Patent GB-719733-A (GB)
Title: Organo tin compounds and compositions containing same
IPC: C07F7/22
Filed: 1952-06-12
Abstract: A resinous composition comprises a halogen-containing synthetic resin and, as stabilizer, an organo-tin compound of the general formula RnSn[SR1(COOR11)x]4-n, wherein R represent an alkyl, aryl, alkaryl or aralkyl radical, R1 represents a divalent or trivalent hydrocarbon radical which may be saturated or unsaturated and aliphatic or aromatic, R11 represents halogen or an alkyl, aryl, alkaryl or aralkyl radical, n is 1, 2 or 3, and x is 1 or 2 (see Group IV (b)). The resin may be a polyvinyl resin containing vinyl halide units, e.g. polyvinyl chloride, and copolymers of vinyl chloride and vinylidene chloride or vinyl acetate, the preferred quantity of organo-tin compound being from 0.5 to 10 per cent. by weight based on the weight of vinyl resin.  The composition may contain a plasticizer, e.g. dioctyl phthalate or a triorgano phosphate such as an alkyl aryl phosphate, tricresyl phosphate or cresyl diphenyl phosphate.  A large number of organo-tin compounds of the above general formula are referred to wherein n is 1, 2 and 3, R represents the methyl, ethyl, n-butyl, lauryl and phenyl radical, and the radical -SR1(COOR11)#c is derived from thiomalic and thioglycollic acids, n-butyl, cyclohexyl, n-octadecyl, 3, 5, 5-trimethylhexyl, decyl, 2, 6, 8-trimethyl-4-nonyl, dihydroabietyl and phenoxyethyl mercaptoacetate, 2-butyloctyl-1 b -mercaptopropionate, diethylene glycol laurate mercaptoacetate, diethylene glycol ricinoleate mercaptoacetate, di-n-butyl thiomalate, methyl thiosalicylate, the 3, 3, 5-trimethylhexyl esters of a -mercaptopropionic, a - and b -mercaptobutyric, a -mercaptodiethylacetic, a - and 5-mercaptovaleric, a - and 6-mercaptocaproic and 7-mercaptohexanoic acids, the n-butyl esters of a -mercaptocapric, a - and 8-mercaptocaprylic, a -mercaptopelargonic, a - and 12-mercaptolauric, a -mercapto palmitic and a -mercaptostearic acids, ethyl a -mercapto-a -ethyl-caproate, ethyl a -mercaptophenylacetate and ethyl a -mercaptodiphenylacetate.ALSO:The invention comprises organo-tin compounds of the general formula RnSn[SR1(COOR11)]x-4n wherein R represents an alkyl, aryl, alkaryl or aralkyl radical, R1 represents a divalent or trivalent hydrocarbon radical which may be saturated or unsaturated and aliphatic or aromatic, R11 represents hydrogen or an alkyl, aryl, alkaryl or aralkyl radical, n is 1, 2 or 3 and x is 1 or 2, and a process for the preparation of the above compounds by reacting organo-tin compounds of the formul  RSnOOH, R2SnO and R3SnOH, R having the above significance, with mercapto-acids and esters thereof of the general formula HSR1(COOR11)x, wherein R1, R11 and x have the above significance, or by reacting organo-tin halides of the formul  RSnX3, R2SnX2 and R3SnX, where R has the above significance and X is a halogen, with the above mercapto-acids and esters thereof in the presence of a hydrogen halide acceptor.  The processes may be carried out at room or slightly elevated temperatures, or at higher temperatures to remove water from those processes where it is formed.  An inert organic solvent may be used in the processes, e.g. toluene, benzene, or methyl alcohol.  The hydrogen halide acceptor may be an oxide, a hydroxide, e.g. sodium hydroxide, a carbonate, e.g. sodium or potassium carbonate, or a tertiary amine, e.g. pyridine.  In the examples a large number of organo-tin compounds of the above general formula are prepared wherein n is 1, 2 or 3, R represents the methyl, ethyl, n-butyl, lauryl and phenyl radicals, and the radical-SR1(COOR11)x is derived from thiomalic and thioglycollic acids, n-butyl, cyclohexyl, n-octadecyl, 3,3,5-trimethylhexyl, decyl, 2,6,8-trimethyl-4-nonyl, dihydroabietyl and phenoxyethyl mercaptoacetate, 2 - butyloctyl - 1 b - mercaptopropionate, diethylene glycol laurate mercaptoacetate, diethylene glycol ricinoleate mercaptoacetate, di-n-butyl thiomalate, methyl thiosalicylate, the 3,3,5-trimethylhexyl esters of a -mercaptopropionic, a - and b -mercaptobutyric, a  - mercaptodiethylacetic, a - and 5-mercaptovaleric, a - and 6-mercaptocaproic and 7-mercaptohexanoic acids, the n-butyl esters of a -mercaptocapric, a - and 8-mercaptocaprylic, a -mercaptopelargonic, a - and 12-mercaptolauric, a -mercaptopalmitic and a -mercaptostearic acids, ethyl a -mercapto-a -ethyl-caproate, ethyl a -mercaptophenylacetate and ethyl a -mercaptodiphenylacetate. Thioacids of the formula HSCH2COOR, where R is the 3,3,5-trimethylhexyl, cyclohexyl, b -phenoxyethyl, n - octadecyl, dihydroabietyl, 2,6,8 - trimethylnonyl - 4, n - butyl and decyl radicals, and radicals of the formul  -CH2CH2OOC-Lauryl and -CH2CH2OOC-(CH2)7-CH= CHCH2CH(OH)(CH2)5CH3 are prepared by esterifying mercaptoacetic acid with the required alcohols. Di-n-butyl thiomalate is prepared by esterifying thiomalic acid with n-butyl alcohol.  2-n-Butyloctyl b -mercaptopropionate is prepared by esterifying b -mercaptopropionic acid with 2-butyl-octanol-1.  Methyl thiosalicylate is prepared by passing anhydrous hydrogen chloride through a boiling methyl alcohol solution of the free acid.  3,5,5 - Trimethylhexyl a  - mercaptopropionate is prepared by treating a -chloropropionic acid with sodium hydrosulphide and esterifying the resulting thio-acid with 3,5,5-trimethylhexanol. In a similar manner the following esters are prepared: 3,5,5-trimethylhexyl b -mercaptobutyrate, 3,5,5 - trimethylhexyl a  - mercaptovalerate, 3,5,5 - trimethylhexyl a  - mercaptocaproate, n - butyl a  - mercaptocaprylate, n - butyl a  - mercaptocaproate, n - butyl a  - mercaptopelargonate, n - butyl a  - mercaptolaurate, n - butyl a  - mercaptopalmitate, n - butyl a  - mercaptostearate, ethyl a  - mercaptophenylacetate, ethyl a  - mercaptodiphenylacetate, 3,5,5 - trimethylhexyl a  - mercaptodiethylacetate and n-butyl a -mercaptopalmitate.  Ethyl a -mercapto-a -ethylcaproate is prepared by treating ethyl a -bromo-a -ethylcaproate with sodium hydrosulphide.  3,5,5 - Trimethylhexyl - a  - mercaptobutyrate is prepared by reacting thiourea with a -bromobutyric acid to form 5-ethylpseudothiohydantoin hydrobromide which is treated with sodium hydroxide to form 3,5,5-trimethyl-a -mercaptobutyric acid and the free acid is esterified with 3,5,5-trimethylhexanol.  3,5,5 - Trimethylhexyl - 5 - mercaptovalerate is prepared by treating 1,3-dibromopropane with phenol in the presence of sodium hydroxide to form 3-phenoxypropyl bromide which is then reacted with diethyl sodiomalonate to form diethyl 3-phenoxypropyl malonate which yields 5-bromovaleric acid on treatment with hydrobromic acid, and the acid is refluxed with thiourea and then treated with sodium hydroxide to form 5-mercaptovaleric acid which is esterified to form 3,5,5-trimethylhexyl 5-mercaptovalerate. By a similar method 3,5,5-trimethylhexyl 6-mercaptocaproate, 3,5,5-trimethylhexyl 7 - mercaptohexanoate, n - butyl 8 - mercaptocaprylate and n - butyl 12 - mercaptolaurate are prepared starting from 1,4-dibromobutane, pentamethylene dibromide, hexamethylene dibromide and decamethylene dibromide respectively.  n-Butyl a -bromocaprate is prepared by treating capric acid with thionyl chloride and bromine to form a -bromocapryl chloride, hydrolysing this compound to form a -bromocapric acid which is esterified with n-butyl alcohol.  By a similar procedure ethyl a -bromopelargonate and n-butyl a -bromolaurate are prepared.  a -Bromo-caproic, caprylic and palmitic acids are prepared by the Hell-Vollhardt-Zelinsky bromination of caproic, caprylic and palmitic acids respectively.ALSO:Rubber accelerators and antioxidants comprise organo-tin compounds of the general formula Rn Sn [SR1(COOR11)x]4-n, wherein R represents an alkyl, aryl, alkaryl or aralkyl radical, R1 represents a divalent or trivalent hydrocarbon radical which may be saturated or unsaturated and aliphatic or aromatic, R11 represents hydrogen or an alkyl, aryl, alkaryl or aralkyl radical, n is 1, 2 or 3, and x is 1 or 2 (see Group IV (b)).  A large number of the above organo-tin compounds are referred to, a typical compound being di-n-butyltin S, S1-bis (nonyl mercaptoacetate).