derivatives, e.g. acrylamide, N-alkyl acrylamides or N,N-dialkyl acrylamides, alkyl esters, benzyl and phenyl esters and methacrylic acid and its corresponding amides and nitriles and esters; and monomeric amides, amides, imides and esters of bicyclo-[2,2,1]-5-heptene carboxylic acids.  The polymers can be readily converted from the salt forms to the free acids which can then be further converted to derivatives thereof by treatment with reagents capable of reacting with free sulphonic acid groups.  The interpolymers of the invention can be used for forming fibres and can also be formed into flexible sheets from their solutions or doses. Such solutions may have incorporated therein suitable fillers, dyes, pigments, lubricants or plasticizers.ALSO:Basic dyes are used to colour interpolymer compositions or fibres derived from polymers comprising units derived from acrylonitrile and units derived from a compound of the formula:-  <FORM:1061022/D1-D2/1> wherein R represents H or CH3, R1 represents H or a straight or branched chain C1 to C7 alkyl group, and M represents an alkali metal atom or an C3-C12 aliphatic tertiary amine or a heterocyclic tertiary amine, n being zero when M is an alkali metal atom and 1 when M is an aliphatic or heterocyclic tertiary amine (see Divisions C2 and C3 for preparation).  Specified dyes are Sevron Blue B, Sevron Brilliant Red 4G, Sevron Green B, Sevron Yellow L, Auramine SP, Calcozine Orange Rs, Rhodamine 5G, Bismarck Brown and Methyl Violet.