| 摘要 |
Synthetic resin compositions comprise as a major constituent a halogen containing synthetic resin and as a stabilizer an organo-tin compound of the general formula <FORM:0711145/IV (a)/1> wherein R and R1 represent the same or different aliphatic, alicyclic or aromatic hydrocarbon radicals, OR11 represents and alkoxy radical derived from an aliphatic, alicyclic or aromatic alcohol, Z represents the acyloxy radical of a monocarboxylic acid or the half ester acyloxy radical of a dicarboxylic acid, and x is a numeral equal to 1 or more. The organo-tin compound may be added before, during or after formation of the halogen-containing synthetic resin, the preferred quantity of stabiliser being in such amounts that 0.1 to 5 per cent. by weight of tin is present based on the weight of resin. Plasticizers, e.g. phthalic acid esters, adipates, phosphates and ricinoleates, and alcohol esters of unsaturated fatty acids may be added to the compositions. The following halogen containing synthetic resins are referred to: polymers of vinyl chloride and copolymers with vinyl acetate, esters, nitriles and amides of acrylic and methacrylic acids, diene compounds, and copolymers with diethyl maleate, diethyl fumarate and maleic anhydride, after chlorinated homo-polymers and copolymers of vinyl chloride, polyvinylidene chloride and copolymers of vinylidene chloride with vinyl chloride, polymers of vinyl chloroacetate and dichlorodivinyl ether, chlorinated polymers of vinyl acetate, acrylic acid and alpha-substituted acrylic acids, polymers of dichlorostyrenes, chlorinated polymers of ethylene, polymers and after-chlorinated polymers of chlorobutadienes and their copolymers with vinyl chloride, and mixtures of any of these resins. The corresponding bromine and fluorine containing synthetic resins also are referred to. In the examples compositions are prepared by milling a mixture of 91) dibutyltin monomethoxy methyl maleate, di-2-ethylhexyl phthalate and a copolymer of 95 per cent. vinyl chloride and 5 per cent. vinyl acetate, (2) dibutyltin methoxy laurate, dioctyl phthalate and vinyl chloride resin, (3) polymeric dibutyltin methoxy acetate, tetrahydro-furfuryl oleate, diphenyl octyl phosphate, dioctyl phthalate and polyvinyl chloride, and (4) dibutyl methoxy methyl maleate, polymeric dibutyltin methoxy methyl maleate, tetrahydrofurfuryl oleate, dibutyl tetrachlorphthalate, di-2-ethylhexyl phthalate and a vinyl chloride diethyl maleate copolymer. The polymeric organo-tin compounds of the above general formula where x is a numeral greater than 1 are prepared by polymerizing an organo-tin compounds of the above general formula where x is 1 (see Group IV(b)), e.g. by heating in the presence of moisture. In an example, a compound of the formula <FORM:0711145/IV (a)/2> where x is approximately 3, is prepared by treating the corresponding monomeric compound with moist air. In a further example, a solution of dibutyltin dimethoxide and polymeric dibutyltin dimethoxide is prepared by heating a solution of the monomeric compound in toluene, and is then reacted with maleic anhydride to form a mixture of compounds of the general formula <FORM:0711145/IV (a)/3> where n is 1 or more.ALSO:The invention comprises organo-tin compounds of the general formula <FORM:0711145/IV (b)/1> wherein R and R1 represent the same or different aliphatic, alicyclic or aromatic hydrocarbon radicals, OR11 represents an alkoxy radical derived from aliphatic, alicyclic or aromatic alcohols and Z represents the acyloxy radical of a monocarboxylic acid or the half ester acyloxy radical of a dicarboxylic acid, and a process for the preparation thereof by reacting the required di-organo tin dihalide in an organic solvent with an alkali metal alcoholate as well as simultaneously or subsequently with a salt of a monocarboxylic acid or a salt of a half ester of a dicarboxylic acid, said salts having a cation forming a halide which is insoluble or difficultly soluble in the solvent. The reaction may be carried out in a solvent which is the alcohol of the alkali alcoholate used in the reaction. The organo tin compounds may be polymerized, e.g. by heating in the presence of moisture, to form polymeric compounds of the general formula <FORM:0711145/IV (b)/2> wherein R, R1, OR11 and Z have the significance indicated above and x is a numeral higher than 1. Di-organo tin dihalides which may be used in the above reaction include dimethyl, diethyl, dipropyl, dibutyl, diamyl, dihexyl, dioctyl, dilauryl, diallyl, dibenzyl, diphenyl and ditolyl tin dichlorides and dibromides. Aliphatic, alicyclic and aromatic alcohols including ether and thioether alcohols may be used to form the ether group, and any of the following alcohols and sulphides may be used:-methyl, ethyl, propyl, allyl, butyl, octyl, furfuryl, tetrahydrofurfuryl, benzyl, cinnamyl, phenylethyl, methoxyethyl, ethoxyethyl, butoxyethyl and methoxyethoxyethyl alcohols, and methyl hydroxyethyl and ethyl hydroxyethyl sulphides. Suitable monocarboxylic acids are formic, acetic, propionic, butyric, valeric, 2-ethylhexoic, caprylic, lauric, myristic, stearic, acrylic, crotonic, oleic, linoleic, ricinoleic, sorbic, furoic, benzoic, cinnamic and phenylacetic acids. The half ester of the dicarboxylic acid may be derived from malonic, succinic, glutaric, adipic, sebacic, fumaric, maleic, itaconic, citraconic or phthalic acid, and the ester group may be derived from any of the alcohols referred to above. In the examples the following compounds are prepared: dibutyltinmethoxylaurate, diphenyltinbutyoxyoleate, diethyltin (ethoxyethoxy) crotonate, dibutyltin monomethoxy methylmaleate, dibutyltin monomethoxy butylmaleate, dibutyltin monomethoxy allylmaleate, dibutyltin monomethoxy tetrahydrofurfurylmaleate, dibutyltin monomethoxy methylsuccinate, dibutyltin monomethoxy methylphthalate, diethyltin monoethoxy ethylsebacate, diphenyltin monomethoxy butylitaconate and dibutyltin monomethoxy methylacetate, and compounds of the formul <FORM:0711145/IV (b)/3> wherein x is approximately 3, and <FORM:0711145/IV (b)/4> wherein n equals 1 or a higher number.ALSO:Chlorinated rubber, rubber hydrochloride and chlorinated rubber hydrochloride, and mixtures thereof, and mixtures of any of these chlorinated rubbers with halogen containing synthetic resins, are stabilized with organo-tin compounds of the general formula <FORM:0711145/V/1> wherein R and R1 represent the same or different aliphatic, alicyclic or aromatic hydrocarbon radicals, OR11 represents an alkoxy radical derived from an aliphatic, alicyclic or aromatic alcohol, Z represents the acyloxy radical of a monocarboxylic acid or the half ester acyloxy radical of a dicarboxylic acid, and x is a numeral equal to 1 or more (see Group IV (b)). |
