Stabilisieren halogenhaltiger Polymerisate

摘要

Polymeric organo-tin compounds of the general formula: wherein n represents a numeral having a value greater than 1, R and R1 represent the same or different monovalent hydrocarbon radicals, SX represents the radical of an aliphatic or aromatic compound, and Y represents the radical SX, an alkoxy radical, the acyloxy radical derived from a monocarboxylic acid or from a polycarboxylic acid in which all but one of the carboxylic groups are blocked by esterification, a radical of the formula: wherein R2 represents hydrogen or a methylene activating group, and R3 and R4 are methylene activating groups, or the radical of a sulphonamide, oxime or imide, are prepared in the case where Y represents SX, an alkoxy radical or the above acyloxy radical, by reacting a polymeric organo-tin alkoxide of the general formula: wherein R2O represents an alkoxy radical and Y1 represents an alkoxy radical or the above acyloxy radical, with the required aliphatic or aromatic mercaptan and removing alcohol formed in the reaction, and in the case where Y represents the radical of the formula: or the radical of a sulphonamide, oxime or imide, by reacting one mol. of the above polymeric organo-tin alkoxide, wherein Y1 represents an alkoxy radical, with one mol. of a compound having an activated methylene group of the formula: wherein R2, R3 and R4 have the above significance, or a sulphonamide, oxime or imide. If SX and Y in the general formula of the desired polymeric organo-tin compounds represent the residues of different aliphatic or aromatic mercapto-compounds, one mol. of the above polymeric organo-tin alkoxide reactant, wherein Y1 represents an alkoxy radical, is reacted with one mol. each of two different required aliphatic or aromatic mercaptans. The polymeric organo-tin alkoxide reactant is preferably a polymeric dialkyl or diaryl tin dimethoxide. An example of a sulphonamide reactant is N-butyl-benzenesulphonamide, an example of an imide reactant is phthalimide, an example of an oxine reactant is cyclohexanone oxime, and examples of reactants having activated methylene groups are referred to in Specification 735,030, and sulphones such as phenylsulphonyl acetone and b -keto-carboxylic acid derivatives are specifically referred to. The monovalent hydrocarbon radicals R1 and R2 may be methyl, ethyl, propyl, butyl, amyl, hexyl, octyl, lauryl, allyl, benzyl, phenyl, tolyl and cyclohexyl radicals. The aliphatic or aromatic mercaptan reactant may be an aliphatic mercaptan containing 8 to 18 carbon atoms, e.g. decyl or dodecyl mercaptan, a thionaphthol, a phenoxyethylmercaptan, a phenoxyethoxyethylmercaptan, thiobenzyl alcohol, a mercapto-alcohol, e.g. thioethylene glycol, a monothiopropylene glycol, thioglycerol or monothiodiethylene glycol, an ester of a mercapto-alcohol, e.g. in which the hydroxyl group is esterified with an aliphatic, aromatic or alicyclic saturated or unsaturated monocarboxylic acid-particularly thioglycol 2-ethylhexoic acid ester, or a mercaptocarboxylic acid ester, e.g. an ester of thioglycollic acid such as ethyl thioglycollate, or an ester of a mono- or dibasic-aliphatic or aromatic mercaptocarboxylic acid such as an ester of beta-thiopropionic, thiolactic, a thiobutyric, alpha-mercaptolauric, acid, thiomalic acid or thiosalicylic acid. In the examples: (1) 2-ethylhexyl thioglycollate is reacted with a dimeric, trimeric and tetrameric dibutyl tin methoxide to form polymeric organo-tin compounds of the formul : and respectively, wherein R1 is the butyl radical and SR is the residue of 2-ethylhexyl thioglycollate; similar compounds may be obtained using other esters of thioglycollic acid, e.g. an ester derived from oleyl alcohol and thioglycollic acid; (2) one mol. of a trimeric dibutyl tin dimethoxide is reacted with one mol. of 2-ethylhexyl thio glycollate and then with one mol. of lauric acid to form an organo-tin compound of the formula: (3) one mol. of dimeric dibutyl tin dimethoxide is reacted with 2-ethylhexyl thioglycollate and then with one mol. of oleyl maleate half ester to form an organo-tin compound of the formula- (4) a trimeric dibutyl tin dimethoxide is reacted as in (3) with 2-ethylhexyl thioglycollate and then with 1,2-propylene glycol maleate half ester to form an organo-tin compound of the formula: (5) tetrameric dibutyl tin dimethoxide is reacted with dodecyl mercaptan to form an organo-tin compound of the formula: (6) a dimeric diethyl tin dimethoxide is reacted with iso-octyl thioglycollate to form an organo-tin compound of the formula: (7) one mol. of a polymeric dibutyl tin dimethoxide prepared according to Example (1) of Specification 694,944 is reacted with one mol. of lauryl mercaptan to form a mixture of monomer and polymer corresponding substantially to the formula: Polymeric compositions comprise a halogen containing synthetic resin and as a stabilizer a polymeric organo-tin compound of the above general formula. The stabilizers may be used in conjunction with other metallic or non-metallic stabilizers such as salts of barium, strontium, calcium, zinc and tin, compounds having one or more epoxy groups in the molecule, substituted phenols and triesters of phosphorus acid. Halogen containing synthetic resins which may be stabilized are polymers of vinyl chloride such as polyvinyl chloride, copolymers of vinyl chloride with vinyl acetate, with esters of acrylic and methacrylic acids, with acrylonitrile, with vinylidene chloride, with diene compounds and with diethyl maleate, diethyl fumarate and maleic anhydride; after-chlorinated polymers and copolymers of vinyl chloride; copolymers of vinyl chloride and vinylidene chloride with unsaturated aldehydes, ketones and ethers such as acrolein, crotonaldehyde, vinyl methyl ketone, vinyl methyl ether and vinyl isobutyl ether; polymers of vinyl chloroacetate and dichlorodivinyl ether; chlorinated polymers of vinyl acetate; chlorinated polymeric esters of acrylic and alpha-substituted acrylic acids; polymers of chlorinated styrenes, e.g. dichlorostyrene; chlorinated polymers of ethylene; polymers and after-chlorinated polymers of chlorobutadienes and their copolymers with vinyl chloride; and mixtures of any of these polymers. The corresponding bromides and fluorides of the above halogen-containing synthetic resins may also be used in the compositions. In the examples compositions are prepared containing (1) polyvinyl chloride, dioctyl phthalate and the trimeric tin di (2-ethylhexyl acetate mercaptide) of Example (1) above; (2) polyvinyl chloride, dioctyl phthalate and an organo-tin compound of the formula in Example (4) above; and (3) polyvinyl chloride and a mixture of monomeric and polymeric organo-tin compounds corresponding substantially to the formula in Example (7) above. Specification 711,145 also is referred to.ALSO:The invention comprises organo-tin compounds of the general formula wherein n represents a numeral having a value greater than 1, R and R1 represent the same or different monovalent hydrocarbon radicals, SX is the radical of an aliphatic or aromatic mercapto compound, and Y represents the radical SX, an alkoxy radical, or the acyloxy radical of a monocarboxylic acid or of a polycarboxylic acid in which all but one of the carboxylic groups are blocked by esterification, a radical of the formula where R2 represents hydrogen or a methyleneactivating group, and R3 and R4 are methyleneactivating groups, or the radical of a sulphonamide, oxime or imide and the preparation thereof in the case where Y represents SX, an alkoxy radical or the above acyloxy radical, by reacting a polymeric organo-tin alkoxide of the general formula wherein R2O represents an alkoxy radical and Y1 represents an alkoxy radical or the above acyloxy radical, with the required aliphatic or aromatic mercaptan and removing the alcohol formed in the reaction, and in the case where Y represents the radical of the formula or the radical of a sulphonamide, oxime or imide, by reacting one mol. of the above polymeric organo-tin alkoxide, wherein Y1 represents an alkoxy radical, with one mol. of the required mercapto compound and one mol. of a compound having an activated methylene group of the formula wherein R2, R3 and R4 have the above signi ficance, or a sulphonamide, oxime or imide. If SX and Y in the general formula of the desired organo-tin compounds are to represent the residues of different aliphatic or aromatic mercapto compounds, one mol. of the polymeric organo-tin alkoxide, where Y1 represents an alkoxy radical, is reacted with one mol., each of two different required aliphatic or aromatic mercaptans. The polymeric organo-tin alkoxide reactant is preferably a polymeric dialkyl or diaryl tin dimethoxide. An example of a sulphonamide reactant is N-butyl-benzenesulphonamide, an example of an imide reactant is phthalimide, an example of an oxime reactant is cyclohexanone oxime, and examples of reactants having activated methylene groups are referred to in Specification 735,030, and sulphones such as phenylsulphonyl acetone and b -keto-carboxylic acid derivatives are specifically referred to. The monovalent hydrocarbon radicals R1 and R2 may be methyl, ethyl, propyl, butyl, amyl, hexyl, octyl, lauryl, allyl, benzyl, phenyl, tolyl and cyclohexyl radicals. The aliphatic or aromatic mercaptan reactant may be an aliphatic mercaptan containing 8 to 18 carbon atoms, e.g. decyl or dodecyl mercaptan, a thionaphthol, a phenoxyethylmercaptan, a phenoxyethoxyet