Patent GB-718393-A (GB)
Title: Improvements relating to new organo-tin compounds
Inventor: CHURCH JAMES MARION
IPC: C07F7/22
Filed: 1952-02-01
Abstract: Halogen-containing organic compounds such as vinyl resins containing polymerized vinyl chloride are stabilized by incorporating therein one or more organo-tin compounds obtained by reacting one or more organo-tin oxides of the general formula R1 R2 SnO, wherein R1 and R2 represent alkyl, aralkyl, alkenyl, alkynyl, aryl or heterocyclic radicals, with one or more aldehydes or ketones.  It is preferred to add from 0.1 to 10 per cent. by weight of said organo-tin compound. In the examples compositions are prepared containing:-polyvinyl chloride, butyl benzyl phthalate, tri-o-cresyl phthalate and the reaction product of dibutyl tin oxide and 2-ethylhexanol; a polyvinyl resin consisting of 85 per cent. vinyl chloride and 15 per cent. vinyl acetate, dioctyl phthalate and the reaction product of diphenyl tin oxide and butyraldehyde; polyvinyl chloride, di-2-ethylhexylphthalate and each of the following organo-tin compounds obtained by reacting dibutyl tin oxide and 2-ethylhexanol, dibutyl tin oxide and benzaldehyde, dimethyl tin oxide and 2-ethylhexanol, dibutyl tin oxide and benzophenone, dibutyl tin oxide and camphor, dibutyl tin oxide and cyclohexanone, dibutyl tin oxide and methyl n-hexyl ketone, and diphenyl tin oxide and acetophenone. The organo-tin compounds obtained by reacting one or more organo-tin oxides of the general formula R1 R2 SnO in which R1 and R2 are alkyl, aralkyl, alkenyl, alkynyl, aryl or heterocyclic radicals with one or more aldehydes may be polymeric compounds.  The aldehydes may condense amongst themselves before reaction with the organo-tin oxides.  The organo-tin oxide is preferably used in a quantity varying from 0.25 to 10 mols per mol of aldehyde or ketone.  The reaction may be carried out at room or elevated temperatures, e.g., from 50 DEG  to 200 DEG C.-preferably at 120 DEG  to 130 DEG C.  If a solvent is used for the reaction, e.g. toluene, carbon tetrachloride, ether, hexane or heptane, the reaction may be carried out at the boiling point of the solvent.  The ketones may be aliphatic, aromatic or heterocyclic ketones, e.g. those having a boiling point of at least 60 DEG C.  Ketones mentioned are acetone, methyl ethyl ketone, methyl n-hexyl ketone, cyclohexanone, benzophenone, acetylfuranes, acetylnaphthalenes and camphor.  The aldehyde, which may have also a boiling point of at least 60 DEG C., may be an aliphatic aldehyde such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, 2-hydroxybutanal, isobutyraldehyde, valeraldehyde, 2-ethylbutanal, n-heptaldehyde, caprylaldehyde, 2-ethylhexanal, aldol of 2-ethylhexanal, acrolein, crotonaldehyde, 2-ethylhexenal, octadecenylaldehyde and propynal, an aromatic aldehyde such as benzaldehyde, salicylaldehyde, anisaldehyde, o-and p-tolualdehyde, o- and p-carbethoxybenzaldehyde, and o- and p-nitrobenzaldehyde, an aralkyl aldehyde such as phenylacetaldehyde and cinnamaldehyde, and a heterocyclic aldehyde such as furfural.  The organo-tin oxide may be a dialkyl-tin oxide in which the alkyl groups may be the same or different and can be substituted, e.g. by hydroxyl, carboxyl, ester or halogen substituents, unsubstituted, straight or branched chain or cyclic groups and preferably contain between 3 and about 16 carbon atoms, a diaryl-or diaralkyl-tin oxide in which the groups may be the same or different, suitable groups being the phenyl, tolyl, xylyl, naphthyl, benzyl, phenethyl and benzohydryl groups, and the groups may contain hydroxy, ester, carboxyl, halogen or alkoxy substituents, a dialkenyl-tin oxide such as a divinyl-, diallyl-, dicrotyl-, dipentenyl-or dicinnamyl-tin oxide, an organo-tin oxide containing a heterocyclic group such as the furyl, furfuryl, thienyl, thenyl, pyridyl and piperidyl group, or an organo-tin oxide containing an alkynyl group such as the ethynyl and propynyl group.  A large number of detailed examples are given.ALSO:Organo-tin compounds are prepared by reacting one or more organo-tin oxides of the general formula R1R2SnO in which R1 and R2 are alkyl, aralkyl, alkenyl, alkynyl, aryl or heterocyclic radicals with one or more aldehydes or ketones.  The aldehydes may condense amongst themselves before reaction with the organo-tin oxides.  The organo-tin oxide may be used in a quantity varying from 0.25 to 10 mols. per mol. of aldehyde or ketone.  The reaction may be carried out at room or elevated temperatures, e.g. from 50 DEG  to 200 DEG  C.-preferably at 120 DEG  to 130 DEG  C.  If a solvent is used for the reaction, e.g. toluene, carbon tetrachloride, ether, hexane or heptane, the reaction may be carried out at the boiling point of the solvent. The ketones may be aliphatic, aromatic or heterocyclic ketones and preferably have a boiling point of at least 60 DEG  C.  Ketones mentioned are acetone, methyl ethyl ketone, methyl n-hexyl ketone, cyclohexanone, benzophenone, acetylfuranes, acetylnaphthalenes and camphor.  The aldehyde, which may have also a boiling point of at least 60 DEG  C., may be an aliphatic aldehyde such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, 3-hydroxybutanal, isobutyraldehyde, valeraldehyde, 2 - ethylbutanal, n-heptaldehyde, caprylaldehyde, 2-ethylhexanal, aldol of 2-ethylhexanal, acrolein, crotonaldehyde, 2-ethylhexanal, octadecenylaldehyde or propynal, an aromatic aldehyde such as benzaldehyde, salicylaldehyde, anisaldehyde, p - or o - tolualdehyde, p - or o - carbethoxybenzaldehyde, or p - or o - nitrobenzaldehyde, an aralkyl aldehyde such as phenylacetaldehyde or cinnamaldehyde, and a heterocyclic aldehyde such as furfural.  The organotin oxide may be a dialkyl-tin oxide in which the alkyl groups may have a straight or branched chain or may be cyclic, and may include such groups as the methyl, ethyl, propyl, butyl, isobutyl, amyl, isoamyl, hexyl, cyclohexyl, octyl, lauryl and cetyl groups, and in which the alkyl groups may be the same or different.  Preferably the alkyl groups contain between 3 and about 16 carbon atoms.  The alkyl groups may be unsubstituted or substituted, e.g. by hydroxy, ester, carboxyl or halogen substitutents.  Diaryl- and diaralkyl-tin oxides may be used also where the groups are the same or different and in which the aryl and aralkyl groups may be any of the phenyl, tolyl, xylyl, naphthyl, benzyl, phenethyl and benzohydryl groups, and may be substituted, e.g. by hydroxy, ester, carboxyl, halogen or alkoxy substituents.  Dialkenyl-tin oxides referred to are the divinyl-, diallyl-, dicrotyl-, dipentenyl- and dicinnamyl-tin oxides. When the organto-tin oxide contains a heterocyclic group, the group may be a furyl, furfuryl, thienyl, thenyl, pyridyl or piperidyl group, and when it contains an alkynyl group, the group may be an ethynyl or propynyl group.  A large number of detailed examples are given.  The organo-tin compound obtained by reacting isobutyraldehyde and dibutyl-tin oxide has the formula <FORM:0718393/IV (b)/1> Halogen-containing organic compounds are stabilized by incorporating one or more of the organo-tin compounds prepared by the process referred to above, e.g. by incorporating from 0.1 to 10 per cent by weight of said organo-tin compounds.  Organic compounds which may be stabilized are chlorinated paraffins containing from 10 to 40 carbon atoms, chlorinated stearates, chlorinated diphenyls and (p,p-dichlorodiphenylmethyl)-trichloromethane.ALSO:Chlorinated rubber is stabilized by incorporating therein one or more organo-tin compounds obtained by reacting one or more organo-tin oxides of the general formula R1R2SnO, wherein R1 and R2 represent alkyl aralkyl, alkenyl, alkynyl, aryl or heterocyclic radicals, with one or more aldehydes or ketones (see Group IV (b)).  It is preferred to add from 0.1 to 10 per cent. by weight of said organo-tin compounds.