US2680107A - Organic derivatives of tetravalent tin and compositions containing the same - Google Patents
Organic derivatives of tetravalent tin and compositions containing the same Download PDFInfo
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- US2680107A US2680107A US289011A US28901152A US2680107A US 2680107 A US2680107 A US 2680107A US 289011 A US289011 A US 289011A US 28901152 A US28901152 A US 28901152A US 2680107 A US2680107 A US 2680107A
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- 239000000203 mixture Substances 0.000 title description 11
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title description 2
- 150000001875 compounds Chemical class 0.000 claims description 13
- -1 mercapto fatty acid Chemical class 0.000 description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 7
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000003381 stabilizer Substances 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000005429 oxyalkyl group Chemical group 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- OWXDBXWIBAHZBD-UHFFFAOYSA-N 2-methyl-2-sulfanyldecanoic acid Chemical compound CCCCCCCCC(C)(S)C(O)=O OWXDBXWIBAHZBD-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229920006387 Vinylite Polymers 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 238000010533 azeotropic distillation Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical compound [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- XOYDCQVJYSOIOE-UHFFFAOYSA-N 2-methyl-2-sulfanylpentadecanoic acid Chemical compound CCCCCCCCCCCCCC(C)(S)C(O)=O XOYDCQVJYSOIOE-UHFFFAOYSA-N 0.000 description 1
- KPKXEDPGKJXFHK-UHFFFAOYSA-N 2-methyl-2-sulfanyltetradecanoic acid Chemical compound CCCCCCCCCCCCC(C)(S)C(O)=O KPKXEDPGKJXFHK-UHFFFAOYSA-N 0.000 description 1
- MOTOSAGBNXXRRE-UHFFFAOYSA-N 2-phenylsulfanylacetic acid Chemical compound OC(=O)CSC1=CC=CC=C1 MOTOSAGBNXXRRE-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 241000156978 Erebia Species 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- GCTFWCDSFPMHHS-UHFFFAOYSA-M Tributyltin chloride Chemical compound CCCC[Sn](Cl)(CCCC)CCCC GCTFWCDSFPMHHS-UHFFFAOYSA-M 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- LUZSPGQEISANPO-UHFFFAOYSA-N butyltin Chemical class CCCC[Sn] LUZSPGQEISANPO-UHFFFAOYSA-N 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 229950005499 carbon tetrachloride Drugs 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- WCRDXYSYPCEIAK-UHFFFAOYSA-N dibutylstannane Chemical compound CCCC[SnH2]CCCC WCRDXYSYPCEIAK-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QGZWYBQTXJMHIW-UHFFFAOYSA-N octane-3-thiol Chemical compound CCCCCC(S)CC QGZWYBQTXJMHIW-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- DZXKSFDSPBRJPS-UHFFFAOYSA-N tin(2+);sulfide Chemical compound [S-2].[Sn+2] DZXKSFDSPBRJPS-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
- C08K5/57—Organo-tin compounds
- C08K5/58—Organo-tin compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/22—Tin compounds
- C07F7/2224—Compounds having one or more tin-oxygen linkages
Definitions
- R stands for a radical selected from the group consisting of .alkyl, aryl, oxyalkyl and oxyaryl, and the furfuryl and tetrahydrofurf-uryl radicals
- X for the anion of a mercapto fatty acid having from to 20 carbon atoms
- n for an integral number from 1 to 3.
- R examples for R are alkyls, such as methyl, ethyl, butyl, octyl, dodecyl, and octadecyl; aryls, such as phenyl, tolyl, or xylyl; oxyalkyl and oxyaryl, such as Cal-I70, CAI-I90, CsHrzO, Cal-I50, CsI-I4(CH3)O; CeHs(CH3)2O; and the furfuryl and tetrahydrofurfuryl groups.
- alkyls such as methyl, ethyl, butyl, octyl, dodecyl, and octadecyl
- aryls such as phenyl, tolyl, or xylyl
- oxyalkyl and oxyaryl such as Cal-I70, CAI-I90, CsHrzO, Cal-I50, CsI
- Examples for X are anions of mercapto fatty acids, such as dodecyl mercapto isobutyric acid, octyl mercapto propionic acid, benzyl mercapto isobutyric acid, and phenyl mercapto acetic acid.
- mercapto fatty acids such as dodecyl mercapto isobutyric acid, octyl mercapto propionic acid, benzyl mercapto isobutyric acid, and phenyl mercapto acetic acid.
- dodecyl mercapto propionic acid and butyl tin compounds the products may have the following formulas:
- novel tin compounds according to our inj vention are oily liquids of high viscosity or solids gmelting at low temperatures, Whose composition has in each case been ascertained by analysis.
- a general method to prepare these compounds is first to prepare the desired mercapto fatty acid and subsequently to react the acid with an organic tin oxide, or a stannonic acid containing 5 Claims. fwi. 260-45115) an organic radical, or to react the alkali metal salt of the acid with an organic tin halide.
- Example 1 The preparation of dibutyl-tin di-dodecyl mercapto isobutyrate (3H3 (C4H9)iS]1-(O O C. CH. CH2. S C 2H25)z To 800 g. n-dodecyl mercaptan are added 2 g. sodium-methylate. To this mixture 400 g. methylmethacrylate are added slowly While stirring. An exothermic reaction occurs and the temperature rises spontaneously to about C. By the further addition of the methylmethacrylate, the reaction mixture is maintained at this temperature. Gradually, the viscosity of the solution increases. When the whole amount of methylmethacrylate has been added, one more gram of sodium methylate is added without causing a rise in temperature. Thereafter, the solution is heated on a boiling water bath for /2 hour.
- the reaction mixture is filtered in order to remove slight impurities, and benzene is distilled off. In the filtrate, there remains an oily residue.
- Example 2 Preparation of tributyl-tin octyl mercapto propionate (021%) 3511(OOCCH2CH2SC8H1T) Octyl mercapto propionic acid is prepared in precisely the same way as in Example 1 from:
- novel compounds made according to the method described above may be used for various purposes. They are excellent stabilizers for chlorinated resins or other high molecular weight halogenated material, and may be used as antioxidants. They may also be interesting as such, or as intermediates for pharmaceuticals and cosmetics. As to their use for stabilizing chlorine-containing organic compositions, we wish to emphasize the superiority of these products above compounds of similar structure, such as dibutyl tin dilaurate. The presence of the sulfur in the molecule increases the compatibility with the product to be stabilized. Furthermore, the sulfur present acts as an antioxidant which improves the stabilizing efiect.
- the amount of the compounds to be used as stabilizers is from 0.1 to 10% by weight of the resinous composition.
- Example 4 100 parts of vinylite VYNW (vinyl chloride and acetate copolymer), 50 parts of dicotylphthalate, and 2 parts of the product of Example I as stabilizer are mixed by tumbling for a period of one hour. The whole mass is then transferred to a Banbury mixer and fused for 10 min. at a temperature of approximately 300 F. It is then dropped and transferred to a warmup mill, whose roll temperature is likewise maintained at 300 F. The material is then fed as needed to a 3 or 4 roll calender. The roll temperatures of the calender range from 280350 F. The vinyl compound is calendered into a film at .004 inch or any other desirable gage.
- Example 5 A comparison test was made in which chlo rinated parafiin was heated over a period of time, without any addition on the one hand, and with addition of a stabilizer made according to the invention on the other hand.
- Example 6 The following procedure is used to advantage in making a finished solution of the resin.
- the proportion of solvent used will vary with the concentration of solution desired, as, for instance, from 500 to 3,000 parts of solvent to parts of the vinyl chloride resin used.
- R stands for a radical selected from the group consisting of alkyl, aryl, oxyalkyl and oxyaryl, and the furfuryl and tetrahydrofurfuryl radicals
- X for the anion of a mercapto fatty acid selected from the group consisting of alkyl and aryl mercapto fatty acids having from 5 to 20 carbon atoms
- n for an integral number from 1 to 3.
- a stabilized chlorine-containing resinous composition containing 0.1% to 10% by weight of the compound of claim 1.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Patented June 1, 1954 UNITED STATES PATENT OFFICE ORGANIC DERIVATIVES OF TETRAVALENT TIN AND COMPOSITIONS THE SAME CONTAINING William E. Leistner, Brooklyn, and Arthur 0. Becker, Richmond Hill, N. Y., assignors to Argus Chemical Laboratory, Inc., a corporation of New York No Drawing. Application May 20, 1952, Serial No. 289,011
wherein R stands for a radical selected from the group consisting of .alkyl, aryl, oxyalkyl and oxyaryl, and the furfuryl and tetrahydrofurf-uryl radicals, X for the anion of a mercapto fatty acid having from to 20 carbon atoms, and n for an integral number from 1 to 3.
Examples for R are alkyls, such as methyl, ethyl, butyl, octyl, dodecyl, and octadecyl; aryls, such as phenyl, tolyl, or xylyl; oxyalkyl and oxyaryl, such as Cal-I70, CAI-I90, CsHrzO, Cal-I50, CsI-I4(CH3)O; CeHs(CH3)2O; and the furfuryl and tetrahydrofurfuryl groups.
Examples for X are anions of mercapto fatty acids, such as dodecyl mercapto isobutyric acid, octyl mercapto propionic acid, benzyl mercapto isobutyric acid, and phenyl mercapto acetic acid. Taking as specific examples the dodecyl mercapto propionic acid and butyl tin compounds, the products may have the following formulas:
The novel tin compounds according to our inj vention are oily liquids of high viscosity or solids gmelting at low temperatures, Whose composition has in each case been ascertained by analysis.
They are soluble in many organic solvents, for instance in ether, benzene, toluene, chloroform, carbontetrachloride, etc.
A general method to prepare these compounds is first to prepare the desired mercapto fatty acid and subsequently to react the acid with an organic tin oxide, or a stannonic acid containing 5 Claims. fwi. 260-45115) an organic radical, or to react the alkali metal salt of the acid with an organic tin halide.
The invention will now be illustrated by a number of examples, but it should be understood that these are given by way of illustration and not of limitation and that many variations in the compounds given and the amounts indicated can be made without departing from the spirit of the invention and the scope of the appended claims.
Example 1 The preparation of dibutyl-tin di-dodecyl mercapto isobutyrate (3H3 (C4H9)iS]1-(O O C. CH. CH2. S C 2H25)z To 800 g. n-dodecyl mercaptan are added 2 g. sodium-methylate. To this mixture 400 g. methylmethacrylate are added slowly While stirring. An exothermic reaction occurs and the temperature rises spontaneously to about C. By the further addition of the methylmethacrylate, the reaction mixture is maintained at this temperature. Gradually, the viscosity of the solution increases. When the whole amount of methylmethacrylate has been added, one more gram of sodium methylate is added without causing a rise in temperature. Thereafter, the solution is heated on a boiling water bath for /2 hour.
After cooling down, a solution of 160 g. NaOH in 700 cc. water is slowly added with stirring, which causes a slight rise in temperature. After addition of the whole amount of NaOI-I, the mixture is heated to 100 C. for one hour, in order to complete hydrolysis. On cooling, the reaction mixture solidifies to a soaplike mass. This is acidified with HCl, whereby the mercapto acid separates as an oil. V
g. dry acid 25 g. dibutyl-tin oxide, and
50 cc. benzene, to which 0.1 g. paratoluene sulfonic acid was added,
are refluxed for about 1 hour, whereby 1.7 cc. water are removed by azeotropic distillation.
The reaction mixture is filtered in order to remove slight impurities, and benzene is distilled off. In the filtrate, there remains an oily residue.
which solidifies in the ice box and melts again at room temperature.
Analysis Sn S calc l4. 5 7. 9 found 14. 1 8.
Example 2 Preparation of tributyl-tin octyl mercapto propionate (021%) 3511(OOCCH2CH2SC8H1T) Octyl mercapto propionic acid is prepared in precisely the same way as in Example 1 from:
292 g. ethylhexyl mercaptan, and
175 g. methyl acrylate in the presence of 2 g. sodium methylate as catalyst.
22 g. of the dry acid were neutralized with 4 g. NaOI-I, and
32.5 g. tri butyl--tin chloride and 50 cc. benzene were added.
The resulting mixture was refluxed for 1 hour,
and the sodium chloride formed was filtered oil. The residue of the filtrate after distilling oil the solvent is very similar to the product of Example 1.
Analysis Sn S Cale 23. 3 G. 3 Found 22. 8 6. 2
Example 3 Preparation of isopropyl-tin tribenzylmercapto isobutyrate CHi C3H7SH(O o 0611.01.12. s CHZC Hs):
In the same way as in Examples 1 and 2 benzyl mercapto-isobutyric acid was prepared from were refluxed for 1 hour and 8.5 cc. water removed by azeotropic distillation. Slight impurities are filtered off and benzene is removed by distillation.
The residue is in appearance and properties similar to the material obtained according to Example 1. Analysis:
Cale. values 15. 0 12. 2 Found values 15.1 12. l
The novel compounds made according to the method described above may be used for various purposes. They are excellent stabilizers for chlorinated resins or other high molecular weight halogenated material, and may be used as antioxidants. They may also be interesting as such, or as intermediates for pharmaceuticals and cosmetics. As to their use for stabilizing chlorine-containing organic compositions, we wish to emphasize the superiority of these products above compounds of similar structure, such as dibutyl tin dilaurate. The presence of the sulfur in the molecule increases the compatibility with the product to be stabilized. Furthermore, the sulfur present acts as an antioxidant which improves the stabilizing efiect.
The amount of the compounds to be used as stabilizers is from 0.1 to 10% by weight of the resinous composition.
In the following, examples will be given for the manufacture of plastic compositions in which the compound according to the present invention is used as a stabilizer.
Example 4 100 parts of vinylite VYNW (vinyl chloride and acetate copolymer), 50 parts of dicotylphthalate, and 2 parts of the product of Example I as stabilizer are mixed by tumbling for a period of one hour. The whole mass is then transferred to a Banbury mixer and fused for 10 min. at a temperature of approximately 300 F. It is then dropped and transferred to a warmup mill, whose roll temperature is likewise maintained at 300 F. The material is then fed as needed to a 3 or 4 roll calender. The roll temperatures of the calender range from 280350 F. The vinyl compound is calendered into a film at .004 inch or any other desirable gage.
Example 5' A comparison test was made in which chlo rinated parafiin was heated over a period of time, without any addition on the one hand, and with addition of a stabilizer made according to the invention on the other hand.
In this test, a nitrogen current was passed through chlorinated paraffin containing 4.0% chlorine, at a temperature of 150 F. for 12 hours. During the test, the paraffin lost chlorine.
The same chlorinated paraffin, to which 3% of the product obtained in Example 3 were added, was treated in a similar manner and showed a loss of only 1.1% chlorine after 12 hours.
Example 6 The following procedure is used to advantage in making a finished solution of the resin. We use 100 parts of vinylite VYNW (vinyl chloride and acetate copolymer) along with parts of tricresylphosphate. ihis is weighed into a dry blender; 1 part of stabilizer (made as described in Example 2) is then added. The whole mass is agitated by tumbling for 30 minutes and then transferred to a 2-roll mill whose roll temperatures are about 240 F. The mass is fluidized on the mill and then sheeted into strips which are added to a mixture consisting of 3 parts of methyl ethyl ketone and 1 part of toluene in a conventional mixer. The compound is agitated at room temperature in the mixer until complete solution results. The proportion of solvent used will vary with the concentration of solution desired, as, for instance, from 500 to 3,000 parts of solvent to parts of the vinyl chloride resin used.
What we claim is:
1. As a new compound, a product corresponding to the formula wherein R stands for a radical selected from the group consisting of alkyl, aryl, oxyalkyl and oxyaryl, and the furfuryl and tetrahydrofurfuryl radicals, X for the anion of a mercapto fatty acid selected from the group consisting of alkyl and aryl mercapto fatty acids having from 5 to 20 carbon atoms, and n for an integral number from 1 to 3.
2. As a new compound, dibutyl tin di-dodecylmercapto-isobutyrate.
3. As a new compound, tributyl tin octylmercaptopropionate.
4. As a new compound, isopropyl tin tribenzylmercapto-isobutyrate.
5. A stabilized chlorine-containing resinous composition containing 0.1% to 10% by weight of the compound of claim 1.
References Cited in the fiie Of this patent UNITED STATES PATENTS Number Name Date 2,479,918 Fincke et a1 Aug. 23, 1949 2,489,518 Burt Nov. 29, 1949 2,591,675 Church et a1 Apr. 8, 1952 2,592,926 Mack et a1 Apr. 15, 1952
Claims (1)
1. AS A NEW COMPOUND, A PRODUCT CORRESPONDING TO THE FORMULA
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US289011A US2680107A (en) | 1952-05-20 | 1952-05-20 | Organic derivatives of tetravalent tin and compositions containing the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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US289011A US2680107A (en) | 1952-05-20 | 1952-05-20 | Organic derivatives of tetravalent tin and compositions containing the same |
Publications (1)
Publication Number | Publication Date |
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US2680107A true US2680107A (en) | 1954-06-01 |
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Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US289011A Expired - Lifetime US2680107A (en) | 1952-05-20 | 1952-05-20 | Organic derivatives of tetravalent tin and compositions containing the same |
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Country | Link |
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US (1) | US2680107A (en) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2855417A (en) * | 1952-12-03 | 1958-10-07 | Metal & Thermit Corp | Organotin compounds and process of preparation |
US2867641A (en) * | 1954-07-02 | 1959-01-06 | Metal & Thermit Corp | Hydrocarbontinborates |
US2910452A (en) * | 1954-06-26 | 1959-10-27 | Saint Gobain | Polyvinyl chloride and poly alkyl tin mercaptosuccinates |
US3209017A (en) * | 1961-09-22 | 1965-09-28 | Carlisle Chemical Works | Dihydrocarbyl tin salts of trithiocarbodiglycolic acid |
US3271338A (en) * | 1961-11-27 | 1966-09-06 | Geigy Chem Corp | Polyvinyl halide stabilizers comprising sulfur-containing compounds and metal salts of epoxidized fatty acids |
US4020090A (en) * | 1971-11-19 | 1977-04-26 | Albright & Wilson Limited | Organotin compounds |
US5055606A (en) * | 1989-08-16 | 1991-10-08 | Witco Corporation | Alkylthiopropionic pentaerythritol esters and solvent refining thereof |
US5057622A (en) * | 1989-08-16 | 1991-10-15 | Witco Corporation | 3-alkylthiopropionic acids and derivatives |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2479918A (en) * | 1948-04-15 | 1949-08-23 | Monsanto Chemicals | Stabilized vinyl chloride resins |
US2489518A (en) * | 1948-12-15 | 1949-11-29 | Bakelite Corp | Stabilized vinyl chloride resins |
US2591675A (en) * | 1949-03-31 | 1952-04-08 | Metal & Thermit Corp | Organotin compounds and compositions containing the same |
US2592926A (en) * | 1948-10-29 | 1952-04-15 | Advance Solvents & Chemical Co | Halogen-containing resins stabilized with polymeric organo-tin dialkoxides |
-
1952
- 1952-05-20 US US289011A patent/US2680107A/en not_active Expired - Lifetime
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2479918A (en) * | 1948-04-15 | 1949-08-23 | Monsanto Chemicals | Stabilized vinyl chloride resins |
US2592926A (en) * | 1948-10-29 | 1952-04-15 | Advance Solvents & Chemical Co | Halogen-containing resins stabilized with polymeric organo-tin dialkoxides |
US2489518A (en) * | 1948-12-15 | 1949-11-29 | Bakelite Corp | Stabilized vinyl chloride resins |
US2591675A (en) * | 1949-03-31 | 1952-04-08 | Metal & Thermit Corp | Organotin compounds and compositions containing the same |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2855417A (en) * | 1952-12-03 | 1958-10-07 | Metal & Thermit Corp | Organotin compounds and process of preparation |
US2910452A (en) * | 1954-06-26 | 1959-10-27 | Saint Gobain | Polyvinyl chloride and poly alkyl tin mercaptosuccinates |
US2867641A (en) * | 1954-07-02 | 1959-01-06 | Metal & Thermit Corp | Hydrocarbontinborates |
US3209017A (en) * | 1961-09-22 | 1965-09-28 | Carlisle Chemical Works | Dihydrocarbyl tin salts of trithiocarbodiglycolic acid |
US3271338A (en) * | 1961-11-27 | 1966-09-06 | Geigy Chem Corp | Polyvinyl halide stabilizers comprising sulfur-containing compounds and metal salts of epoxidized fatty acids |
US4020090A (en) * | 1971-11-19 | 1977-04-26 | Albright & Wilson Limited | Organotin compounds |
US5055606A (en) * | 1989-08-16 | 1991-10-08 | Witco Corporation | Alkylthiopropionic pentaerythritol esters and solvent refining thereof |
US5057622A (en) * | 1989-08-16 | 1991-10-15 | Witco Corporation | 3-alkylthiopropionic acids and derivatives |
US5198486A (en) * | 1989-08-16 | 1993-03-30 | Witco Corporation | S-alkylthiopropionic acids and derivatives |
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