Patent GB-840908-A (GB)
Title: Sulpho esters of alpha-methylene carboxylic acids and polymers thereof
IPC: C07C309/12
Filed: 1958-03-13
Abstract: The invention comprises homopolymers of sulpho esters having the general formula CH2 = C(R)COO-QSO3M, wherein R represents hydrogen, halogen or an aliphatic, cycloaliphatic, aromatic or heterocyclic radical, Q represents a divalent aliphatic (which may be aromatic substituted), cycloaliphatic or aromatic radical (which may be aliphatic substituted), having its free valency bonds on different carbon atoms and M is a cation e.g. hydrogen, an alkali or alkaline earth or other metal, ammonium or an organic amine, and interpolymers of two or more of these sulpho esters.  The polymers may be obtained by polymerizing the monomers in the mass, in solution or dispersed in non-solvent liquid media and if desired with the aid of heat, ionizing radiation or free-radical catalysts.  The polymers may be used as or in the preparation of soil conditioners, stabilizers for aqueous colloidal dispersions and emulsions (e.g. polymer latexes), surface-active agents, anti-static finishes for textiles and plastics, adhesives, paper and textile sizes and dye assistants. Examples describe the homo-polymerization of 2-sodio sulpho ethyl acrylate, 2-sodio sulpho ethyl methacrylate, p-sodio sulpho phenyl acrylate and methacrylate and the use of the first-mentioned homopolymer in the conditioning of soil and the thickening of an aqueous latex of a copolymer of styrene and 1,3-butadiene.  Numerous other sulpho esters are mentioned.ALSO:The invention comprises sulpho-esters of the general formula CH2=C(R)CO2.Q.SO3M wherein R represents a hydrogen or halogen atom or an aliphatic, cycloaliphatic, aromatic or heterocyclic radical, Q represents a divalent aliphatic (which may be aryl-substituted), cycloaliphatic or aromatic (which may be aliphatic substituted) radical having its free valency bonds on two different carbon atoms and M is a cation.  They may be prepared by mixing an acyl halide CH2 \SC C(R).COX with a hydroxy sulphonic acid compound HO-Q-SO3M, dispersing the mixture in an inert liquid medium and heating, X representing a halogen atom and R, Q and M being as defined above.  A polymerization inhibitor may be present.  When Q represents a divalent aliphatic radical, reaction is preferably effected at the boiling-point of the reaction medium with rapid removal of hydrogen halide to prevent its addition to the double bond of the esterproduct.  When a hydroxy aromatic sulphonic acid is used it is preferably reacted in the form of its hydroxyl salt, e.g. NaOC6H5SO3Na; this reaction is preferably effected in an aqueous alkaline medium at 0-25 DEG  C.  These embodiments yield the sulpho-esters in salt form from which the free acids may be obtained by treatment with a hydrogen active cationexchange resin; any desired salt may then be obtained by neutralization of the sulpho-acid ester. Specified salts are those of the alkali and alkaline earth metals, ammonia and other ammonium bases, e.g. amines.  It is stated that in some instances the sulpho-esters derived from hydroxy aliphatic sulphonic acid compounds may be prepared using the a -methylene carboxylic acids preferably with azeotropic removal of the water of reaction.  The sulphoesters may be homo- or inter-polymerized (see Group IV (a)).  They may also be used in the preparation of soil conditioners, stabilizers for polymer latexes and other aqueous dispersions and emulsions, surface-active agents, adhesives, dye assistants and sizes for textiles and paper.  In examples: (1) acrylolyl chloride is added dropwise to a refluxing mixture of sodium isethionate in dichlorbenzene yielding 2-sodio sulpho ethyl acrylate and a lesser amount of 2-sodio sulpho ethyl b -chloro propionate; (2) the same acrylate is prepared by heating glacial acrylic acid with isethionic acid, using p-methoxy phenol as stabilizer and azeotropically distilling off water with benzene and the resulting 2-sulpho ethyl acrylate is recovered in the form of its Na salt; 2-sodio sulpho ethyl methacrylate and a mixture of 1-sodio sulpho 2-propyl and 2-sodio sulpho 1-propyl acrylates and may be some of the corresponding chloropropionates are prepared by each of the methods of (1) and (2); (7) p-sodio sulpho phenyl methacrylate is prepared by slowly adding methacrylolyl chloride to a mixture of the disodium salt of p-phenol sulphonic acid and sodium nitrite (stabilizer) in water at 5 DEG  C. while maintaining a pH of 10; the acrylate is prepared similarly.  Numerous other reagents are specified including acryloyl chlorides and bromides wherein R may be chlorine, phenyl, cyclohexyl or phenyl and various hydroxy alkane sulphonic acids containing such substituents as chlorine, bromine, methyl, chlormethyl, methoxy and phenyl, phenol sulphonic acid and hydroxy ethoxy benzene sulphonic acid and their salts.  Numerous sulpho esters derived therefrom are listed.ALSO:Sulpho esters of the general formula CH2=C(R)COO.Q.SO3M, wherein R represents a hydrogen or halogen atom or an aliphatic, cycloaliphatic, aromatic or heterocyclic monovalent radical, Q represents an aliphatic (which may be aromatic-substituted), cycloaliphatic or aromatic (which may be aliphatic substituted) divalent radical and M represents hydrogen or other cation, their homopolymers and interpolymers of two or more such esters are used as soil-conditioners.  Example 13 describes the use of homopolymerised 2-sodio sulpho ethyl acrylate in treating a silt loam soil.  Numerous examples of the monomers, polymers and interpolymers are specified.  Their preparation is described (see Groups IV(a) and IV(b)).