CA1156448A - Stabilisers for pvc - Google Patents
Stabilisers for pvcInfo
- Publication number
- CA1156448A CA1156448A CA000366277A CA366277A CA1156448A CA 1156448 A CA1156448 A CA 1156448A CA 000366277 A CA000366277 A CA 000366277A CA 366277 A CA366277 A CA 366277A CA 1156448 A CA1156448 A CA 1156448A
- Authority
- CA
- Canada
- Prior art keywords
- mixture
- mol
- tin
- octyl
- stabilisers
- 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
- 239000003381 stabilizer Substances 0.000 title abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 33
- ZMHZSHHZIKJFIR-UHFFFAOYSA-N octyltin Chemical class CCCCCCCC[Sn] ZMHZSHHZIKJFIR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 7
- 229920001169 thermoplastic Polymers 0.000 claims description 6
- 239000004416 thermosoftening plastic Substances 0.000 claims description 6
- INTLMJZQCBRQAT-UHFFFAOYSA-K trichloro(octyl)stannane Chemical compound CCCCCCCC[Sn](Cl)(Cl)Cl INTLMJZQCBRQAT-UHFFFAOYSA-K 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- LQRUPWUPINJLMU-UHFFFAOYSA-N dioctyl(oxo)tin Chemical compound CCCCCCCC[Sn](=O)CCCCCCCC LQRUPWUPINJLMU-UHFFFAOYSA-N 0.000 claims description 4
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 4
- 125000005907 alkyl ester group Chemical group 0.000 claims description 3
- SBOSGIJGEHWBKV-UHFFFAOYSA-L dioctyltin(2+);dichloride Chemical compound CCCCCCCC[Sn](Cl)(Cl)CCCCCCCC SBOSGIJGEHWBKV-UHFFFAOYSA-L 0.000 claims description 3
- KGHLYBKDIPRXHA-UHFFFAOYSA-N octyl(oxo)tin Chemical compound CCCCCCCC[Sn]=O KGHLYBKDIPRXHA-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 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 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 150000002367 halogens Chemical class 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000004800 polyvinyl chloride Substances 0.000 description 11
- 229920000915 polyvinyl chloride Polymers 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052718 tin Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- -1 fatty acid esters Chemical class 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000012170 montan wax Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- LXDHBOICPCPCKD-UHFFFAOYSA-N tetradecyl 2-sulfanylacetate Chemical compound CCCCCCCCCCCCCCOC(=O)CS LXDHBOICPCPCKD-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- RZRNAYUHWVFMIP-KTKRTIGZSA-N 1-oleoylglycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-KTKRTIGZSA-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
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004908 Emulsion polymer Substances 0.000 description 1
- 239000004610 Internal Lubricant Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical class [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical class [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical class [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- LMDIIDPLWVGXKM-UHFFFAOYSA-N decyl 2-sulfanylacetate Chemical compound CCCCCCCCCCOC(=O)CS LMDIIDPLWVGXKM-UHFFFAOYSA-N 0.000 description 1
- HGQSXVKHVMGQRG-UHFFFAOYSA-N dioctyltin Chemical compound CCCCCCCC[Sn]CCCCCCCC HGQSXVKHVMGQRG-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- TVMDUMQNXXNGMG-UHFFFAOYSA-N dodecyl 2-sulfanylacetate Chemical compound CCCCCCCCCCCCOC(=O)CS TVMDUMQNXXNGMG-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- RZRNAYUHWVFMIP-HXUWFJFHSA-N glycerol monolinoleate Natural products CCCCCCCCC=CCCCCCCCC(=O)OC[C@H](O)CO RZRNAYUHWVFMIP-HXUWFJFHSA-N 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 1
- WDRMFQRBFDVBPJ-UHFFFAOYSA-N hexadecyl 2-sulfanylacetate Chemical compound CCCCCCCCCCCCCCCCOC(=O)CS WDRMFQRBFDVBPJ-UHFFFAOYSA-N 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000007775 late Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical class [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229940071127 thioglycolate Drugs 0.000 description 1
- CWERGRDVMFNCDR-UHFFFAOYSA-M thioglycolate(1-) Chemical compound [O-]C(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-M 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
- 238000004383 yellowing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
- C07F7/226—Compounds with one or more Sn-S linkages
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Abstract The invention relates to mixtures of n-octyl tin compounds of the formulae (I) and (II) n-C8H17Sn(SCH2COOR)3 (I) (n-C8H17)2Sn(SCH2COOR)2 (II), wherein R is alkyl of 10 to 16 carbon atoms, and the molar ratio of (I) to (II) is 1 to 3. These mixtures can be used as stabilisers for PVC.
Description
Case 3-12623/CGM 2~5 Novel s~al~Llisers for PVC
The present invention relates to novel organo-tin stabilisers, to the production and use thereof, and to the PVC stabilised therewith.
Organo-tin compounds have long been employed as useful stabilisers for polyvinyl chloride (PVC)~ For example, British pa~ent specification 1 4~4 771 discloses n-oc~yl-tin-tris-(t~ra-decylthioglycolate) as stabiliser for PVC which, in accordance with Example 1, is prepared from 91% of octyl tin oxide and 9% of dioctyl tin oxide, and thus contains a small amount of the correspondîng dioctyl tin compound.
It has been found that these known stabilisers do not in all cases satisfy the requirements of practice. In addition to the respective organo-tin stabiliser, therefore, further stabilisers and/or auxiliaries are commonly used, whlch often have an adverse effect on each other. In particular, the very common concurrent use of lubricants is observed to have an adverse influence on the efectiveness of the known stabilisers for PVC. For example, the octyl tin stabiliser referred to above has a marked negative influence ~on account of the concurrently employed glycerol monooleate lubricant which is commerciallg available as Loxlol ~ G lo.
It is the object of the present invention to provide stabilisers for PVC which do not have these drawbacks, or have them only to an insignificant degree, and which, in particular, are much less impaired in their effectiveness bg concurrently employed lubricants.
E~ ~
L 1~44 Accordingly, ttle present invent:ion relates to mixtures o~ n-oc~yl ~in co~npo~ ds of the forrnulae (I) and (II) n-C8H17Sn(SCH2COOR)3 (I) (n-CgH17)2Sn(SCH2COOR)2 (II) , wherein R i5 alkyl of 10 to 16 carbon atomsS and the molar ratio of (I) to (II) is 1 to 3.
Alkyl radicals R are in particular straight-chain and preferably contain 12 and/or 14 carbon atoms, such that, in mixtures of C12 and C14, the final products (I) and (II~
preferably contain at least 60a/o mol.% of C14. Accordingly, R is most preferably n-C12H25, n-C14H29, and, in particular, mixtures thereof.
The molar ratio of (I) to (II) of 1 to 3 means that, preferably, compound (I) is present in greater amount, especially 55 to 76 mol.~tO, most preferably 60 to 75 mol.V/
as against 45 to 24 mol.% and 40 to 25 mol.% respectively of (II~.
The novel mixtures of compounds (I) and (II) of this invention are useful stabilisers for PVC compared with those of the prior art, especially in respect of dependence on lubricants. The stabilisers of the invention therefore do not have the drawbacks of the prior art, or have them only ~o a substantially lesser degree, which was not to be expected.
The novel mixtures can be obtained by methods which are known per se, especially in accordance with British paten~ specification 1 494 771 referred to at the outset, for example by reacting an alkyl ester of thioglycollic acid of the formula HSCH2COOR with a mixture of mo~ooctyl tin oxide or octyl stannonic acid and dioctyl tin oxide, in which mixture the molar amount o the ~onooctyl tin compound is 55 to 76 mol.%. The réac~ion can be carriad out T"ith or wlthout a solvent, by heating the components and removing the water of reaction.
A further method consists in reacting the above deined ester with a mixture of octyl tin trichloride and dioctyl tin dichloride, said mixture containing 55 to 76 mol.% of octyl tin trichloride, in the presence o a base. It is pre~erred to carry out the reaction in the presence of a water-immiscible organic solvent~ such as a hydrocarbon or a halogenated hydrocarbon, e.g. toluene. Examples of suitable bases are triethylamine, aqueous sodium hydroxide or aqueous sodium bicarbonate solution. ~he starting materials are known and commercially available.
The novel stabiliser mixtures can be added to chlorina~ed thermoplastics in the usual amounts, preerably 0.01 to 10% by weight, especially 0.1 to 5% by weight, and, most preferably, 0.2 to 2% by weight, based on the chlorinated thermoplastic.
Preferred chlorinated thermoplastics are vinyl chloride polymers or copolymers. Preferred polymers are suspension and mass polymers, and emulsion polymers which have been washed and therefore of low emulsi~ier content. Examples o~
suitable comonomers for the copolymers are: vinylidene chloride, trans-dichloroethane, e~hylene, p~opylene, butylene, maleic acid, acrylic acid, fumaric acid, and itaconic acld.
Further suitable polymers are post-chlorinated polyolefins.
The stabilised thermoplastics are obtained by known methods by incorporating the stabilisers and, i desired, further stabilisers, in the polymer. A homogeneous mixture of stabiliser and polyvinyl chloride can be obtained e g.
using a two-roll mixer in ~he temperature rcinge ~rom 150 to 210C. Depending on lhe end use o~ ~he moulding compourld, further additives can also be incorporated hefore or simultaneously with the incorporation of the stabiliser.
Examples of further additlves are: Iubricants, preferably montan waxes or glycerol esters, plasticisers, fillers, modifiers such as impact strength additives, pigments, light sta~ilisers, UV absorbers, antioxidants or further co-stabilisers, e.g. phosphites or epoxidised fatty acid esters.
In addition, the metal salts of barium, strontium, calcium zinc, cadmium, lead, tin and magnesiurn with phenols or carboxylic acids (fatty acids, epoxidised fatty acids) can be used concurrently. Mixtures of calcium and zinc carbox~lates, in which the carboxylate group can contain 8 to 20 carbon atoms, have proved particularly advantageous.
The thermoplastics can be processed to moulded articles by the conventional moulding methods, e.g. by extrusion, injection moulding or calendering.
The invention is illustrated by the ollowing non-limitative Examples.
Example 1: A mixture of 236.8 g (0.70 mole) of n-octyl tin trichloride, 124.8 g (0.30 mole) of di-n-octyl tin dichloride and 779.0 g (2.70 moles) of tetradecyl thioglycolate is dissolved in 500 ml of toluene. With efficient stirring, a solution of 108.0 g (2.70 moles) of sodium hydroxide in 300 ml of water is then added dropwise in the course oE 1 hour while keeping the temperature at 50C. Stirring is continued for 20 minutes when the addition is complete, Toluene together with residual water is distilled off from the organic phase. After filtration over a filter aid (Celite ~),the produc~ is obtained in the form of a light yellow liquid in a yield of 1032 g (99% of theory).
4 ~
Analysis: % Sn 'YOS
found: 11.3 8.2 calculated: 11.4 8.3 The product (stabiliser 1) is a mixture of 70 mol.~/~ of n-octyl-sn-(scH2coo-cl4H29)3 and 30 mol.% o (n-octyl)2-Sn-(SCH2C00-Cl4 H29)2 Fxample 2: a) Thioglycolate startin~ material The following components are dissolved in 800 ml of toluene:
285.5 g (3.1 moles) of freshly distilled thioglycollic acid with a SH value of 36.9%, 610.8 g (3.0 gram-equivalents) o a mixture of alcohols consisting of 64.o% by weight of tetra-decanol, 33.0% by weight of dodecanol, 1.5% by weight o decanol and 1.5% by weight of hexadecanol~ and 2 g o p-toluenesulfonic acid. The mixture is heated to reflux under argon and the water of reaction is removed with the aid of a separator. When the reaction is complete, the solution is cooled and washed once with 5% sodium bicarbonate solution and three times with distilled water. After distilling off the toluene, the reaction product is obtained in the form of a colourless liquid in a yield of 828 g (99.4% of theory).
The SH value is 11.8% by weight (calculated: 11.91% by weight). The product has the following composition:
60.8 mol.% of tetradecyl thioglycolate 36.1 mol.% of dodecyl thioglycolate l.9 mol.% of decyl thioglycolate and 1.2 mol.% of hexadecyl thioglycolate.
b) Mixture of octyl tin cornpounds A mixture of 165.6 g (0.647 mole) of monooctyl tin oxide and 127.5 g (0~353 mole) of dioctyl tin oxide (Sn content 40.5%) is reacted with 735.1 g (2.647 gram-equivalents) of the ester of Example 2 a). With stirring, the batch is heated 1 1 SjB4~8 for 1 hour at 13 mbar to 100C while removing water of reac~ion. Af~er flltration, ~he reaction product is obtained in the form of a llght yellow liquid in a yield o 994.5 g (99/0 of theory3.
Analysis: % Sn % S
found: 11.6 8.2 calculated: 11~81 8.45 The product (stabiliser 2) is a mixture of 64.7 mol.% of n-octyl-sn-(scH2coo-clo-l6H2l-33)3 (n oct~l)2-sn-sc~2coo-clo-l6H2l-33)2 Example 3: Test of heat stability A dry blend consisting of 100 parts of S-PVC (K-value 60), 0.2 part of montan wax, 1.0 part of an internal lubricant as indicated in the tables, and an organo-tin stabiliser in an amount of 1 part per 100 parts of PVC (see Table 1) and corresponding to an amount of 0.158 g of Sn per 100 parts of PVC (see Table 2), is rolled on a laboratory mixer roll at 200C (parts are by weight). The action is tested by taking samples of sheet at intervals of 3 minutes and determining the degree of yellowing by means of the Yellowness Index (YI) in accordance with the tes~ method of ASTM D 1925-70.
The results are reported in Tables 1 and 2.
~_ ~d co r~ It~
O ~ r l i_ __ X O U~) ~ CO
a~ ' r~ ~ ~O
- O Ei 0~ ~ u~
~: X ¢ ~ c~l n ~n ~ 4 4~ ~ a~--O r-l ~ ~ ~;t I~ rr~
R a a ~ ~ ~ s~ ~
0~, q~ '~ ~ $ .
_ ~ ____ _ P~
O
X ~ ~i' C) ~ O --~ C~l e ~ u~ ~ ,~ ~
~a c~
oo oo r_ o e a __ _ _ J- ~ U~ o~ u~
~ ~ E~ ~ ~ u~
a~ cq .__ ~ X o U~ ~_ ~ C~l_ CO ~ ~ ~
~ ~ ~ ~ ~ a~ ~
.,, .
~ P~ ~ ~
.~ O i3 o~ ~D ~o ~s~
~1 ,~ _ ,_ ~ a) u~ r~
O ~ ~ ~ :
c~ ~ . - o -I
8 ~ ~ ~ ~ ~
C~l ~ ~ ~ ~ ~
~ ~ .'' o ~3 ~
~ ~ ~ o o ~d ~ ~ . X ' P~ ~ ~o ~o, ~ o _ _ ,~
o (~) ~ ,~
.~ o o ~
.
C~ ~.
.~ ~ P~
~d .~ a~ ~
~ td ~ ~1 C~
.. E3 u h O
J h u~ O r~ ~
a~ O ~LI o~ r-l :
C~l aJ ~ ~ ~1 ~
r~l ~1 ~1 U ~ E~
,n t~ u~ u~ ~ ~a cd al ~ a) J- X
E~ ~: ~ u ~a ~, E~
The present invention relates to novel organo-tin stabilisers, to the production and use thereof, and to the PVC stabilised therewith.
Organo-tin compounds have long been employed as useful stabilisers for polyvinyl chloride (PVC)~ For example, British pa~ent specification 1 4~4 771 discloses n-oc~yl-tin-tris-(t~ra-decylthioglycolate) as stabiliser for PVC which, in accordance with Example 1, is prepared from 91% of octyl tin oxide and 9% of dioctyl tin oxide, and thus contains a small amount of the correspondîng dioctyl tin compound.
It has been found that these known stabilisers do not in all cases satisfy the requirements of practice. In addition to the respective organo-tin stabiliser, therefore, further stabilisers and/or auxiliaries are commonly used, whlch often have an adverse effect on each other. In particular, the very common concurrent use of lubricants is observed to have an adverse influence on the efectiveness of the known stabilisers for PVC. For example, the octyl tin stabiliser referred to above has a marked negative influence ~on account of the concurrently employed glycerol monooleate lubricant which is commerciallg available as Loxlol ~ G lo.
It is the object of the present invention to provide stabilisers for PVC which do not have these drawbacks, or have them only to an insignificant degree, and which, in particular, are much less impaired in their effectiveness bg concurrently employed lubricants.
E~ ~
L 1~44 Accordingly, ttle present invent:ion relates to mixtures o~ n-oc~yl ~in co~npo~ ds of the forrnulae (I) and (II) n-C8H17Sn(SCH2COOR)3 (I) (n-CgH17)2Sn(SCH2COOR)2 (II) , wherein R i5 alkyl of 10 to 16 carbon atomsS and the molar ratio of (I) to (II) is 1 to 3.
Alkyl radicals R are in particular straight-chain and preferably contain 12 and/or 14 carbon atoms, such that, in mixtures of C12 and C14, the final products (I) and (II~
preferably contain at least 60a/o mol.% of C14. Accordingly, R is most preferably n-C12H25, n-C14H29, and, in particular, mixtures thereof.
The molar ratio of (I) to (II) of 1 to 3 means that, preferably, compound (I) is present in greater amount, especially 55 to 76 mol.~tO, most preferably 60 to 75 mol.V/
as against 45 to 24 mol.% and 40 to 25 mol.% respectively of (II~.
The novel mixtures of compounds (I) and (II) of this invention are useful stabilisers for PVC compared with those of the prior art, especially in respect of dependence on lubricants. The stabilisers of the invention therefore do not have the drawbacks of the prior art, or have them only ~o a substantially lesser degree, which was not to be expected.
The novel mixtures can be obtained by methods which are known per se, especially in accordance with British paten~ specification 1 494 771 referred to at the outset, for example by reacting an alkyl ester of thioglycollic acid of the formula HSCH2COOR with a mixture of mo~ooctyl tin oxide or octyl stannonic acid and dioctyl tin oxide, in which mixture the molar amount o the ~onooctyl tin compound is 55 to 76 mol.%. The réac~ion can be carriad out T"ith or wlthout a solvent, by heating the components and removing the water of reaction.
A further method consists in reacting the above deined ester with a mixture of octyl tin trichloride and dioctyl tin dichloride, said mixture containing 55 to 76 mol.% of octyl tin trichloride, in the presence o a base. It is pre~erred to carry out the reaction in the presence of a water-immiscible organic solvent~ such as a hydrocarbon or a halogenated hydrocarbon, e.g. toluene. Examples of suitable bases are triethylamine, aqueous sodium hydroxide or aqueous sodium bicarbonate solution. ~he starting materials are known and commercially available.
The novel stabiliser mixtures can be added to chlorina~ed thermoplastics in the usual amounts, preerably 0.01 to 10% by weight, especially 0.1 to 5% by weight, and, most preferably, 0.2 to 2% by weight, based on the chlorinated thermoplastic.
Preferred chlorinated thermoplastics are vinyl chloride polymers or copolymers. Preferred polymers are suspension and mass polymers, and emulsion polymers which have been washed and therefore of low emulsi~ier content. Examples o~
suitable comonomers for the copolymers are: vinylidene chloride, trans-dichloroethane, e~hylene, p~opylene, butylene, maleic acid, acrylic acid, fumaric acid, and itaconic acld.
Further suitable polymers are post-chlorinated polyolefins.
The stabilised thermoplastics are obtained by known methods by incorporating the stabilisers and, i desired, further stabilisers, in the polymer. A homogeneous mixture of stabiliser and polyvinyl chloride can be obtained e g.
using a two-roll mixer in ~he temperature rcinge ~rom 150 to 210C. Depending on lhe end use o~ ~he moulding compourld, further additives can also be incorporated hefore or simultaneously with the incorporation of the stabiliser.
Examples of further additlves are: Iubricants, preferably montan waxes or glycerol esters, plasticisers, fillers, modifiers such as impact strength additives, pigments, light sta~ilisers, UV absorbers, antioxidants or further co-stabilisers, e.g. phosphites or epoxidised fatty acid esters.
In addition, the metal salts of barium, strontium, calcium zinc, cadmium, lead, tin and magnesiurn with phenols or carboxylic acids (fatty acids, epoxidised fatty acids) can be used concurrently. Mixtures of calcium and zinc carbox~lates, in which the carboxylate group can contain 8 to 20 carbon atoms, have proved particularly advantageous.
The thermoplastics can be processed to moulded articles by the conventional moulding methods, e.g. by extrusion, injection moulding or calendering.
The invention is illustrated by the ollowing non-limitative Examples.
Example 1: A mixture of 236.8 g (0.70 mole) of n-octyl tin trichloride, 124.8 g (0.30 mole) of di-n-octyl tin dichloride and 779.0 g (2.70 moles) of tetradecyl thioglycolate is dissolved in 500 ml of toluene. With efficient stirring, a solution of 108.0 g (2.70 moles) of sodium hydroxide in 300 ml of water is then added dropwise in the course oE 1 hour while keeping the temperature at 50C. Stirring is continued for 20 minutes when the addition is complete, Toluene together with residual water is distilled off from the organic phase. After filtration over a filter aid (Celite ~),the produc~ is obtained in the form of a light yellow liquid in a yield of 1032 g (99% of theory).
4 ~
Analysis: % Sn 'YOS
found: 11.3 8.2 calculated: 11.4 8.3 The product (stabiliser 1) is a mixture of 70 mol.~/~ of n-octyl-sn-(scH2coo-cl4H29)3 and 30 mol.% o (n-octyl)2-Sn-(SCH2C00-Cl4 H29)2 Fxample 2: a) Thioglycolate startin~ material The following components are dissolved in 800 ml of toluene:
285.5 g (3.1 moles) of freshly distilled thioglycollic acid with a SH value of 36.9%, 610.8 g (3.0 gram-equivalents) o a mixture of alcohols consisting of 64.o% by weight of tetra-decanol, 33.0% by weight of dodecanol, 1.5% by weight o decanol and 1.5% by weight of hexadecanol~ and 2 g o p-toluenesulfonic acid. The mixture is heated to reflux under argon and the water of reaction is removed with the aid of a separator. When the reaction is complete, the solution is cooled and washed once with 5% sodium bicarbonate solution and three times with distilled water. After distilling off the toluene, the reaction product is obtained in the form of a colourless liquid in a yield of 828 g (99.4% of theory).
The SH value is 11.8% by weight (calculated: 11.91% by weight). The product has the following composition:
60.8 mol.% of tetradecyl thioglycolate 36.1 mol.% of dodecyl thioglycolate l.9 mol.% of decyl thioglycolate and 1.2 mol.% of hexadecyl thioglycolate.
b) Mixture of octyl tin cornpounds A mixture of 165.6 g (0.647 mole) of monooctyl tin oxide and 127.5 g (0~353 mole) of dioctyl tin oxide (Sn content 40.5%) is reacted with 735.1 g (2.647 gram-equivalents) of the ester of Example 2 a). With stirring, the batch is heated 1 1 SjB4~8 for 1 hour at 13 mbar to 100C while removing water of reac~ion. Af~er flltration, ~he reaction product is obtained in the form of a llght yellow liquid in a yield o 994.5 g (99/0 of theory3.
Analysis: % Sn % S
found: 11.6 8.2 calculated: 11~81 8.45 The product (stabiliser 2) is a mixture of 64.7 mol.% of n-octyl-sn-(scH2coo-clo-l6H2l-33)3 (n oct~l)2-sn-sc~2coo-clo-l6H2l-33)2 Example 3: Test of heat stability A dry blend consisting of 100 parts of S-PVC (K-value 60), 0.2 part of montan wax, 1.0 part of an internal lubricant as indicated in the tables, and an organo-tin stabiliser in an amount of 1 part per 100 parts of PVC (see Table 1) and corresponding to an amount of 0.158 g of Sn per 100 parts of PVC (see Table 2), is rolled on a laboratory mixer roll at 200C (parts are by weight). The action is tested by taking samples of sheet at intervals of 3 minutes and determining the degree of yellowing by means of the Yellowness Index (YI) in accordance with the tes~ method of ASTM D 1925-70.
The results are reported in Tables 1 and 2.
~_ ~d co r~ It~
O ~ r l i_ __ X O U~) ~ CO
a~ ' r~ ~ ~O
- O Ei 0~ ~ u~
~: X ¢ ~ c~l n ~n ~ 4 4~ ~ a~--O r-l ~ ~ ~;t I~ rr~
R a a ~ ~ ~ s~ ~
0~, q~ '~ ~ $ .
_ ~ ____ _ P~
O
X ~ ~i' C) ~ O --~ C~l e ~ u~ ~ ,~ ~
~a c~
oo oo r_ o e a __ _ _ J- ~ U~ o~ u~
~ ~ E~ ~ ~ u~
a~ cq .__ ~ X o U~ ~_ ~ C~l_ CO ~ ~ ~
~ ~ ~ ~ ~ a~ ~
.,, .
~ P~ ~ ~
.~ O i3 o~ ~D ~o ~s~
~1 ,~ _ ,_ ~ a) u~ r~
O ~ ~ ~ :
c~ ~ . - o -I
8 ~ ~ ~ ~ ~
C~l ~ ~ ~ ~ ~
~ ~ .'' o ~3 ~
~ ~ ~ o o ~d ~ ~ . X ' P~ ~ ~o ~o, ~ o _ _ ,~
o (~) ~ ,~
.~ o o ~
.
C~ ~.
.~ ~ P~
~d .~ a~ ~
~ td ~ ~1 C~
.. E3 u h O
J h u~ O r~ ~
a~ O ~LI o~ r-l :
C~l aJ ~ ~ ~1 ~
r~l ~1 ~1 U ~ E~
,n t~ u~ u~ ~ ~a cd al ~ a) J- X
E~ ~: ~ u ~a ~, E~
Claims (6)
1. A mixture of n-octyl tin compounds of the formulae (I) and (II) n-C8H17Sn(SCH2COOR)3 (I) (n-C8H17)2Sn(SCH2COOR)2 (II) wherein R is alkyl of 10 to 16 carbon atoms and the molar ratio of (I) to (II) is 1 to 3.
2. A mixture according to claim 1, wherein R is n-C12H25, n-C14H29 or a mixture thereof.
3. A mixture according to claim 1, wherein R contains at least 60 mol.% of n-C14H29.
4. A mixture according to claim 1, which contains 60-75 mol.% of compound (I) and 40-25 mol.% of compound (II).
5. A stabilised halogen-containing thermoplastic which contains a mixture according to claim 1.
6. A process for obtaining a mixture according to claim 1, which process comprises reacting an alkyl ester of thio-glycollic acid of the formula HSCH2COOR with a mixture of monooctyl tin oxide or octyl stannonic acid and dioctyl tin oxide, said mixture containing 55-76 mol.% of the monooctyl tin compound, or reacting an alkyl ester of thioglycollic acid of the formula HSCH2COOR with a mixture of octyl tin trichloride and dioctyl tin dichloride, said mixture containing 55-76 mol.% of octyl tin trichloride, in the presence of a base.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1087079 | 1979-12-07 | ||
| CH10870/79-4 | 1979-12-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1156448A true CA1156448A (en) | 1983-11-08 |
Family
ID=4367703
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000366277A Expired CA1156448A (en) | 1979-12-07 | 1980-12-05 | Stabilisers for pvc |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0032106B1 (en) |
| JP (1) | JPS5692942A (en) |
| BR (1) | BR8007964A (en) |
| CA (1) | CA1156448A (en) |
| DE (1) | DE3063632D1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5002702A (en) * | 1987-07-10 | 1991-03-26 | Sandoz Ltd. | Stabilizer compositions comprising a thiophosphate and an organo tin compound |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4988750A (en) * | 1981-07-17 | 1991-01-29 | Schering Ag | Non-toxic stabilizer for halogenated polymer |
| NL8202252A (en) * | 1981-07-17 | 1983-02-16 | Schering Ag | NON-TOXIC STABILIZER MIXTURE FOR HALOGEN-CONTAINING POLYMERS. |
| EP0081458B1 (en) * | 1981-12-04 | 1986-05-07 | Ciba-Geigy Ag | Continuous process for preparing alkyl tin thiocarboxylic acid esters |
| JPS58154747A (en) * | 1982-03-09 | 1983-09-14 | Nitto Kasei Kk | Chlorine-containing resin composition |
| DE3370806D1 (en) * | 1982-12-10 | 1987-05-14 | Hoechst Co American | Radiation-resistant vinyl chloride resin compositions |
| GB2139625B (en) * | 1983-05-03 | 1987-05-13 | Ciba Geigy Ag | Novel organo-tin pvc stabilisers |
| FR2599373B1 (en) * | 1986-05-30 | 1989-06-16 | Ciba Geigy Ag | POLY- (VINYL CHLORIDE) COMPOSITIONS STABILIZED BY LAURYLSTANNIC COMPOUNDS, APPLICATION OF THESE COMPOSITIONS AND METHOD FOR STABILIZING MOLDING MATERIALS |
| EP0433473A1 (en) * | 1989-12-18 | 1991-06-26 | Chemische Werke München Otto Bärlocher GmbH | Method for the direct synthesis of organotin compounds and their use |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2171963A1 (en) * | 1972-02-17 | 1973-09-28 | Synthetic Products Co | Organotin mercapto acid esters prepn - in continuous heat exchange zone |
| GB1346999A (en) * | 1970-10-02 | 1974-02-13 | Interstab Ltd | Stabilisers for vinyl chloride resins |
| GB1510974A (en) * | 1975-05-19 | 1978-05-17 | M & T Chemicals Inc | Stabilized vinyl chloride resins |
-
1980
- 1980-12-01 DE DE8080810371T patent/DE3063632D1/en not_active Expired
- 1980-12-01 EP EP80810371A patent/EP0032106B1/en not_active Expired
- 1980-12-05 CA CA000366277A patent/CA1156448A/en not_active Expired
- 1980-12-05 BR BR8007964A patent/BR8007964A/en unknown
- 1980-12-08 JP JP17305880A patent/JPS5692942A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5002702A (en) * | 1987-07-10 | 1991-03-26 | Sandoz Ltd. | Stabilizer compositions comprising a thiophosphate and an organo tin compound |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3063632D1 (en) | 1983-07-07 |
| BR8007964A (en) | 1981-06-23 |
| JPS6364466B2 (en) | 1988-12-12 |
| EP0032106A2 (en) | 1981-07-15 |
| EP0032106B1 (en) | 1983-06-01 |
| EP0032106A3 (en) | 1981-08-05 |
| JPS5692942A (en) | 1981-07-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US2832751A (en) | Polyvinyl chloride stabilized with butyl tin s, s', s" tris | |
| CA1114597A (en) | Stabilizer systems and vinyl halide resin compositions containing same | |
| CA1156448A (en) | Stabilisers for pvc | |
| US5109046A (en) | Liquid organotinthioalkanol stabilizer compositions and vinyl halide resin compositions containing the same | |
| US3095427A (en) | Hydrocarbyltin salts of epoxyalkylsubstituted succinic acids | |
| US4396552A (en) | Novel metal mercaptides of esters of β-mercaptoalkanols | |
| EP0048841A1 (en) | Stabilizer for synthetic resins | |
| US4743640A (en) | Alpha, beta-unsaturated carbonyl-containing carbonate stabilizers for chlorinated polymers | |
| US3534121A (en) | Organotin composition and resins stabilized therewith | |
| US4021407A (en) | Synergistic organotin borate stabilizer compositions and resins containing same | |
| US3293273A (en) | Organotin mercapto ethylene carboxylates and method for producing same | |
| US2700656A (en) | Plasticized polyvinyl chloride compositions | |
| US4111903A (en) | Organotin compounds and vinyl halide resin compositions stabilized therewith | |
| US3227677A (en) | Polyolefins containing bis(hydrocarbyloxycarbonylalkylthioalkyl) phenols as stabilizers | |
| US3933740A (en) | Halogen containing polymeric resins having improved heat and light stability | |
| EP0623649B1 (en) | Polyol esters of zinc mercaptoacids as heat stabilizers for PVC processing | |
| EP0049166B1 (en) | Hydrolytically stable diphosphites useful as antioxidants | |
| US3232905A (en) | Vinyl halide resins stabilized with hydrocarbyl tin epoxy-alkyl succinates | |
| US3546162A (en) | Ortho-ester stabilized polyvinylchloride resins | |
| US4125500A (en) | Cyclic phosphites of sugar alcohols and polymers stabilized therewith | |
| US4374945A (en) | Thioglycolate and thiopropionate secondary stabilizers | |
| US4146530A (en) | Dicyclophosphites and organic polymers stabilized with said phosphites and their use as stabilizers | |
| US4546136A (en) | Organotin-containing composition for the stabilization of polymers of vinyl chloride | |
| US3138570A (en) | Vinyl resin solutions stabilized by a polymeric organophosphorus compound | |
| US3833519A (en) | Stabilizers for vinyl chloride-containing resins |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |