CA1170031A - Mixtures of organo-tin compounds - Google Patents
Mixtures of organo-tin compoundsInfo
- Publication number
- CA1170031A CA1170031A CA000429807A CA429807A CA1170031A CA 1170031 A CA1170031 A CA 1170031A CA 000429807 A CA000429807 A CA 000429807A CA 429807 A CA429807 A CA 429807A CA 1170031 A CA1170031 A CA 1170031A
- Authority
- CA
- Canada
- Prior art keywords
- organo
- tin
- alkyl
- mixtures
- iii
- 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.)
- Expired
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 30
- 229920000642 polymer Polymers 0.000 claims abstract description 14
- 229920003023 plastic Polymers 0.000 claims abstract description 12
- 239000004033 plastic Substances 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 150000007942 carboxylates Chemical class 0.000 claims abstract description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052760 oxygen Chemical group 0.000 claims abstract description 3
- 239000001301 oxygen Chemical group 0.000 claims abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 3
- 239000011593 sulfur Substances 0.000 claims abstract description 3
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims abstract 2
- -1 2-ethylhexyl Chemical group 0.000 claims description 29
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 239000004952 Polyamide Substances 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims description 2
- 150000003077 polyols Chemical class 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims 1
- 239000012190 activator Substances 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000003381 stabilizer Substances 0.000 abstract description 5
- 239000004800 polyvinyl chloride Substances 0.000 description 10
- 229920000915 polyvinyl chloride Polymers 0.000 description 10
- 239000004604 Blowing Agent Substances 0.000 description 7
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000004611 light stabiliser Substances 0.000 description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 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 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000004608 Heat Stabiliser Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 235000006708 antioxidants Nutrition 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 150000002688 maleic acid derivatives Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000001421 myristyl 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])[H] 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical class OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- JOEQHIQLTUBRAX-UHFFFAOYSA-N C(CCCCCCC(C)C)(=O)[Sn] Chemical compound C(CCCCCCC(C)C)(=O)[Sn] JOEQHIQLTUBRAX-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- GLHCIBDSDRCWMI-UHFFFAOYSA-N O-(2-ethylhexyl) propanethioate Chemical compound C(CC)(=S)OCC(CCCC)CC GLHCIBDSDRCWMI-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 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
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- CWERGRDVMFNCDR-UHFFFAOYSA-N alpha-mercaptoacetic acid Natural products OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 125000002511 behenyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- HVBLYMFPMVEUAW-UHFFFAOYSA-M butyl-(3-dodecoxy-3-oxopropyl)sulfanyl-sulfanylidenetin Chemical compound CCCCCCCCCCCCOC(=O)CCS[Sn](=S)CCCC HVBLYMFPMVEUAW-UHFFFAOYSA-M 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000003901 ceryl 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])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
- 239000007795 chemical reaction product Substances 0.000 description 1
- 125000002704 decyl 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])* 0.000 description 1
- 150000001470 diamides Chemical class 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 125000003136 n-heptyl 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])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000001196 nonadecyl 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])C([H])([H])[H] 0.000 description 1
- ZMHZSHHZIKJFIR-UHFFFAOYSA-N octyltin Chemical compound CCCCCCCC[Sn] ZMHZSHHZIKJFIR-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920000131 polyvinylidene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Abstract of the Disclosure Mixture consisting of an organo-tin mercaptide of the formula (II) or (III) (II) , (III), and an organo-tin carboxylate of the formula IV or V
(IV) ,
(IV) ,
Description
03~
1 ~ .
Case 3-12247/CGM 224/1-3/~_ CANADA
Mixtures of organo-tin compounds The present invPntion relates to mixtures of organo-tin compounds and to chlorinated polymers and foamed plastics materials which contain these mixtures.
Mixtures consisting of an organo-tin mercaptide and an organo-tin compound selected from the group consisting of organo-t;n, organo-tin carboxylate, organo-tin alcoholate or organo-tin oxide, are described as effective thermostabilisers in German Offenlegungs-schrift 1 926 949. A mixture consisting of an organo-tin thioglycolic acid ester and an organo~tin compound as described above is speci-fically disclosed in this publication.
As it is known that organo-tin mercaptides lower the impact strength of rigid polymers, there is considerable interest in highly effec-tive sta-~ilisers which can be employed in small amounts.
Organo-tin compounds are also employed as activators for the manu-facture of foamed articles composed of plastics. These articles are ordinarily manufactured ~y known methods, for example by in-jection moulding, by blending the plastics material with a suitable blowing agent and choosing the processing temperature such that it is above the decomposition temperature of the blowing agent.
Often, however, the decomposition temperature is too high above the processing temperature, so that the blowing agent cannot be uséd alone. For this reason, activators are often employed which hasten Lhe decomposition of the blowing agent and/or the decompo-sition temperature.
,. ~
3~
It has now been found that a mixture of organo-tin compounds and of an organo-tin mercaptopropionic acid ester imparts surprisingly good light and heat stability to chlorinated polymers and, in addition, is an effective activator for the manufacture of foamed plastics.
Accordingly, the present invention provides mixtures consisting of an organo-tin mercaptide of the formula II or III
(R )n-Sn(-S-cH2cHz~cOOR )3-n (II) X
R -sn-s-cH2cH2-cooR (III) 5 and an organo-tin carboxylate of the formula IV or V
(R ~ Sn(-OOC-R6)2 (IV) R -COO-Sn---O---Sn-OOC-R (V) in which formulae R is Cl-Clz alkyl, X is sulfur or oxygen, R lS
the -S-CH2CH2-CooR5 or -X-Sn(R ) (S-CH~CH2-COOR )3 group, in which R and X are as defined above, R is C8-C14 alkyl, n is 1 or
1 ~ .
Case 3-12247/CGM 224/1-3/~_ CANADA
Mixtures of organo-tin compounds The present invPntion relates to mixtures of organo-tin compounds and to chlorinated polymers and foamed plastics materials which contain these mixtures.
Mixtures consisting of an organo-tin mercaptide and an organo-tin compound selected from the group consisting of organo-t;n, organo-tin carboxylate, organo-tin alcoholate or organo-tin oxide, are described as effective thermostabilisers in German Offenlegungs-schrift 1 926 949. A mixture consisting of an organo-tin thioglycolic acid ester and an organo~tin compound as described above is speci-fically disclosed in this publication.
As it is known that organo-tin mercaptides lower the impact strength of rigid polymers, there is considerable interest in highly effec-tive sta-~ilisers which can be employed in small amounts.
Organo-tin compounds are also employed as activators for the manu-facture of foamed articles composed of plastics. These articles are ordinarily manufactured ~y known methods, for example by in-jection moulding, by blending the plastics material with a suitable blowing agent and choosing the processing temperature such that it is above the decomposition temperature of the blowing agent.
Often, however, the decomposition temperature is too high above the processing temperature, so that the blowing agent cannot be uséd alone. For this reason, activators are often employed which hasten Lhe decomposition of the blowing agent and/or the decompo-sition temperature.
,. ~
3~
It has now been found that a mixture of organo-tin compounds and of an organo-tin mercaptopropionic acid ester imparts surprisingly good light and heat stability to chlorinated polymers and, in addition, is an effective activator for the manufacture of foamed plastics.
Accordingly, the present invention provides mixtures consisting of an organo-tin mercaptide of the formula II or III
(R )n-Sn(-S-cH2cHz~cOOR )3-n (II) X
R -sn-s-cH2cH2-cooR (III) 5 and an organo-tin carboxylate of the formula IV or V
(R ~ Sn(-OOC-R6)2 (IV) R -COO-Sn---O---Sn-OOC-R (V) in which formulae R is Cl-Clz alkyl, X is sulfur or oxygen, R lS
the -S-CH2CH2-CooR5 or -X-Sn(R ) (S-CH~CH2-COOR )3 group, in which R and X are as defined above, R is C8-C14 alkyl, n is 1 or
2, and R is C10-C30 alkyl, the weight ratio of II:IV or III:IV
being in the range from 9:1 to 1:9.
R as Cl-C12 alkyl is e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl, tert.-butyl n-amyl, iso-amyl, n-hexyl, n-heptyl, n-octyl, n-dodecyl. Preferably, R is methyl, n-butyl, n-amyl, n-hexyl and ., ~7~1~3~
being in the range from 9:1 to 1:9.
R as Cl-C12 alkyl is e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl, tert.-butyl n-amyl, iso-amyl, n-hexyl, n-heptyl, n-octyl, n-dodecyl. Preferably, R is methyl, n-butyl, n-amyl, n-hexyl and ., ~7~1~3~
3 --n-octyl. Most preferably, R is methyl, n-butyl and n-octyl.
R can be the group -S-CH2CH2-CooR5, wherein R5 is C6~C14 alkyl, e.g. 2-ethylhexyl, decyl, dodecyl, isotridecyl, tetradecyl. R
is preferably 2-ethylhexyl, dodecyl and isotridecyl, especially 2-ethylhexyl and isotridecyl.
R can be the group -S-CH2CH2-CooR5, wherein R5 is C6~C14 alkyl, e.g. 2-ethylhexyl, decyl, dodecyl, isotridecyl, tetradecyl. R
is preferably 2-ethylhexyl, dodecyl and isotridecyl, especially 2-ethylhexyl and isotridecyl.
4 b th group -X-Sn(Rl) (S-CH2CH2-COOR )3-n~ 5 and n are as defined above. Preferably,R is -S-CH2CH2-COOR , R as C10-C30 alkyl is e.g. decyll dodecyl, isotridecyl, tetradecyl, iso-octadecyl, nonadecyl, docosyl, hexacosyl.
Preferabiy, R6 is C10-C22 alkyl, most preferably 16-methylheptadecyl, iso-nonyl and n-undecyl.
Examples of compounds of the formula II are:
octyl-tin tris(dodecyl-~-mercaptopropionate)-dibutyl-tin bis(isotridecyl-~-mercaptopropionate) dibutyl-tin bis(2-efhylhexyl-~-mercaptopropionate) bis(dibutyl-tin 2-ethylhexyl-~-mercaptopropionate? oxide.
The preferred compound of the formula II is dibutyl-tin bis(2-ethylhexyl-~-mercaptopropionate)O
A preferred example oE the compound of che formula III is butyl(2-dodecyloxycarbonylethylmercapto)-tin sulfide.
Examples of the compounds of the formulae IVresp.V are:
dibutyl-tin dilaurate bis(dibutyl isodecanoyl-tin) oxide dibuf:yl-tin di-isooctadecylate.
~,....
3~
The preferred compound of the formula IV is dibutyl-tin di-isoocta-decylate.
The chlorinated polymers which contain the stabiliser mixture of the invention can be homopolymers, e.g. polyvinyl chloride, poly-vinylidene chlor;de etc. Suitable polymers are emulsion, suspension and mass polyvinyl chloride. The polymers can also be copol~ners which have been obtained by copolymerising vinyl chloride or vinylidene chloride with other ethylenically unsaturated monomers.
Ethylenically unsaturated monomers are compounds which contain polymerisable C C double bonds, and comprise acrylates, e.g. acrylic acid, ethyl acrylate9 acrylonitrile; vinyl monomers, e.g. styrene, vinyl acetate; maleic acid derivatives, e.g. maleic aci~, maleates, maleic anhydride.
The mixtures of this invention can also be employed as activators for foaming plastics materials. These plastics materials can be chlorinated polymers, such as those described above; but polyesters, polylactones? polyamides, polyethers, polycarbonates and, preferably, polyols, are also suitable~
It is especially preferred to use the mixtures of this invention in polymers based on polyvinyl chloride, especially in PVC, viz. both in plasticised PVC and in rigid PVC. Rigid PVC ~hich has been stabilised with the mixtures of this invention is most suitable for external use.
Organo-tin carboxylates as light and heat stabilisers Eor halogenated polymers have been described in the above mentioned German Offen-legungsschrift 1 92~ 949 in combination with organo-tin mercapto-rarboxylates These latter are also known from US patent specifi-cation 3 642 677.
~7~3~
The organo~tin carboxylates can be obtained by simple rection of the alkali salts of the acid in question with a water-soluble salt of tin.
A particularly uncomplicated method of manufacture is to react the carboxylic acid, mercaptan and tin reactants simultaneously.
The amount of organo-tin compounds in the substrates depends on economic and technical aspects. ~s a rule, 0.1 to 3 ~ by weight, based on the polymer, especially 0.3 to 2 % by weight, is added.
The weight ratio of organo~tin compounds of the formulae II:IV
or III:IV in the mixtures of the invention is 9:1 to 1:9, preferably 9:1 to 6:4.
If desired, it is possible to add to the stabilised polymer mixtures of the invention 0.1 to 5 % by weight, preferably 0.5 to 3 % by weight, of conventional additives, especially anti-oxidants, light stabilisers or mixtures thereof. Examples of such additives are:
antioxidants, such as 2,6-dialkylphenols, e.g. 2,4,6-tri-tert.-butyl-phenol, 2,6-di-tert.-butyl-4-methylphenyl, 2-tert.-butyl-4,6-di-methylphenol, the ~-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propionie acid ester of pentaerythritol ~IRGANOX ~ 1010) or the same ester of stearyl alcohol (IRGANOX ~ 1076), and others such as bisphenol ~ A, UV-absorbers and light stabilisers such as 2-(Z'-hydroxyphenyl)-benztriaæoles, 2,4-bis(2'-hydroxyphenyl)-~-s-triazines, 2-hydroxy-benzophenones, 1,3-bis-(2'-hydroxybenzoyl)~benzenes, esters of un-substituted or substituted benæoie aeids, aerylates, and also nickel eompounds, sterically hindered amines, oxalie diamides, or other additives, e.g. plasticisers, lubricants, emulsifiers9 fillers, carbon black, asbestos, kaolin, tale, glass fibres, pigments, fluorescent whitening agents, flame retardants, antistatic agents.
,~ .
.
The mixture of organo-tin compounds of this invention can be blended with the polymer by known methods in known mixing devices. To this end, it is possible to add the blowing agent for foamed plastics material together with the organo-tin activa~or, or to blend the activator with a plastics material which already contains the blowing agent. In oLder to obtain as homogeneous mixtures as possiblej it is advantageous to blend the individual components in powder form. It is possible, however, to use plastics granulates, in whic~
case a binder can additionally be employed for better adhesion of the blowing agent and/or the organo-tin activator.
The mixtures of the present invention are surprisingly effective heat and light stabilisers. Owing to their excellent light protective action, the stabilised polymer is especially suitable for external use. In addition, the mixtures of the invention are surprisingly effective activators for the manufacture of foamed plastics.
The invention is illustrated in more detail by the following Examples, in which parts and percentages are by weight unless otherwise stated.
~xam ~ Dibutyl-tin bis(-2-ethylhexyl-~-mercaptopropionate) -- - . , 25.0 g (Q.l mole) of dibutyl-tin oæide is reacted with 43.6 g of 2-ethylhexyL thiopropionate at 110C under a water jet vacuum until the water of reaction has been completely removed.
Sn (found): 17.1 %; n20 = 1.5015.
3~.
Example 2~
(C H ~ Sn(OOC-C H23)-0-Sn{-C4Hg)2(00C 11 23 4 9 ~ ( 2 2 8 17)2 (30 %) 39.6 g ~0.159 mole) of dibutyl-tin oxide are reacted with 31.8 g (0.159 mole) of lauric acid at 110C while removing the water of reaction. The resultant fluid reaction product is mixed with 30 g of dibutyl-tin bis (2-ethylhexyl-~-mercaptopropionate) obtained in accordance with Example 1.
Sn (found) : 24.5 %, n20 = 1.4928 The weight ratio of II:V is 1:2.3.
Application Tes_ Example 3: Mill ageing test A dry blend consisting of 100 parts of PVC (Vestolit ~ HIS 6882), 4 parts of TiO2 and 2.5 parts of stabiliser mixture of Example 2 is subjected to a mill ageing test at 200C, and samples are taken at 3 minute intervals to determine the Yellowness Index.
Yellowness Index (Y.I.) _ i~ _ __ _ _. ~ . ~
mins, 3 6 9 12 15 18 21 24 27 30 33 36 . _ Y.I. 6.7 7.4 8.3 9.0 9.9 11.5 12.5 14.3 16.9 20.7 28.2 37.7 _ _ _ ~1~7~3~L
Example 4: Weathering test 100 parts of PVC are mixed with 0.2 part of Tinuvin ~ 320 and 2.5 parts of the stabiliser mixture in a high-speed mixer.
The mixture is rolled to a sheet for 5 minutes at 180C on a laboratory roll mill, and from this sheet a 0.5 mm transparent sheet is pressed at 180C on a daylight-press. This sheet is exposed to an accelerated weathering test (Xenotest ~ 150 lamp~ Original Hanau Quarzlampen GmbH, Hanau, West Germany). The weathering cycle comprises 29 minutes exposure to xenon-arc radiation and 1 minute exposure to artificial rain. Exposure is effected in rotation.
In the table below, h indicates the total weathering time in hours.
The test values indicate the course of yellowing (Yellowness Indices)O
The weathering test as described above is carried out using a dry blend consisting of 100 parts of PVC (Vestolit~ HIS 6882), 4 parts of titanium dioxide and 2.5 parts of the stabiliser mixture of Example 2. The results are reported in the following tableO
Time ~ O ~ 2400 ~ 4800 ~ 7200 ~ 9600 ~ 12000 Y~Ii 8.2 5.2 4.8 4.1 4.4 5.7 .._ _ _ . ._ Even after 12000 weathering, the sheet exhibits no discolouration.
Preferabiy, R6 is C10-C22 alkyl, most preferably 16-methylheptadecyl, iso-nonyl and n-undecyl.
Examples of compounds of the formula II are:
octyl-tin tris(dodecyl-~-mercaptopropionate)-dibutyl-tin bis(isotridecyl-~-mercaptopropionate) dibutyl-tin bis(2-efhylhexyl-~-mercaptopropionate) bis(dibutyl-tin 2-ethylhexyl-~-mercaptopropionate? oxide.
The preferred compound of the formula II is dibutyl-tin bis(2-ethylhexyl-~-mercaptopropionate)O
A preferred example oE the compound of che formula III is butyl(2-dodecyloxycarbonylethylmercapto)-tin sulfide.
Examples of the compounds of the formulae IVresp.V are:
dibutyl-tin dilaurate bis(dibutyl isodecanoyl-tin) oxide dibuf:yl-tin di-isooctadecylate.
~,....
3~
The preferred compound of the formula IV is dibutyl-tin di-isoocta-decylate.
The chlorinated polymers which contain the stabiliser mixture of the invention can be homopolymers, e.g. polyvinyl chloride, poly-vinylidene chlor;de etc. Suitable polymers are emulsion, suspension and mass polyvinyl chloride. The polymers can also be copol~ners which have been obtained by copolymerising vinyl chloride or vinylidene chloride with other ethylenically unsaturated monomers.
Ethylenically unsaturated monomers are compounds which contain polymerisable C C double bonds, and comprise acrylates, e.g. acrylic acid, ethyl acrylate9 acrylonitrile; vinyl monomers, e.g. styrene, vinyl acetate; maleic acid derivatives, e.g. maleic aci~, maleates, maleic anhydride.
The mixtures of this invention can also be employed as activators for foaming plastics materials. These plastics materials can be chlorinated polymers, such as those described above; but polyesters, polylactones? polyamides, polyethers, polycarbonates and, preferably, polyols, are also suitable~
It is especially preferred to use the mixtures of this invention in polymers based on polyvinyl chloride, especially in PVC, viz. both in plasticised PVC and in rigid PVC. Rigid PVC ~hich has been stabilised with the mixtures of this invention is most suitable for external use.
Organo-tin carboxylates as light and heat stabilisers Eor halogenated polymers have been described in the above mentioned German Offen-legungsschrift 1 92~ 949 in combination with organo-tin mercapto-rarboxylates These latter are also known from US patent specifi-cation 3 642 677.
~7~3~
The organo~tin carboxylates can be obtained by simple rection of the alkali salts of the acid in question with a water-soluble salt of tin.
A particularly uncomplicated method of manufacture is to react the carboxylic acid, mercaptan and tin reactants simultaneously.
The amount of organo-tin compounds in the substrates depends on economic and technical aspects. ~s a rule, 0.1 to 3 ~ by weight, based on the polymer, especially 0.3 to 2 % by weight, is added.
The weight ratio of organo~tin compounds of the formulae II:IV
or III:IV in the mixtures of the invention is 9:1 to 1:9, preferably 9:1 to 6:4.
If desired, it is possible to add to the stabilised polymer mixtures of the invention 0.1 to 5 % by weight, preferably 0.5 to 3 % by weight, of conventional additives, especially anti-oxidants, light stabilisers or mixtures thereof. Examples of such additives are:
antioxidants, such as 2,6-dialkylphenols, e.g. 2,4,6-tri-tert.-butyl-phenol, 2,6-di-tert.-butyl-4-methylphenyl, 2-tert.-butyl-4,6-di-methylphenol, the ~-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propionie acid ester of pentaerythritol ~IRGANOX ~ 1010) or the same ester of stearyl alcohol (IRGANOX ~ 1076), and others such as bisphenol ~ A, UV-absorbers and light stabilisers such as 2-(Z'-hydroxyphenyl)-benztriaæoles, 2,4-bis(2'-hydroxyphenyl)-~-s-triazines, 2-hydroxy-benzophenones, 1,3-bis-(2'-hydroxybenzoyl)~benzenes, esters of un-substituted or substituted benæoie aeids, aerylates, and also nickel eompounds, sterically hindered amines, oxalie diamides, or other additives, e.g. plasticisers, lubricants, emulsifiers9 fillers, carbon black, asbestos, kaolin, tale, glass fibres, pigments, fluorescent whitening agents, flame retardants, antistatic agents.
,~ .
.
The mixture of organo-tin compounds of this invention can be blended with the polymer by known methods in known mixing devices. To this end, it is possible to add the blowing agent for foamed plastics material together with the organo-tin activa~or, or to blend the activator with a plastics material which already contains the blowing agent. In oLder to obtain as homogeneous mixtures as possiblej it is advantageous to blend the individual components in powder form. It is possible, however, to use plastics granulates, in whic~
case a binder can additionally be employed for better adhesion of the blowing agent and/or the organo-tin activator.
The mixtures of the present invention are surprisingly effective heat and light stabilisers. Owing to their excellent light protective action, the stabilised polymer is especially suitable for external use. In addition, the mixtures of the invention are surprisingly effective activators for the manufacture of foamed plastics.
The invention is illustrated in more detail by the following Examples, in which parts and percentages are by weight unless otherwise stated.
~xam ~ Dibutyl-tin bis(-2-ethylhexyl-~-mercaptopropionate) -- - . , 25.0 g (Q.l mole) of dibutyl-tin oæide is reacted with 43.6 g of 2-ethylhexyL thiopropionate at 110C under a water jet vacuum until the water of reaction has been completely removed.
Sn (found): 17.1 %; n20 = 1.5015.
3~.
Example 2~
(C H ~ Sn(OOC-C H23)-0-Sn{-C4Hg)2(00C 11 23 4 9 ~ ( 2 2 8 17)2 (30 %) 39.6 g ~0.159 mole) of dibutyl-tin oxide are reacted with 31.8 g (0.159 mole) of lauric acid at 110C while removing the water of reaction. The resultant fluid reaction product is mixed with 30 g of dibutyl-tin bis (2-ethylhexyl-~-mercaptopropionate) obtained in accordance with Example 1.
Sn (found) : 24.5 %, n20 = 1.4928 The weight ratio of II:V is 1:2.3.
Application Tes_ Example 3: Mill ageing test A dry blend consisting of 100 parts of PVC (Vestolit ~ HIS 6882), 4 parts of TiO2 and 2.5 parts of stabiliser mixture of Example 2 is subjected to a mill ageing test at 200C, and samples are taken at 3 minute intervals to determine the Yellowness Index.
Yellowness Index (Y.I.) _ i~ _ __ _ _. ~ . ~
mins, 3 6 9 12 15 18 21 24 27 30 33 36 . _ Y.I. 6.7 7.4 8.3 9.0 9.9 11.5 12.5 14.3 16.9 20.7 28.2 37.7 _ _ _ ~1~7~3~L
Example 4: Weathering test 100 parts of PVC are mixed with 0.2 part of Tinuvin ~ 320 and 2.5 parts of the stabiliser mixture in a high-speed mixer.
The mixture is rolled to a sheet for 5 minutes at 180C on a laboratory roll mill, and from this sheet a 0.5 mm transparent sheet is pressed at 180C on a daylight-press. This sheet is exposed to an accelerated weathering test (Xenotest ~ 150 lamp~ Original Hanau Quarzlampen GmbH, Hanau, West Germany). The weathering cycle comprises 29 minutes exposure to xenon-arc radiation and 1 minute exposure to artificial rain. Exposure is effected in rotation.
In the table below, h indicates the total weathering time in hours.
The test values indicate the course of yellowing (Yellowness Indices)O
The weathering test as described above is carried out using a dry blend consisting of 100 parts of PVC (Vestolit~ HIS 6882), 4 parts of titanium dioxide and 2.5 parts of the stabiliser mixture of Example 2. The results are reported in the following tableO
Time ~ O ~ 2400 ~ 4800 ~ 7200 ~ 9600 ~ 12000 Y~Ii 8.2 5.2 4.8 4.1 4.4 5.7 .._ _ _ . ._ Even after 12000 weathering, the sheet exhibits no discolouration.
Claims (5)
1. A mixture consisting of an organo-tin mercaptide of the formula II or III
(II) (III) , and of an organo-tin carboxylate of the formula IV or V
(IV) (V) , in which formulae R1 is C1-C12 alkyl, X is sulfur or oxygen, R4 is the -S-CH2CH2-COOR5 or -X-Sn(R1)n(S-CH2CH2-COOR5)3-n group, in which R1 and X are as defined above, R5 is C8-C14 alkyl, n is 1 or 2, and R6 is C10-C30 alkyl, the weight ratio of II:IV or III IV
being in the range from 9:1 to 1:9.
(II) (III) , and of an organo-tin carboxylate of the formula IV or V
(IV) (V) , in which formulae R1 is C1-C12 alkyl, X is sulfur or oxygen, R4 is the -S-CH2CH2-COOR5 or -X-Sn(R1)n(S-CH2CH2-COOR5)3-n group, in which R1 and X are as defined above, R5 is C8-C14 alkyl, n is 1 or 2, and R6 is C10-C30 alkyl, the weight ratio of II:IV or III IV
being in the range from 9:1 to 1:9.
2. A mixture according to claim 1, wherein R4 in the compound of the formula (II) is the -S-CH2CH2-COOR5 group, in which R5 is C8-C14 alkyl.
3. A mixture according to claim 27 wherein R5 is 2-ethylhexyl.
4. A mixture according to claim 1, wherein R6 is n-undecyl.
5. A chlorinated homo- and copolymer and a foamed plastics material, as chlorinated polymers, polyesters, polylactones, polyamides, polyoethers, polycarbonates and polyols, containing a mixture according to claim 1.
PO 7.3 RU/rz*
PO 7.3 RU/rz*
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000429807A CA1170031A (en) | 1979-02-22 | 1983-06-06 | Mixtures of organo-tin compounds |
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1787/79-5 | 1979-02-22 | ||
| CH178779 | 1979-02-22 | ||
| CH1087279 | 1979-12-07 | ||
| CH10872/79-8 | 1979-12-07 | ||
| CA000346076A CA1152735A (en) | 1979-02-22 | 1980-02-20 | Mixtures of organotin compounds |
| CA000429807A CA1170031A (en) | 1979-02-22 | 1983-06-06 | Mixtures of organo-tin compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1170031A true CA1170031A (en) | 1984-07-03 |
Family
ID=27426220
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000429807A Expired CA1170031A (en) | 1979-02-22 | 1983-06-06 | Mixtures of organo-tin compounds |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1170031A (en) |
-
1983
- 1983-06-06 CA CA000429807A patent/CA1170031A/en not_active Expired
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