EP0365577A1 - Verfahren zur stabilisierung von mischungen auf basis von halogenhaltigen polymeren - Google Patents
Verfahren zur stabilisierung von mischungen auf basis von halogenhaltigen polymerenInfo
- Publication number
- EP0365577A1 EP0365577A1 EP19880905881 EP88905881A EP0365577A1 EP 0365577 A1 EP0365577 A1 EP 0365577A1 EP 19880905881 EP19880905881 EP 19880905881 EP 88905881 A EP88905881 A EP 88905881A EP 0365577 A1 EP0365577 A1 EP 0365577A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- mixtures
- halogen
- functions
- halides
- minutes
- 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.)
- Pending
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 12
- 239000000203 mixture Substances 0.000 title claims description 31
- 238000000034 method Methods 0.000 title claims description 18
- 230000008569 process Effects 0.000 title claims description 8
- 230000000087 stabilizing effect Effects 0.000 title description 4
- -1 Thiol compounds Chemical class 0.000 claims abstract description 32
- 150000004820 halides Chemical class 0.000 claims abstract description 8
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 11
- 150000002367 halogens Chemical class 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 9
- 229910001507 metal halide Inorganic materials 0.000 claims description 9
- 150000005309 metal halides Chemical class 0.000 claims description 9
- 239000003017 thermal stabilizer Substances 0.000 claims description 8
- 150000002894 organic compounds Chemical class 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims description 4
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 4
- 229920005862 polyol Polymers 0.000 claims description 4
- 150000003077 polyols Chemical class 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 230000032050 esterification Effects 0.000 claims description 3
- 238000005886 esterification reaction Methods 0.000 claims description 3
- 239000000314 lubricant Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- FPBWSPZHCJXUBL-UHFFFAOYSA-N 1-chloro-1-fluoroethene Chemical group FC(Cl)=C FPBWSPZHCJXUBL-UHFFFAOYSA-N 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 230000000703 anti-shock Effects 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000000975 dye Substances 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 claims description 2
- 239000000806 elastomer Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 150000004676 glycans Chemical class 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 150000002772 monosaccharides Chemical class 0.000 claims description 2
- 239000004014 plasticizer Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 229920001282 polysaccharide Polymers 0.000 claims description 2
- 239000005017 polysaccharide Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 2
- 150000001733 carboxylic acid esters Chemical class 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 claims 1
- 239000008187 granular material Substances 0.000 claims 1
- 150000002366 halogen compounds Chemical class 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 229910052748 manganese Inorganic materials 0.000 claims 1
- 150000007522 mineralic acids Chemical class 0.000 claims 1
- 239000006072 paste Substances 0.000 claims 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims 1
- 239000000843 powder Substances 0.000 claims 1
- 238000007792 addition Methods 0.000 description 8
- 239000003381 stabilizer Substances 0.000 description 8
- 230000009466 transformation Effects 0.000 description 7
- 238000002156 mixing Methods 0.000 description 5
- 230000009467 reduction Effects 0.000 description 4
- 235000012424 soybean oil Nutrition 0.000 description 4
- 239000003549 soybean oil Substances 0.000 description 4
- 230000006641 stabilisation Effects 0.000 description 4
- 238000011105 stabilization Methods 0.000 description 4
- INTLMJZQCBRQAT-UHFFFAOYSA-K trichloro(octyl)stannane Chemical compound CCCCCCCC[Sn](Cl)(Cl)Cl INTLMJZQCBRQAT-UHFFFAOYSA-K 0.000 description 4
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 3
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 3
- 239000012768 molten material Substances 0.000 description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 3
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 3
- 239000002671 adjuvant Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000006077 pvc stabilizer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 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
- HLRRSFOQAFMOTJ-UHFFFAOYSA-L 6-methylheptyl 2-[[2-(6-methylheptoxy)-2-oxoethyl]sulfanyl-dioctylstannyl]sulfanylacetate Chemical compound CC(C)CCCCCOC(=O)CS[Sn](CCCCCCCC)(CCCCCCCC)SCC(=O)OCCCCCC(C)C HLRRSFOQAFMOTJ-UHFFFAOYSA-L 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920012485 Plasticized Polyvinyl chloride Polymers 0.000 description 1
- 206010047289 Ventricular extrasystoles Diseases 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 1
- 229960005215 dichloroacetic acid Drugs 0.000 description 1
- SBOSGIJGEHWBKV-UHFFFAOYSA-L dioctyltin(2+);dichloride Chemical compound CCCCCCCC[Sn](Cl)(Cl)CCCCCCCC SBOSGIJGEHWBKV-UHFFFAOYSA-L 0.000 description 1
- NJDNXYGOVLYJHP-UHFFFAOYSA-L disodium;2-(3-oxido-6-oxoxanthen-9-yl)benzoate Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=CC(=O)C=C2OC2=CC([O-])=CC=C21 NJDNXYGOVLYJHP-UHFFFAOYSA-L 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZMHZSHHZIKJFIR-UHFFFAOYSA-N octyltin Chemical compound CCCCCCCC[Sn] ZMHZSHHZIKJFIR-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
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
-
- 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
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
-
- 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
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
-
- 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
Definitions
- the present invention relates to a process for stabilizing blends based on halogenated polymers or copolymers during their transformation, as well as the stabilization systems provided for this purpose.
- the method of the invention involves compositions stabili ⁇ cient for the protection of polymers and copolymers of halogen-containing and, in particular, polymers and copolymers of vinyl chloride (PVC), against the adverse effects of es heat, during their passage through processing machines such as calenders, extruders, kneaders, injection and coating machines and gelification tunnels. This process ensures the desired initial color and maintains color stability and thermal stability for sufficiently long periods of time.
- PVC vinyl chloride
- thermal stabilizers chemical compounds, commonly called thermal stabilizers, whose role is fourfold: a) to ensure at the start the desired color or the absence of coloring, b) maintaining the initial color of the molten material, without annoying change, for a sufficient duration; c) prevent thermal degradation of the molten material for a sufficiently long period and, d) in the case of finished products which must be transparent, not to compromise the intrinsic transparency of the polymer.
- the temperature of the melt is, in the case of PVC, between 160 ° C and 230 ° C, depending on different factors: nature of PVC (plasticized 'or rigid), K-value of PVC and finally the shear speed which the molten material undergoes in the machine.
- the temperature is, for plasticized PVC, between 160 ° C and 190 ° C and for rigid PVC, between 200 ° C and 230 ° C.
- the duration of the color stability and that of the thermal stability are, for a given mixture, inversely proportional to the temperature of the melt. Each time the temperature increases by 10 ° C, these times decrease by about half. This means, for example, that a system of thermal stabilizers which is satisfactory for the transformation of a mixture of PVC plasticized at 180 ° C, may be totally unsuitable for the transformation of rigid PVC at 220 ° C.
- organotin oxides or with organo-antimony oxides (DE-C-1 217609).
- R methyl, butyl or octyl.
- this type of stabilizer is the only one to satisfy, in the best condition of simplicity, the quadruple role mentioned above, in the case of transformation of rigid PVC at temperatures ranging from 200 ° C to 230 ° C .
- These stabilizers are used, almost exclusively, for the transformation of PVC into transparent rigid sheets and films, into hollow bodies - except bottles for mineral water, for organo-leptic reasons - and into rigid tubes in the United States and Japan and partly also in Europe, replacing lead stabilizers.
- the main disadvantages of these stabilizers are the complexity of their manufacture, the high rate of tin, from 1 to 20% and the high price.
- the object of the present invention is to provide thermal stabilizer compositions capable of fulfilling the performance of stabilizers of the thio-organotin type in the transformation of rigid PVCs while having significant advantages: simplicity of manufacture, reduction of the quantity of metal to around 1% and very significant reduction in the cost of stabilization.
- the inventor has surprisingly discovered that the addition, to a mixture of rigid PVC containing one or more -SH functions (thiol compound), of a very small amount of a metallic or organometallic halide had the effect of 'remarkably improve the initial color, to extend both the duration of color stability and the duration of thermal stability.
- metal halides - without organic radicals - added in very small quantities to PVC mixtures containing thiol compound produce effects similar to the additions of organometallic halide; however, the intensity of these effects depends on the level of acidity of the metal halide.
- the process for stabilizing halo-vinyl resins according to the invention is characterized in that it consists in adding, to the polymer to be protected, a system consisting of at least one organic compound containing one or more -SH- functions and a very small amount of at least one halide chosen from metallic and organometallic halides.
- halogenated resins to which the invention applies are the homopolymers and / or copolymers of vinyl chloride, of vinylidene chloride, of chlorofluoroethylene with the following comonomers: vinyl acetate, acrylonitrile, maleic anhydride, ethylene, propylene and other monomer copolymerizable with vinyl halides, as well as halogenated polyolefins and other halogenated polymers and elastomers, natural or synthetic.
- the thiol compounds used in the process according to the invention have the following general formula:
- - R is the remainder of a monohydroxyl alcohol of any chemical nature such as: aliphatic, olefinic, cyclic, heterocyclic, aromatic, or the rest . of a monomeric polyol such as: glycerol, glycoi, pentaerythritis, sorbitol, pentites, hexites, monosaccharides, or the rest of a polymeric polyol such as polyethylene glycol, polypropylene glycol, polyvinyl alcohol, cellulose, starch and other polysaccharides , R being able to carry various functions such as etheroxide, -carboxylic ester -thiocarbonic, -sulfonic or / and ester of other anorganic acids.
- a monomeric polyol such as: glycerol, glycoi, pentaerythritis, sorbitol, pentites, hexites, monosaccharides, or the rest of a polymeric polyol such as polyethylene
- - R '-SH is the remainder of a monoacid or of a polycarboxylic acid, containing one or more -SH functions, linked to R by esterification, such as, for example, -thioglycolic acid, -mercaptopropionic acid, -mercaptosuccinique, -dimercaptosuccinique, -thiosalicyiique.
- - x is the number of -SH linked to R '.
- the added amount of organic compound containing one or more -SH function (s) is between 0.1 and 5 parts by weight per 100 parts by weight of resin and preferably between 0.3 and 1.5 parts by weight per 100 parts by weight of resin.
- organometallic halides used in the process according to the invention have the following general formula:
- R is an aliphatic, cyclic, heterocyclic, aromatic organic residue, containing or not containing radicals and / or simple or mixed functions.
- - n is the number of R linked to the metal Me.
- - Me Sn, Al, B, Sb, Fe, Cd, Zn, Ti, Hg, Bi, Mn or Ga.
- - Me is a metal of which the halogen salt gives, in aqueous solution of approximately 35 meq. of halogen per liter of distilled water at around 23 ° C, a pH equal to or less than 5, preferably a pH equal to or less than 3.
- - v is the valence of Me.
- - Hal chlorine, bromine, iodine, fluorine.
- the term mixture corresponds to the material intended for processing, obtained by homogenization of several components and the basic component of which is one or more polymers or / and halogenated copolymers and comprising, in addition to the adjuvants I, II or / and III described above, one or more other components such as: anti-shock additives, processing aids, known PVC stabilizers, plasticizers, fillers, dyes, anti-static agents and any usual adjuvant.
- PVC mixtures the components of which are specified in each example, are prepared in a rapid laboratory mixer.
- the quantities of the components are indicated in part by weight per 100 parts by weight of PVC (pcr).
- the quantities of organo-metallic halide and metal halide are, in addition, indicated in brackets by the content in halogen, expressed in milliequivents of halogen per kg of PVC.
- Test method for determining the initial color, color stability and thermal stability.
- a 60 gram portion of the mixture is subjected to kneading on a laboratory cylinder mixer, the cylinders of which are heated to 210 ° C. by circulation of oil.
- the diameter of the two cylinders is 250 mm.
- the distance between the cylinders is kept constant during the test at 0.6 mm.
- the respective rotational speed of the cylinders is 18 rpm and 20 rpm.
- a sample of a small rectangle is taken every minute of mixing.
- the samples are fixed successively on a cardboard display.
- the initial color is assessed visually on the sample at two minutes. Color stability is determined by the duration of mixing leading to a noticeable change in the original color.
- the thermal stability is determined by the mixing time leading to the color changing to dark brown or dark red.
- the thiol compound, pentaerythritis tetra-mercaptoacetate is prepared in the laboratory by esterification of one mole of pentaerythritis containing approximately 4% of -OH functions, with four moles of mercaptoacetic acid, of iodometric purity of 99.96.
- the acid is first introduced into the reactor with 2% water and 0.25% para-toluene sulfonic acid. At 80 ° C, pentaerythritis is added; then the temperature is maintained at 145 ° C until the release of water stops. ' 0.25% of lime carbonate is then introduced and hot filtration is carried out.
- organotin chloride there is a limit on the rate of addition of organotin chloride, after which a reduction in color and thermal stability occurs.
- the metal halide is introduced into the mixture in the form of a very dilute aqueous solution by dissolving, in 250 cc of distilled water, 0.77 grams of SnCl. 5H 2 0 or one gram of chemically pure CdCl-2,5H_O.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Saccharide Compounds (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Polyesters Or Polycarbonates (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8709279A FR2617175B1 (fr) | 1987-06-26 | 1987-06-26 | Procede de stabilisation des resines halogeno-vinyliques lors de leur transformation |
| FR8709279 | 1987-06-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0365577A1 true EP0365577A1 (de) | 1990-05-02 |
Family
ID=9352725
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP19880905881 Pending EP0365577A1 (de) | 1987-06-26 | 1988-06-22 | Verfahren zur stabilisierung von mischungen auf basis von halogenhaltigen polymeren |
| EP88420212A Expired - Lifetime EP0299882B1 (de) | 1987-06-26 | 1988-06-22 | Verfahren zur Stabilisierung von Mischungen auf der Basis von halogenhaltigen Polymeren |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP88420212A Expired - Lifetime EP0299882B1 (de) | 1987-06-26 | 1988-06-22 | Verfahren zur Stabilisierung von Mischungen auf der Basis von halogenhaltigen Polymeren |
Country Status (17)
| Country | Link |
|---|---|
| US (1) | US5166241A (de) |
| EP (2) | EP0365577A1 (de) |
| JP (1) | JPH02504038A (de) |
| KR (1) | KR890701674A (de) |
| CN (1) | CN1043723A (de) |
| AT (1) | ATE87952T1 (de) |
| AU (1) | AU625411B2 (de) |
| BR (1) | BR8807588A (de) |
| CA (1) | CA1335012C (de) |
| DE (1) | DE3880033T2 (de) |
| ES (1) | ES2040885T3 (de) |
| FR (1) | FR2617175B1 (de) |
| HU (1) | HU205962B (de) |
| IL (1) | IL88604A (de) |
| RO (1) | RO105578B1 (de) |
| WO (1) | WO1988010282A1 (de) |
| ZA (1) | ZA889283B (de) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6790892B1 (en) * | 1995-05-10 | 2004-09-14 | Rohm And Haas Company | Latent mercaptans as multi-functional additives for halogen-containing polymer compositions |
| US20020103277A1 (en) * | 1995-05-10 | 2002-08-01 | Tod C. Duvall | Synergistic blend of a metal-based stabilizer or lewis acid and a free mercaptan for enhanced pvc stabilization |
| AU682287B2 (en) * | 1995-05-10 | 1997-09-25 | Morton International, Inc. | Latent mercaptans as multi-functional additives for halogen-containing polymer compositions |
| US7105109B2 (en) * | 1995-05-10 | 2006-09-12 | Rohm And Haas Company | Latent mercaptans as stabilizers for halogen-containing polymer compositions |
| CA2280441A1 (en) * | 1998-09-16 | 2000-03-16 | Morton International, Inc. | Combination of an organothio compound and a zinc mercapto ester as heat stabilizer in pvc processing |
| EP1201706A1 (de) * | 2000-10-24 | 2002-05-02 | Rohm And Haas Company | Halogen enthaltende Polymerzusammensetzung stabilisiert durch ein latentes Mercaptan und durch eine Mischung aus Zinkcarboxylat und Zinkchlorid |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2563772A (en) * | 1949-03-22 | 1951-08-07 | Shell Dev | High molecular weight halogen-containing organic materials stabilized with iron salts |
| US3063963A (en) * | 1958-10-13 | 1962-11-13 | Eastman Kodak Co | Stabilized polymers of vinylidene chloride or vinyl chloride containing a sulfur compound and a tin compound |
| US3715333A (en) * | 1969-11-13 | 1973-02-06 | M & T Chemicals Inc | Polyvinylchloride stabilization with mixtures of tin salts |
| SU519446A1 (ru) * | 1974-02-04 | 1976-06-30 | Институт химии АН СССР | Стабилизирующа смесь |
| US4021407A (en) * | 1976-06-28 | 1977-05-03 | Cincinnati Milacron, Inc. | Synergistic organotin borate stabilizer compositions and resins containing same |
| US4159261A (en) * | 1977-01-26 | 1979-06-26 | Dart Industries Inc. | Stabilization of vinyl halide resins |
| FR2434835A1 (fr) * | 1978-08-29 | 1980-03-28 | Elf Aquitaine | Perfectionnement a la stabilisation de resines halogeno-vinyliques |
| JPS55160044A (en) * | 1979-05-31 | 1980-12-12 | Adeka Argus Chem Co Ltd | Stabilized halogen-containing resin composition |
| JPS562336A (en) * | 1979-06-22 | 1981-01-12 | Adeka Argus Chem Co Ltd | Stabilized halogen-containing resin composition |
| FR2491871A1 (fr) * | 1980-10-10 | 1982-04-16 | Ato Chimie | Perfectionnement a la sterilisation d'objets en polymeres halogeno-vinyliques par des rayonnements ionisants, et resines pour sa realisation |
| US4360619A (en) * | 1981-02-26 | 1982-11-23 | Carstab Corporation | Stabilizer compositions and polymers containing same |
| US4665114A (en) * | 1982-02-04 | 1987-05-12 | Morton Thiokol Inc. | Stabilizer compositions and polymers containing same |
-
1987
- 1987-06-26 FR FR8709279A patent/FR2617175B1/fr not_active Expired
-
1988
- 1988-06-22 JP JP63505520A patent/JPH02504038A/ja active Pending
- 1988-06-22 RO RO143511A patent/RO105578B1/ro unknown
- 1988-06-22 AU AU19668/88A patent/AU625411B2/en not_active Ceased
- 1988-06-22 WO PCT/FR1988/000332 patent/WO1988010282A1/fr not_active Ceased
- 1988-06-22 EP EP19880905881 patent/EP0365577A1/de active Pending
- 1988-06-22 KR KR1019890700355A patent/KR890701674A/ko not_active Ceased
- 1988-06-22 HU HU884233A patent/HU205962B/hu not_active IP Right Cessation
- 1988-06-22 AT AT88420212T patent/ATE87952T1/de not_active IP Right Cessation
- 1988-06-22 CA CA000570128A patent/CA1335012C/fr not_active Expired - Fee Related
- 1988-06-22 ES ES198888420212T patent/ES2040885T3/es not_active Expired - Lifetime
- 1988-06-22 BR BR888807588A patent/BR8807588A/pt not_active Application Discontinuation
- 1988-06-22 EP EP88420212A patent/EP0299882B1/de not_active Expired - Lifetime
- 1988-06-22 US US07/457,768 patent/US5166241A/en not_active Expired - Fee Related
- 1988-06-22 DE DE88420212T patent/DE3880033T2/de not_active Expired - Fee Related
- 1988-12-06 IL IL88604A patent/IL88604A/xx not_active IP Right Cessation
- 1988-12-12 ZA ZA889283A patent/ZA889283B/xx unknown
- 1988-12-27 CN CN88105832A patent/CN1043723A/zh active Pending
Non-Patent Citations (1)
| Title |
|---|
| See references of WO8810282A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2040885T3 (es) | 1993-11-01 |
| EP0299882A1 (de) | 1989-01-18 |
| KR890701674A (ko) | 1989-12-21 |
| US5166241A (en) | 1992-11-24 |
| DE3880033T2 (de) | 1994-01-27 |
| BR8807588A (pt) | 1990-05-29 |
| AU625411B2 (en) | 1992-07-09 |
| HU205962B (en) | 1992-07-28 |
| ZA889283B (en) | 1989-12-27 |
| CN1043723A (zh) | 1990-07-11 |
| FR2617175A1 (fr) | 1988-12-30 |
| HUT51311A (en) | 1990-04-28 |
| JPH02504038A (ja) | 1990-11-22 |
| FR2617175B1 (fr) | 1989-10-27 |
| ATE87952T1 (de) | 1993-04-15 |
| RO105578B1 (ro) | 1992-09-25 |
| CA1335012C (fr) | 1995-03-28 |
| AU1966888A (en) | 1989-01-19 |
| DE3880033D1 (de) | 1993-05-13 |
| WO1988010282A1 (fr) | 1988-12-29 |
| EP0299882B1 (de) | 1993-04-07 |
| IL88604A (en) | 1992-09-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5106898A (en) | Stabilizer composition for use in halogen-containing resins | |
| CA2065566C (fr) | Compositions de polymere halogene stabilisees a l'aide d'un additif mineral | |
| FR2458567A1 (fr) | Composition de faible toxicite pour la stabilisation thermique des resines organiques et resine de chlorure de polyvinyle en comportant application | |
| FR2458568A1 (fr) | Composition a base d'un sel metallique d'acide gras superieur, d'un alcool polyhydroxylique et d'un compose de magnesium, destinee a stabiliser une resine d'halogenure de vinyle et resine stabilisee avec cette composition | |
| EP0365577A1 (de) | Verfahren zur stabilisierung von mischungen auf basis von halogenhaltigen polymeren | |
| FR2645163A1 (fr) | Procede de stabilisation des polymeres halogenes | |
| NO833488L (no) | Stabilisering av polymerer ved bruk av citratsalter | |
| JP3224753B2 (ja) | Ｐｖｃ加工用熱安定剤／潤滑剤およびその製造法 | |
| US11692091B2 (en) | Resin composition for injection molding | |
| US5929152A (en) | Compositions containing vinylidene fluoride polymers which are stabilized to heat | |
| FR2657356A1 (fr) | Lubrifiants pour compositions thermoplastiques, compositions en comportant, procede de preparation et procede de fabrication de bouteilles. | |
| EP0596020A1 (de) | Stabilisator-zusammensetzung und damit stabilisierte polymerzusammensetzungen | |
| FR2619386A1 (fr) | Composition de resine thermoplastique a teneur en halogene | |
| EP0024754B1 (de) | Gegen Wärme stabilisierte, PVC enthaltende Zusammensetzungen | |
| US6825256B2 (en) | Stability improvement of carbon monoxide ethylene copolymer in pvc compound | |
| CA1090931A (fr) | Compositions plastifiees et stabilisees a base de poly (chlorure de vinyle) | |
| JP3556070B2 (ja) | 食品包装フィルム用塩化ビニル系樹脂組成物 | |
| AU605104B2 (en) | Clear polyvinyl chloride articles and compositions | |
| RU2076119C1 (ru) | Полимерная композиция | |
| EP0003156A1 (de) | Gegen Hitze stabilisierte Polyvinylchloridzusammensetzungen, die einen partiellen Ester von Pentaerythritol enthalten | |
| Wegmann et al. | New additive solutions for the PVC industry | |
| JPH08188678A (ja) | 崩壊性ポリオレフィン組成物 | |
| FR2811324A1 (fr) | Stabilisation de polymeres halogenes au moyen de pyrroles ou derives et compositions les comprenant | |
| JPH07107115B2 (ja) | プロピレン系重合体の加工性改良方法 | |
| JPS60184536A (ja) | 塩素化ポリエチレンの安定化方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
| 17P | Request for examination filed |
Effective date: 19891204 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH DE FR GB IT LI NL SE |
|
| RAP3 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: KORNBAUM, SIMON |
|
| XX | Miscellaneous (additional remarks) |
Free format text: VERFAHREN ABGESCHLOSSEN INFOLGE VERBINDUNG MIT 88420212.8/0299882 (EUROPAEISCHE ANMELDENUMMER/VEROEFFENTLICHUNGSNUMMER) VOM 06.08.91. |