US20100280155A1 - Alkyltin Sulfanyl Mercaptocarboxylates Having Terminal Thiol Groups - Google Patents
Alkyltin Sulfanyl Mercaptocarboxylates Having Terminal Thiol Groups Download PDFInfo
- Publication number
- US20100280155A1 US20100280155A1 US12/835,600 US83560010A US2010280155A1 US 20100280155 A1 US20100280155 A1 US 20100280155A1 US 83560010 A US83560010 A US 83560010A US 2010280155 A1 US2010280155 A1 US 2010280155A1
- Authority
- US
- United States
- Prior art keywords
- composition
- pigments
- alkyltin
- group
- copolymers
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Images
Classifications
-
- 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 System
- C07F7/22—Tin compounds
-
- 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 System
- C07F7/22—Tin compounds
- C07F7/226—Compounds with one or more Sn-S linkages
Definitions
- This invention relates to alkyltin thermal stabilizers for halogen-containing resin compositions. More particularly, the present invention relates to alkyltin sulfanyl mercaptocarboxylates having from one to three terminal thiol groups and which are suitable for thermal stabilization of polyvinyl compositions.
- Non-thiol terminated alkyltin stabilizers are also known.
- dimethyltin bis S,S (2-ethylhexanol thioglycolate) and di-n-butyl bis S,S (2-ethylhexanol thiolglycolate) are both commercially available.
- One of the most effective thermal stabilizers is a blend of dimethyltin bis S,S (2-ethylhexanol thioglycolate) and methyltin tris S,S,S (2-ethylhexanol thioglycolate). These compounds are also commercially available.
- the present invention relates to an alkyltin compound having the formula:
- R is a C 1-3 alkyl group
- x is equal to 1 or 2;
- y is equal to 1 or 2.
- organotin compounds may be generally described as condensation products of organotin derivatives (such as oxides and chlorides) and dimercaptoacid esters of ethylene glycol.
- the present invention relates to a composition which includes a halogen-containing resin and an alkyltin compound as described above in an amount effective to stabilize the resin against elevated temperatures, UV light, oxidation and high shear forces.
- FIG. 1 is a graph of yellowness index of sample chips taken at various times during a heat stability test. The graph illustrates the improved color stability of a rigid PVC formulation containing the new tin stabilizer in comparison to control formulations containing other organotin compounds present at the same tin level.
- the alkyltin compounds of Formula 1 preferably have methyl groups for R.
- Alkyltin compounds which come within Formula I and which are particularly preferred include dimethyltin bis(1,2-ethane dithioglycolate), monomethyltin tris(1,2-ethanedithioglycolate), dimethyltin bis(1,2-ethane dimercaptopropionate), monomethylin tris(1,2-ethanedimercaptopropionate) and mixtures thereof.
- alkyltin compounds of the present invention may be prepared via several synthetic routes.
- these alkyltin compounds may be conveniently synthesized using a two-reaction procedure which employs readily available reactants.
- a dithiol ester is prepared by esterification of ethylene glycol with a thioacid in a molar ratio of 1:2 in the presence of a suitable catalyst. It is preferred to use a slight excess (3-5%) of thioglycolic acid.
- Suitable thioacids include mercaptoacetic acid and mercaptopropionic acid.
- Appropriate catalysts include but are not limited to p-toluene sulfonic acid and methane sulfonic acid.
- the esterification reaction may be performed with or without a solvent at an appropriate temperature, for example, 130-150° C. Water formed during the reaction is removed by conventional methods.
- the resulting dithiol ester may be neutralized with an appropriate base such as sodium bicarbonate or potassium carbonate, purified by filtering salt residues and stripped under vacuum to remove moisture, preferably at an elevated temperature such as, for example, 60-80° C.
- an appropriate base such as sodium bicarbonate or potassium carbonate
- the dithiol ester is reacted with an appropriate tin-containing reactant, for example an alkyltin chloride or alkyltin oxide, at the following molar ratios: for dialkyltin derivatives S:Sn>1.5 and for monoalkyltin derivatives S:Sn>1.0.
- an appropriate tin-containing reactant for example an alkyltin chloride or alkyltin oxide
- the resulting alkyltin compound thus contains both Sn—S bonds and free, terminal thiol groups.
- the alkyltin compounds of the present invention impart superior thermal stability to halogen-containing resins.
- resins include polyvinyl chloride (PVC), polyvinyl bromide, polyvinylidene chloride, copolymers of vinyl chloride and vinyl acetate, copolymers of vinyl chloride and vinylidene chloride, copolymers of vinyl chloride and acrylonitrile, copolymers of vinyl chloride and maleic or fumaric esters and copolymers of vinyl chloride and styrene.
- an effective amount of the alkyltin compound is an amount which makes the halogen-containing resin more resistant to discoloration than the resin per se. Generally, an effective amount will range from 0.5 to 1.50 parts stabilizer per hundred parts resin, and will depend on the specific resin and alkyltin compound, as well as the degree of thermal stabilization desired. A preferred amount of alkyltin compound is from 0.8 to 1.2 parts stabilizer per hundred parts resin.
- the alkyltin compound may be added to the halogen-containing resin using techniques and apparatus well known to those of ordinary skill in this art.
- the resin may be mixed with the stabilizer in a high speed mixer for 30-90 seconds to thoroughly disperse the alkyltin compound throughout the resin.
- the halogen-containing resin may also contain known additives as long as their presence does not materially degrade the thermal stability imparted by the alkyltin compounds of the present invention.
- additives include, without limitation, lubricants, fillers, pigments, flame retardants, UV absorbers, impact modifiers and processing aids. These additives may be added to the resin using techniques and apparatus well known to those of ordinary skill in this art.
- Suitable lubricants include calcium stearate, montan wax, fatty acid esters, polyethylene waxes; chlorinated hydrocarbons, glycerol esters and combinations thereof.
- Suitable fillers include titanium oxide, calcium carbonate, kaolin, glass beads, glass fibers, talc, wood flour and mixtures thereof.
- Suitable pigments include azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, diketopyrrolopyrrole pigments and anthraquinone pigments.
- Suitable flame retardants include antimony oxide, molybdates, borates and hydroxystannates.
- Rigid PVC formulations were prepared using the stabilizer of Example 1, the control stabilizers derived from diols of higher (than ethylene glycol) molecular weight and commercially available alkyltin stabilizers, such as dimethyltin-bis(2-ethylhexylthioglycolate) (Mark 1982), dibutyltin-bis(2-ethylhexylthioglycolate) (Mark 292S), and a blend of monomethyltin-tris(2-ethylhexylthioglycolate) with dimethyltin-bis(2-ethylhexylthioglycolate) (Mark 1900).
- the tin content in the formulations was the same for all samples.
- Each PVC compound test sample was placed into a Brabender mixer operated at 190° C. and 65 RPM. Sample chips were taken every three minutes. Fusion time was about the same for all samples.
- Initial color hold refers to yellowing resistance during the first 3 to 10 minutes of the Brabender color stability test.
- Monoalkyltin stabilizers are known to provide an excellent initial color-hold.
- Long term heat stability refers to yellowing resistance at sample times greater than 10 minutes in the Brabender color stability test.
- Dialkyltin stabilizers are known to provide superior long-term heat stability.
- Blends of the monoalkyltin and dialkyltin moieties provide the most efficient balance of both initial color-hold and long-term heat stability.
- One such blend is a mixture of monomethyltin tris-(2-ethylhexylthioglycolate) and dimethyltin bis-(2-ethylhexylthioglycolate), which is commercially available from Crompton Corporation under the tradename Mark 1900.
- the dimethyltin bis(1,2-ethanedithioglycolate) stabilizer of the present invention achieved an initial color stability similar to that of the Mark 1900 blend, as measured by yellowness index (from 3 to about 10 minutes in the Brabender test; see Table 1 and FIG. 1 ).
- the dimethyltin bis(1,2-ethanedithioglycolate) stabilizer was unexpectedly effective in initial color stabilization despite the absence of a monoalkyltin moiety in its composition.
- the dimethyltin bis(1,2-ethanedithioglycolate) stabilizer also exhibited superior long-term heat stability in comparison to the Mark 1900 blend, as demonstrated by the yellowness index curves from 10-15 minutes during the Brabender color stability test.
Abstract
An alkyltin compound of specified formula which has utility as an excellent stabilizer for a halogen-containing resin. The alkyltin compound has from 1-3 terminal thiol groups.
Description
- 1. Field of the Invention
- This invention relates to alkyltin thermal stabilizers for halogen-containing resin compositions. More particularly, the present invention relates to alkyltin sulfanyl mercaptocarboxylates having from one to three terminal thiol groups and which are suitable for thermal stabilization of polyvinyl compositions.
- 2. Description of the Prior Art
- British Patent Specification No. 866,484 generically discloses alkyltin sulfanyl derivatives having terminal thiol groups, which are said to stabilize vinyl resins against the degradative effects of both heat and light. However, no experimental data is provided to quantify these claims for any of these compounds.
- Non-thiol terminated alkyltin stabilizers are also known. For example, dimethyltin bis S,S (2-ethylhexanol thioglycolate) and di-n-butyl bis S,S (2-ethylhexanol thiolglycolate) are both commercially available. One of the most effective thermal stabilizers is a blend of dimethyltin bis S,S (2-ethylhexanol thioglycolate) and methyltin tris S,S,S (2-ethylhexanol thioglycolate). These compounds are also commercially available.
- In one aspect, the present invention relates to an alkyltin compound having the formula:
-
(R)xSn[—S—(CH2)y—COO—CH2—CH2—OOC—(CH2)y—SH]4-x - wherein:
- R is a C1-3 alkyl group;
- x is equal to 1 or 2;
- y is equal to 1 or 2.
- These organotin compounds may be generally described as condensation products of organotin derivatives (such as oxides and chlorides) and dimercaptoacid esters of ethylene glycol.
- In a second aspect, the present invention relates to a composition which includes a halogen-containing resin and an alkyltin compound as described above in an amount effective to stabilize the resin against elevated temperatures, UV light, oxidation and high shear forces.
-
FIG. 1 is a graph of yellowness index of sample chips taken at various times during a heat stability test. The graph illustrates the improved color stability of a rigid PVC formulation containing the new tin stabilizer in comparison to control formulations containing other organotin compounds present at the same tin level. - The alkyltin compounds of Formula 1 preferably have methyl groups for R.
- Alkyltin compounds which come within Formula I and which are particularly preferred include dimethyltin bis(1,2-ethane dithioglycolate), monomethyltin tris(1,2-ethanedithioglycolate), dimethyltin bis(1,2-ethane dimercaptopropionate), monomethylin tris(1,2-ethanedimercaptopropionate) and mixtures thereof.
- Those of ordinary skill in the art will recognize the alkyltin compounds of the present invention may be prepared via several synthetic routes. In a preferred embodiment, these alkyltin compounds may be conveniently synthesized using a two-reaction procedure which employs readily available reactants. First, a dithiol ester is prepared by esterification of ethylene glycol with a thioacid in a molar ratio of 1:2 in the presence of a suitable catalyst. It is preferred to use a slight excess (3-5%) of thioglycolic acid. Suitable thioacids include mercaptoacetic acid and mercaptopropionic acid. Appropriate catalysts include but are not limited to p-toluene sulfonic acid and methane sulfonic acid.
- The esterification reaction may be performed with or without a solvent at an appropriate temperature, for example, 130-150° C. Water formed during the reaction is removed by conventional methods.
- The resulting dithiol ester may be neutralized with an appropriate base such as sodium bicarbonate or potassium carbonate, purified by filtering salt residues and stripped under vacuum to remove moisture, preferably at an elevated temperature such as, for example, 60-80° C.
- In the second stage of the synthesis, the dithiol ester is reacted with an appropriate tin-containing reactant, for example an alkyltin chloride or alkyltin oxide, at the following molar ratios: for dialkyltin derivatives S:Sn>1.5 and for monoalkyltin derivatives S:Sn>1.0. The resulting alkyltin compound thus contains both Sn—S bonds and free, terminal thiol groups.
- The alkyltin compounds of the present invention impart superior thermal stability to halogen-containing resins. Such resins include polyvinyl chloride (PVC), polyvinyl bromide, polyvinylidene chloride, copolymers of vinyl chloride and vinyl acetate, copolymers of vinyl chloride and vinylidene chloride, copolymers of vinyl chloride and acrylonitrile, copolymers of vinyl chloride and maleic or fumaric esters and copolymers of vinyl chloride and styrene.
- An effective amount of the alkyltin compound is an amount which makes the halogen-containing resin more resistant to discoloration than the resin per se. Generally, an effective amount will range from 0.5 to 1.50 parts stabilizer per hundred parts resin, and will depend on the specific resin and alkyltin compound, as well as the degree of thermal stabilization desired. A preferred amount of alkyltin compound is from 0.8 to 1.2 parts stabilizer per hundred parts resin.
- The alkyltin compound may be added to the halogen-containing resin using techniques and apparatus well known to those of ordinary skill in this art. Generally, the resin may be mixed with the stabilizer in a high speed mixer for 30-90 seconds to thoroughly disperse the alkyltin compound throughout the resin.
- The halogen-containing resin may also contain known additives as long as their presence does not materially degrade the thermal stability imparted by the alkyltin compounds of the present invention. Such additives include, without limitation, lubricants, fillers, pigments, flame retardants, UV absorbers, impact modifiers and processing aids. These additives may be added to the resin using techniques and apparatus well known to those of ordinary skill in this art.
- Suitable lubricants include calcium stearate, montan wax, fatty acid esters, polyethylene waxes; chlorinated hydrocarbons, glycerol esters and combinations thereof.
- Suitable fillers include titanium oxide, calcium carbonate, kaolin, glass beads, glass fibers, talc, wood flour and mixtures thereof.
- Suitable pigments include azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, diketopyrrolopyrrole pigments and anthraquinone pigments.
- Suitable flame retardants include antimony oxide, molybdates, borates and hydroxystannates.
- The following Examples illustrate the practice and advantages of specific embodiments of the invention. The Examples are not intended to limit the invention in any manner whatsoever.
- 62 g ethylene glycol was reacted with 191.2 g thioglycolic acid (TGA) in the presence of 1 g p-toluenesulfonic acid (p-TSA) at 110-150° C. Over a period of 5 hours, 34 g water was collected (theory water 36 g). The batch was neutralized with 5 g K2CO3 and filtered to yield 214 g of clear product. The acid value after neutralization was 0.051 meq/g. Mercaptan value by iodine titration was 28.74%. Gas chromatographic analysis showed no ethylene glycol and 12.6% mono-thioglycolate and 80% di-thioglycolate.
- 100.7 g of the di-thioglycolate (1,2-ethane dithioglycolate) was reacted with 50.13 g dimethyltin dichloride dissolved in 150 ml water. The reaction mix was neutralized to pH 6.5 using ammonium hydroxide solution. The crude product was separated from the aqueous phase and stripped at 80° C. and 2-5 mm Hg for 2 hours using a Buchi Rotovapor R-134 evaporator. The product was filtered hot to remove traces of residual salts to yield 104 g of the clear product. Analysis: sulfur found 22.34%, calculated 22.62; tin found 20.75%, calculated 20.85%.
- Corresponding dimethyltin sulfanyl mercaptocarboxylates prepared from 1,3-propylene glycol, 1,4-butanediol and 1,4-cyclohexanedimethanol, respectively, and which were prepared in analogous manner, were used as controls.
- Rigid PVC formulations were prepared using the stabilizer of Example 1, the control stabilizers derived from diols of higher (than ethylene glycol) molecular weight and commercially available alkyltin stabilizers, such as dimethyltin-bis(2-ethylhexylthioglycolate) (Mark 1982), dibutyltin-bis(2-ethylhexylthioglycolate) (Mark 292S), and a blend of monomethyltin-tris(2-ethylhexylthioglycolate) with dimethyltin-bis(2-ethylhexylthioglycolate) (Mark 1900). The tin content in the formulations was the same for all samples. Each PVC compound test sample was placed into a Brabender mixer operated at 190° C. and 65 RPM. Sample chips were taken every three minutes. Fusion time was about the same for all samples.
- Color stability was determined from sample chips using a Hunter Lab colorimeter measuring Yellowness Index (YI) (lower YI signifies lesser discoloration as a result of thermal decomposition and, therefore, superior thermal stabilization). See Table 1 and
FIG. 1 . -
TABLE 1 Yellowness Index of PVC and analytical data on heat stabilizers Mark Mark Mark 1,3-propanediol 1,4-CHDM EG 1,4-BG Time, min. 1900 1982 292S derivative derivative derivative derivative 3 4.18 4.35 5.91 4.49 6.00 3.59 5.72 6 6.28 7.84 11.46 7.29 8.77 5.99 8.31 9 8.09 9.96 14.29 8.93 10.97 7.93 9.76 12 12.55 16.13 19.78 13.01 15.84 11.21 15.29 15 20.69 33.30 34.03 21.37 26.21 18.41 25.12 Stabilizer Tin content, % 19.40 19.67 18.08 18.65 15.62 20.85 19.00 Stabilizer added, phr 1.20 1.18 1.29 1.25 1.49 1.12 1.23 Tin amount added, phr 0.23 0.23 0.23 0.23 0.23 0.23 0.23 Note: “1,3-propanediol derivative” is dimethyl bis (1,3-propane dithioglycolate); “1,4-CHDM derivative” is dimethyltin bis(1,4-cyclohexane dithioglycolate); “EG derivative” is dimethyltin bis (1,2-ethane dithioglycolate); and “1,4-BG derivative” is dimethyltin bis(1,4-butane dithioglycolate). “Initial color hold” refers to yellowing resistance during the first 3 to 10 minutes of the Brabender color stability test. Monoalkyltin stabilizers are known to provide an excellent initial color-hold. “Long term heat stability” refers to yellowing resistance at sample times greater than 10 minutes in the Brabender color stability test. Dialkyltin stabilizers are known to provide superior long-term heat stability. - Blends of the monoalkyltin and dialkyltin moieties provide the most efficient balance of both initial color-hold and long-term heat stability. One such blend is a mixture of monomethyltin tris-(2-ethylhexylthioglycolate) and dimethyltin bis-(2-ethylhexylthioglycolate), which is commercially available from Crompton Corporation under the tradename Mark 1900.
- Added at the same tin content, the dimethyltin bis(1,2-ethanedithioglycolate) stabilizer of the present invention achieved an initial color stability similar to that of the Mark 1900 blend, as measured by yellowness index (from 3 to about 10 minutes in the Brabender test; see Table 1 and
FIG. 1 ). In other words, the dimethyltin bis(1,2-ethanedithioglycolate) stabilizer was unexpectedly effective in initial color stabilization despite the absence of a monoalkyltin moiety in its composition. - The dimethyltin bis(1,2-ethanedithioglycolate) stabilizer also exhibited superior long-term heat stability in comparison to the Mark 1900 blend, as demonstrated by the yellowness index curves from 10-15 minutes during the Brabender color stability test.
- Although the present invention has been described in great detail with respect to preferred forms, many changes and variations are possible and will be apparent to those skilled in the art after reading the foregoing description. It is therefore to be understood that the present invention may be practiced otherwise than as specifically described herein without departing from the spirit and scope thereof.
Claims (17)
1. An alkyltin compound of Formula 1:
Rx—Sn[—S—(CH2)y—COO—CH2—CH2—OOC—(CH2)y—SH]4-x
Rx—Sn[—S—(CH2)y—COO—CH2—CH2—OOC—(CH2)y—SH]4-x
wherein:
R is a methyl group;
x is equal to 2; and
y is equal to 1.
2. (canceled)
3. (canceled)
4. A composition comprising a halogen-containing resin and an alkyltin compound of claim 1 in an amount effective to stabilize the resin against elevated temperatures.
5. The composition of claim 4 , wherein said halogen-containing resin is a member of the group consisting of polyvinyl chloride, polyvinyl bromide, polyvinylidene chloride, copolymers of vinyl chloride and vinyl acetate, copolymers of vinyl chloride and vinylidene chloride, copolymers of vinyl chloride and acrylonitrile, copolymers of vinyl chloride and maleic or fumaric esters and copolymers of vinyl chloride and styrene.
6. The composition of claim 4 , wherein said effective amount is within a range of from 0.5 to 1.8 parts stabilizer per hundred parts resin.
7. The composition of claim 6 , wherein said range is from 0.8 to 1.2 parts stabilizer per hundred parts resin.
8. The composition of claim 5 , further comprising at least one additive selected from the group consisting of lubricants, fillers, pigments, flame retardants, UV absorbers, impact modifiers and processing aids.
9. The composition of claim 8 , wherein said lubricants are selected from the group consisting of calcium stearate, montan wax, fatty acid esters, polyethylene waxes, chlorinated hydrocarbons, glycerol esters and combinations thereof.
10. The composition of claim 8 , wherein said fillers are selected from the group consisting of titanium oxide, calcium carbonate, kaolin, glass beads, glass fibers, talc, wood flour and mixtures thereof.
11. The composition of claim 8 , wherein said pigments are selected from the group consisting of azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, diketopyrrolopyrrole pigments and anthraquinone pigments.
12. The composition of claim 8 , wherein said flame retardants are selected from the group consisting of antimony oxide, molybdates, borates and hydroxystannates.
13. A method for preparation of the alkyltin compound of claim 1 , comprising i) esterifying ethylene glycol with a thioacid in a molar ratio of 1:2 in the presence of a suitable catalyst to produce a dithiol ester; and ii) reacting said dithiol ester with a tin-containing reactant at the following molar ratios: for dialkyltin derivatives S:Sn>1.5.
14. The method of claim 13 , wherein said tin-containing reactant is an alkyltin chloride or alkyltin oxide.
15. A method of stabilizing initial color of PVC consisting of adding to the PVC about 1.1 phr of dimethyltin bis(1,2-ethane dithioglycolate), wherein the PVC has a yellow index of about 3.6 at 3 minutes.
16. The method of claim 15 , wherein the PVC has a Yellow index of about 6 at 6 minutes.
17. The method of claim 16 wherein the PVC has a yellow index of about 7.9 at 9 minutes.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/835,600 US20100280155A1 (en) | 2005-05-05 | 2010-07-13 | Alkyltin Sulfanyl Mercaptocarboxylates Having Terminal Thiol Groups |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/124,464 US7767740B2 (en) | 2005-05-05 | 2005-05-05 | Alkyltin sulfanyl mercaptocarboxylates having terminal thiol groups |
US12/835,600 US20100280155A1 (en) | 2005-05-05 | 2010-07-13 | Alkyltin Sulfanyl Mercaptocarboxylates Having Terminal Thiol Groups |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/124,464 Continuation US7767740B2 (en) | 2005-05-05 | 2005-05-05 | Alkyltin sulfanyl mercaptocarboxylates having terminal thiol groups |
Publications (1)
Publication Number | Publication Date |
---|---|
US20100280155A1 true US20100280155A1 (en) | 2010-11-04 |
Family
ID=36686023
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/124,464 Expired - Fee Related US7767740B2 (en) | 2005-05-05 | 2005-05-05 | Alkyltin sulfanyl mercaptocarboxylates having terminal thiol groups |
US12/835,600 Abandoned US20100280155A1 (en) | 2005-05-05 | 2010-07-13 | Alkyltin Sulfanyl Mercaptocarboxylates Having Terminal Thiol Groups |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/124,464 Expired - Fee Related US7767740B2 (en) | 2005-05-05 | 2005-05-05 | Alkyltin sulfanyl mercaptocarboxylates having terminal thiol groups |
Country Status (8)
Country | Link |
---|---|
US (2) | US7767740B2 (en) |
EP (1) | EP1877413A1 (en) |
JP (1) | JP2008540736A (en) |
KR (1) | KR20080004570A (en) |
CN (1) | CN101171258A (en) |
BR (1) | BRPI0610478A2 (en) |
CA (1) | CA2606309A1 (en) |
WO (1) | WO2006121647A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102304145A (en) * | 2011-07-22 | 2012-01-04 | 浙江海普顿新材料股份有限公司 | Methyl tin reverse thioester and preparation method thereof |
CN106124690A (en) * | 2016-06-17 | 2016-11-16 | 浙江海普顿新材料股份有限公司 | Indirect iodometric processes measures the method for antimony content in methyl stannum antimony composite thermal stabilizer |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7781504B2 (en) * | 2006-12-05 | 2010-08-24 | Galata Chemicals, Llc | Alkyltin sulfanyl diester thiols |
US8575250B2 (en) * | 2009-04-15 | 2013-11-05 | Rohm And Haas Company | Stabilized polymer compositions |
JP6082750B2 (en) * | 2011-11-30 | 2017-02-15 | ローム アンド ハース カンパニーRohm And Haas Company | Stabilized composition of halogenated polymer |
CN102516308B (en) * | 2011-11-30 | 2014-12-17 | 浙江海普顿新材料股份有限公司 | Aromatic sulfo antimonic acid ester, and preparation method and application thereof |
WO2014028943A1 (en) | 2012-08-17 | 2014-02-20 | Metabolix, Inc. | Biobased rubber modifiers for polymer blends |
WO2014194220A1 (en) | 2013-05-30 | 2014-12-04 | Metabolix, Inc. | Recyclate blends |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2752325A (en) * | 1952-05-23 | 1956-06-26 | Argus Chemical Lab Inc | Reaction products of an organic tin compound with a glycol ester of a mercaptocarboxylic acid, and high molecular weight halogenated materials stabilized therewith |
US4111903A (en) * | 1976-05-03 | 1978-09-05 | Tenneco Chemicals, Inc. | Organotin compounds and vinyl halide resin compositions stabilized therewith |
US4546136A (en) * | 1983-05-18 | 1985-10-08 | Akzo N.V. | Organotin-containing composition for the stabilization of polymers of vinyl chloride |
US6180832B1 (en) * | 1999-05-27 | 2001-01-30 | Crompton Corporation | Preparation of peroxyketals |
US6225510B1 (en) * | 1999-12-10 | 2001-05-01 | Crompton Corporation | Preparation of di-t-alkyl peroxides and t-alkyl hydroperoxides from n-alkyl ethers |
US6379711B1 (en) * | 1999-02-05 | 2002-04-30 | Crompton Corporation | Phosphomolybdic acid stabilizer for hydrogen peroxide |
US6756431B2 (en) * | 2002-04-09 | 2004-06-29 | Crompton Corporation | Heterocyclic tin flame retardants/smoke suppressants and halogen-containing polymer composition containing same |
US6835328B2 (en) * | 2002-07-08 | 2004-12-28 | Crompton Corporation | Overbased metal carbonate/carboxylate microemulsions and halogen-containing polymers containing same |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB748228A (en) | 1952-05-23 | 1956-04-25 | Argus Chemical Lab Inc | Organic derivatives of tetravalent tin and compositions containing the same |
NL113311C (en) | 1958-10-23 | 1900-01-01 | ||
JPS5120250A (en) * | 1974-08-12 | 1976-02-18 | Cincinnati Milacron Chem | JUKISUZUGAN JUANTEIZAI |
JPS6485244A (en) * | 1987-09-25 | 1989-03-30 | Dainippon Ink & Chemicals | Resin composition for polyvinyl chloride tile |
JPH02296854A (en) * | 1989-05-11 | 1990-12-07 | Tokuyama Sekisui Ind Corp | Stabilization of chlorinated vinyl chloride resin |
JPH05156110A (en) * | 1991-12-09 | 1993-06-22 | Sekisui Chem Co Ltd | Vinyl chloride resin composition |
-
2005
- 2005-05-05 US US11/124,464 patent/US7767740B2/en not_active Expired - Fee Related
-
2006
- 2006-04-28 CA CA002606309A patent/CA2606309A1/en not_active Abandoned
- 2006-04-28 EP EP06758755A patent/EP1877413A1/en not_active Withdrawn
- 2006-04-28 CN CNA2006800152277A patent/CN101171258A/en active Pending
- 2006-04-28 JP JP2008510075A patent/JP2008540736A/en active Pending
- 2006-04-28 KR KR1020077025491A patent/KR20080004570A/en not_active Application Discontinuation
- 2006-04-28 WO PCT/US2006/016310 patent/WO2006121647A1/en active Application Filing
- 2006-04-28 BR BRPI0610478-9A patent/BRPI0610478A2/en not_active IP Right Cessation
-
2010
- 2010-07-13 US US12/835,600 patent/US20100280155A1/en not_active Abandoned
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2752325A (en) * | 1952-05-23 | 1956-06-26 | Argus Chemical Lab Inc | Reaction products of an organic tin compound with a glycol ester of a mercaptocarboxylic acid, and high molecular weight halogenated materials stabilized therewith |
US4111903A (en) * | 1976-05-03 | 1978-09-05 | Tenneco Chemicals, Inc. | Organotin compounds and vinyl halide resin compositions stabilized therewith |
US4546136A (en) * | 1983-05-18 | 1985-10-08 | Akzo N.V. | Organotin-containing composition for the stabilization of polymers of vinyl chloride |
US6379711B1 (en) * | 1999-02-05 | 2002-04-30 | Crompton Corporation | Phosphomolybdic acid stabilizer for hydrogen peroxide |
US6180832B1 (en) * | 1999-05-27 | 2001-01-30 | Crompton Corporation | Preparation of peroxyketals |
US6225510B1 (en) * | 1999-12-10 | 2001-05-01 | Crompton Corporation | Preparation of di-t-alkyl peroxides and t-alkyl hydroperoxides from n-alkyl ethers |
US6756431B2 (en) * | 2002-04-09 | 2004-06-29 | Crompton Corporation | Heterocyclic tin flame retardants/smoke suppressants and halogen-containing polymer composition containing same |
US6835328B2 (en) * | 2002-07-08 | 2004-12-28 | Crompton Corporation | Overbased metal carbonate/carboxylate microemulsions and halogen-containing polymers containing same |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102304145A (en) * | 2011-07-22 | 2012-01-04 | 浙江海普顿新材料股份有限公司 | Methyl tin reverse thioester and preparation method thereof |
CN106124690A (en) * | 2016-06-17 | 2016-11-16 | 浙江海普顿新材料股份有限公司 | Indirect iodometric processes measures the method for antimony content in methyl stannum antimony composite thermal stabilizer |
Also Published As
Publication number | Publication date |
---|---|
US7767740B2 (en) | 2010-08-03 |
CN101171258A (en) | 2008-04-30 |
KR20080004570A (en) | 2008-01-09 |
WO2006121647A1 (en) | 2006-11-16 |
BRPI0610478A2 (en) | 2012-01-10 |
US20060252859A1 (en) | 2006-11-09 |
JP2008540736A (en) | 2008-11-20 |
EP1877413A1 (en) | 2008-01-16 |
CA2606309A1 (en) | 2006-11-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US20100280155A1 (en) | Alkyltin Sulfanyl Mercaptocarboxylates Having Terminal Thiol Groups | |
US8088937B2 (en) | Alkyltin sulfanyl diester thiols | |
US3115509A (en) | Chemical product and process | |
US4104292A (en) | Method for preparing organotin compounds | |
US4021407A (en) | Synergistic organotin borate stabilizer compositions and resins containing same | |
US4111903A (en) | Organotin compounds and vinyl halide resin compositions stabilized therewith | |
US20100190902A1 (en) | Alkyltin sulfanyl ester thiols | |
JPS62111951A (en) | Novel unsaturated carboxylic ester, its use and chlorinated polymer stabilized by said ester | |
US20070161728A1 (en) | Organic Thiol Stabilizers and Plasticizers for Halogen-Containing Polymers | |
US3818062A (en) | Unsaturated organi-tin mercaptides, their preparation and use | |
CA1055955A (en) | Organotin mercapto dicarboxylic acid esters and compositions | |
JP3729858B2 (en) | Aromatic ether alcohol-containing alkyl-thio-glycolate PVC stabilizer for precipitation prevention | |
US4546136A (en) | Organotin-containing composition for the stabilization of polymers of vinyl chloride | |
US3208969A (en) | Vinyl halide resins stabilized with di-organo tin aromatic dimercapto compounds | |
US5354508A (en) | Organotin stabilizer mixture | |
US3221036A (en) | Dihydrocarbyltin compounds of bis-phenols | |
EP0124833A1 (en) | Heat stabilizers for halogenated resins | |
US3833519A (en) | Stabilizers for vinyl chloride-containing resins | |
US4307028A (en) | Preparation of organo-tin compounds | |
US7087193B2 (en) | Stabilizer composition for use in polyvinyl chloride formulations having a mixture of at least one organotin sulfide, at least one oranotin chloride, and at least one free mercaptan | |
GB748228A (en) | Organic derivatives of tetravalent tin and compositions containing the same | |
JPS6126793B2 (en) | ||
JPS607639B2 (en) | Organic tin mercapto dicarboxylic acid ester | |
JPS625189B2 (en) | ||
CS216891B1 (en) | Method of preparation of combined organo-stannate compounds and utilization thereof for thermal stabilization of the polyvinylchloride |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |