WO2011054536A1 - Stabilizer compositions having low zinc content for window profiles - Google Patents
Stabilizer compositions having low zinc content for window profiles Download PDFInfo
- Publication number
- WO2011054536A1 WO2011054536A1 PCT/EP2010/006775 EP2010006775W WO2011054536A1 WO 2011054536 A1 WO2011054536 A1 WO 2011054536A1 EP 2010006775 W EP2010006775 W EP 2010006775W WO 2011054536 A1 WO2011054536 A1 WO 2011054536A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- halogen
- stabilizer composition
- polymers according
- containing polymers
- stabilizer
- Prior art date
Links
- 239000003381 stabilizer Substances 0.000 title claims abstract description 80
- 239000000203 mixture Substances 0.000 title claims abstract description 62
- 239000011701 zinc Substances 0.000 title claims abstract description 28
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 24
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229920000642 polymer Polymers 0.000 claims abstract description 50
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 44
- 150000002367 halogens Chemical class 0.000 claims abstract description 44
- 229920005989 resin Polymers 0.000 claims abstract description 6
- 239000011347 resin Substances 0.000 claims abstract description 6
- -1 perchlorate compound Chemical class 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000000314 lubricant Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 229920005862 polyol Polymers 0.000 claims description 5
- 150000003077 polyols Chemical class 0.000 claims description 5
- 239000004593 Epoxy Substances 0.000 claims description 4
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- 239000000344 soap Substances 0.000 claims description 4
- 239000004604 Blowing Agent Substances 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 239000004014 plasticizer Substances 0.000 claims description 2
- ISAKRJDGNUQOIC-UHFFFAOYSA-N Uracil Chemical compound O=C1C=CNC(=O)N1 ISAKRJDGNUQOIC-UHFFFAOYSA-N 0.000 claims 2
- 150000002736 metal compounds Chemical class 0.000 claims 2
- YNGDWRXWKFWCJY-UHFFFAOYSA-N 1,4-Dihydropyridine Chemical compound C1C=CNC=C1 YNGDWRXWKFWCJY-UHFFFAOYSA-N 0.000 claims 1
- 229920000877 Melamine resin Polymers 0.000 claims 1
- 239000012963 UV stabilizer Substances 0.000 claims 1
- 150000001413 amino acids Chemical class 0.000 claims 1
- 230000003078 antioxidant effect Effects 0.000 claims 1
- 239000008187 granular material Substances 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims 1
- 239000000155 melt Substances 0.000 claims 1
- 229910000000 metal hydroxide Inorganic materials 0.000 claims 1
- 150000004692 metal hydroxides Chemical class 0.000 claims 1
- 229910044991 metal oxide Inorganic materials 0.000 claims 1
- 150000004706 metal oxides Chemical class 0.000 claims 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims 1
- 229940035893 uracil Drugs 0.000 claims 1
- 239000004800 polyvinyl chloride Substances 0.000 description 22
- 229920000915 polyvinyl chloride Polymers 0.000 description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- 239000011575 calcium Substances 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 229910052791 calcium Inorganic materials 0.000 description 6
- 150000001735 carboxylic acids Chemical class 0.000 description 6
- 239000010457 zeolite Substances 0.000 description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 5
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 230000006641 stabilisation Effects 0.000 description 5
- 238000011105 stabilization Methods 0.000 description 5
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 159000000003 magnesium salts Chemical class 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 4
- 235000010215 titanium dioxide Nutrition 0.000 description 4
- 239000001993 wax Substances 0.000 description 4
- 150000003751 zinc Chemical class 0.000 description 4
- 0 *N(C(N(*)C(N1*)=O)=O)C1=O Chemical compound *N(C(N(*)C(N1*)=O)=O)C1=O 0.000 description 3
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000004609 Impact Modifier Substances 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 159000000007 calcium salts Chemical class 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 3
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 3
- 229960002920 sorbitol Drugs 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 2
- SERLAGPUMNYUCK-DCUALPFSSA-N 1-O-alpha-D-glucopyranosyl-D-mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO[C@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O SERLAGPUMNYUCK-DCUALPFSSA-N 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- OYIFNHCXNCRBQI-UHFFFAOYSA-N 2-aminoadipic acid Chemical compound OC(=O)C(N)CCCC(O)=O OYIFNHCXNCRBQI-UHFFFAOYSA-N 0.000 description 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N 4-nonylphenol Chemical compound CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 2
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 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 description 2
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 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 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229930195725 Mannitol Natural products 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000003862 amino acid derivatives Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzene-1,2,3-tricarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 229960002246 beta-d-glucopyranose Drugs 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- NZZIMKJIVMHWJC-UHFFFAOYSA-N dibenzoylmethane Chemical compound C=1C=CC=CC=1C(=O)CC(=O)C1=CC=CC=C1 NZZIMKJIVMHWJC-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 125000004925 dihydropyridyl group Chemical group N1(CC=CC=C1)* 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229960001031 glucose Drugs 0.000 description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 2
- MNUOZFHYBCRUOD-UHFFFAOYSA-N hydroxyphthalic acid Natural products OC(=O)C1=CC=CC(O)=C1C(O)=O MNUOZFHYBCRUOD-UHFFFAOYSA-N 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 235000010439 isomalt Nutrition 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000594 mannitol Substances 0.000 description 2
- 235000010355 mannitol Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920002959 polymer blend Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 229960004889 salicylic acid Drugs 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- 235000010356 sorbitol Nutrition 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 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
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 150000003752 zinc compounds Chemical class 0.000 description 2
- HDTRYLNUVZCQOY-UHFFFAOYSA-N α-D-glucopyranosyl-α-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OC1C(O)C(O)C(O)C(CO)O1 HDTRYLNUVZCQOY-UHFFFAOYSA-N 0.000 description 1
- VCWMRQDBPZKXKG-ZNVDUFQESA-N (1s,2r,4s,5s)-6-[(2r,3r,4s,5r,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxycyclohexane-1,2,3,4,5-pentol Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@@H]1OC1[C@@H](O)[C@H](O)C(O)[C@H](O)[C@@H]1O VCWMRQDBPZKXKG-ZNVDUFQESA-N 0.000 description 1
- QBYIENPQHBMVBV-HFEGYEGKSA-N (2R)-2-hydroxy-2-phenylacetic acid Chemical compound O[C@@H](C(O)=O)c1ccccc1.O[C@@H](C(O)=O)c1ccccc1 QBYIENPQHBMVBV-HFEGYEGKSA-N 0.000 description 1
- HIWPGCMGAMJNRG-NCFXGAEVSA-N (2s,3r,4s,5s,6r)-6-(hydroxymethyl)-3-[(2s,3r,4s,5s,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxyoxane-2,4,5-triol Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 HIWPGCMGAMJNRG-NCFXGAEVSA-N 0.000 description 1
- PFCRQPBOOFTZGQ-RGXJTGTOSA-N (3s,4r,5r)-1,3,5,6-tetrahydroxy-4-[(2r,3r,4s,5s,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxyhexan-2-one Chemical compound OCC(=O)[C@@H](O)[C@@H]([C@H](O)CO)O[C@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O PFCRQPBOOFTZGQ-RGXJTGTOSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- PAWSVPVNIXFKOS-IHWYPQMZSA-N (Z)-2-aminobutenoic acid Chemical compound C\C=C(/N)C(O)=O PAWSVPVNIXFKOS-IHWYPQMZSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- JKODVQHJSDDYJO-UHFFFAOYSA-N 1-(4-acetylphenyl)-18-methoxyoctadecan-1-one Chemical compound COCCCCCCCCCCCCCCCCCC(=O)C1=CC=C(C(C)=O)C=C1 JKODVQHJSDDYJO-UHFFFAOYSA-N 0.000 description 1
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 1
- LRQGFQDEQPZDQC-UHFFFAOYSA-N 1-Phenyl-1,3-eicosanedione Chemical compound CCCCCCCCCCCCCCCCCC(=O)CC(=O)C1=CC=CC=C1 LRQGFQDEQPZDQC-UHFFFAOYSA-N 0.000 description 1
- BKUAQOCVPRDREL-UHFFFAOYSA-N 1-Phenyl-1,3-octadecanedione Chemical compound CCCCCCCCCCCCCCCC(=O)CC(=O)C1=CC=CC=C1 BKUAQOCVPRDREL-UHFFFAOYSA-N 0.000 description 1
- PYPCDBLMVZWDGV-UHFFFAOYSA-N 1-phenyl-1,3-hexadecanedione Chemical compound CCCCCCCCCCCCCC(=O)CC(=O)C1=CC=CC=C1 PYPCDBLMVZWDGV-UHFFFAOYSA-N 0.000 description 1
- CVBUKMMMRLOKQR-UHFFFAOYSA-N 1-phenylbutane-1,3-dione Chemical compound CC(=O)CC(=O)C1=CC=CC=C1 CVBUKMMMRLOKQR-UHFFFAOYSA-N 0.000 description 1
- VGYZKPWMARHMDW-UHFFFAOYSA-N 1-phenyltetradecane-1,3-dione Chemical compound CCCCCCCCCCCC(=O)CC(=O)C1=CC=CC=C1 VGYZKPWMARHMDW-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 1
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- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- NMRPBPVERJPACX-UHFFFAOYSA-N octan-3-ol Chemical compound CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-M oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC([O-])=O ZQPPMHVWECSIRJ-KTKRTIGZSA-M 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002895 organic esters Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-N palmitic acid group Chemical group C(CCCCCCCCCCCCCCC)(=O)O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- VCAFTIGPOYBOIC-UHFFFAOYSA-N phenyl dihydrogen phosphite Chemical class OP(O)OC1=CC=CC=C1 VCAFTIGPOYBOIC-UHFFFAOYSA-N 0.000 description 1
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical class OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 150000004291 polyenes Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 239000011591 potassium Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 239000006077 pvc stabilizer Substances 0.000 description 1
- 229940079889 pyrrolidonecarboxylic acid Drugs 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- OVVGHDNPYGTYIT-BNXXONSGSA-N rutinose Chemical compound O[C@@H]1[C@H](O)[C@@H](O)[C@H](C)O[C@H]1OC[C@@H]1[C@@H](O)[C@H](O)[C@@H](O)[C@H](O)O1 OVVGHDNPYGTYIT-BNXXONSGSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- PZDOWFGHCNHPQD-VNNZMYODSA-N sophorose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](C=O)O[C@@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O PZDOWFGHCNHPQD-VNNZMYODSA-N 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical class C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- CNUJLMSKURPSHE-UHFFFAOYSA-N trioctadecyl phosphite Chemical compound CCCCCCCCCCCCCCCCCCOP(OCCCCCCCCCCCCCCCCCC)OCCCCCCCCCCCCCCCCCC CNUJLMSKURPSHE-UHFFFAOYSA-N 0.000 description 1
- MGMXGCZJYUCMGY-UHFFFAOYSA-N tris(4-nonylphenyl) phosphite Chemical compound C1=CC(CCCCCCCCC)=CC=C1OP(OC=1C=CC(CCCCCCCCC)=CC=1)OC1=CC=C(CCCCCCCCC)C=C1 MGMXGCZJYUCMGY-UHFFFAOYSA-N 0.000 description 1
- DECPGQLXYYCNEZ-UHFFFAOYSA-N tris(6-methylheptyl) phosphite Chemical compound CC(C)CCCCCOP(OCCCCCC(C)C)OCCCCCC(C)C DECPGQLXYYCNEZ-UHFFFAOYSA-N 0.000 description 1
- 150000004043 trisaccharides Chemical class 0.000 description 1
- RULSWEULPANCDV-PIXUTMIVSA-N turanose Chemical compound OC[C@@H](O)[C@@H](O)[C@@H](C(=O)CO)O[C@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O RULSWEULPANCDV-PIXUTMIVSA-N 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 229940098697 zinc laurate Drugs 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- JDLYKQWJXAQNNS-UHFFFAOYSA-L zinc;dibenzoate Chemical compound [Zn+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 JDLYKQWJXAQNNS-UHFFFAOYSA-L 0.000 description 1
- GPYYEEJOMCKTPR-UHFFFAOYSA-L zinc;dodecanoate Chemical compound [Zn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O GPYYEEJOMCKTPR-UHFFFAOYSA-L 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
- C08K5/0091—Complexes with metal-heteroatom-bonds
-
- 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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
Definitions
- the invention relates to a low-zinc composition for the stabilization of halogen-containing polymers, in particular polyvinyl chloride (PVC) .
- PVC polyvinyl chloride
- Halogen-containing polymers or plastics or molded articles produced therefrom tend to undergo substantial changes during their production process and due to the effect of environmental influences. For example, these types of plastics may decompose or discolor under the influence of heat and / or light. To stabilize halogen-containing polymers, therefore, a very wide variety of substances or mixtures have already been used.
- a halogen-containing polymer e.g. Polyvinyl chloride (PVC)
- PVC Polyvinyl chloride
- metal carboxylates as stabilizers in the resin.
- melt-molding process causes blackening of the polymer, it is common practice to add a co-stabilizer.
- a co-stabilizer There are a variety of combinations of inorganic and organic compounds known as stabilizers for halogen-containing polymers.
- the calcium salt causes a fundamental stabilization of the halogen-containing polymer by the binding of the liberated hydrochloric acid as calcium chloride.
- the calcium salt is occasionally combined with a magnesium salt to the above base """or replaced by a magnesium salt.
- the calcium or magnesium salt may be used in combination with zinc salts based on o.o. organic acids are used.
- the zinc salts having the formula 1 depicted above give the halogen-containing polymer a good color because they can substitute the labile chlorine atoms on the halogen-containing polymer (PVC).
- Zinc chloride is formed during this reaction. This chloride is known to the chemist as Lewis acids. It is capable of binding more than two chloride ions as shown in Formula 2. As a result, the chloride catalyzes the decomposition of the halogen-containing polymer and reduces the stability.
- comparable zinc contents for stabilizer combinations for PVC profiles can be found at a comparable amount as shown in Tab. 1.
- Zinc contents ⁇ 2.0% can be found only at a significantly higher input quantity, which has significant cost disadvantages for the user.
- Such stabilizer combinations make it possible to produce plastic profiles with good thermal and light stability " in combination with a good initial color.”
- the light and weathering stability is attributed, among other things, to the presence of zinc compounds by the person skilled in the art, but zinc as well as lead, tin and sulfur become an element considered unsustainable in the literature (C. Azar, J. Holmberg, K.
- a PVC stabilizer composition has advantageous properties, particularly when using the composition for the plastic profiles, when the Zn content is limited within a very narrow range. Therefore, there is a need to provide stabilizer combinations that have the better properties than the usual stabilizer compositions.
- Tab. 1 shows an overview of zinc contents of (window) profile stabilizer combinations in the Patent literature (patent number, example, amount of stabilizer combination used in phr, zinc content in%, application)
- Patent no. Example use amount% Zn application
- the present invention is therefore based on the object of providing new low-zinc stabilizer compositions at a use amount ⁇ 4.5 phr, which are particularly suitable for PVC profiles, without having the above-mentioned disadvantages of the known stabilizers.
- This object is achieved by providing a stabilizer composition with Zinc contents of 0.5 to 1.5% at a use rate ⁇ 4.5 phr for PVC profiles.
- the initial color and the color retention of the halogen-containing material can be significantly improved compared to other organic and inorganic costabilizers when used in applications that are used outdoors, for example in profiles.
- the stabilizer compositions according to the invention moldings of halogen-containing polymers can easily be produced which enable optimum performance in use and which are comparable to PVC stabilization commodities based on stabilizer compositions for PVC profiles. This stabilizing effect also occurs when the PVC contains further stabilizers, co-stabilizers or adjuvants.
- the present invention also relates to the use of the invention
- Stabilizer composition for the stabilization of PVC profiles, as well as the PVC profiles, the one
- the low-zinc stabilizer composition of the present invention can be used for halogen-containing polymers.
- halogen-containing polymers may be thermoplastic halogen-containing polymers, for example, but not limited to, polyvinyl chloride (PVC), polyvinylidene chloride, chlorinated or chlorosulfonated polyethylene, chlorinated
- Polypropylene or chlorinated ethylene / vinyl acetate copolymer or similar compounds are particularly advantageous.
- Particularly advantageous are polymers of the PVC type, i. Vinyl chloride homopolymers and copolymers of vinyl chloride with other monomers.
- the stabilizer compositions for halogen-containing polymers according to the present invention contain at least one zinc compound.
- Stabilizer composition according to the present invention may be added in total in an amount of about 1 to 4.5 parts per 100 parts of resin (phr).
- Stabilizer composition in an amount of about 2.0 to 4.3 phr added, for example in an amount of about 2.5 to about 3.8.
- the stabilizer composition used according to the invention can be added individually to the polymer or to the polymer mixture. However, it is also possible to add the combination according to the invention together with other (co) stabilizers or the auxiliaries listed below to the polymer or a polymer mixture.
- a dosage in the extruder for example in the Vacuum zone, also encompassed by the present invention.
- the stabilizer composition according to the invention may further comprise one or more additional additives, such as, for example, primary stabilizers, co-stabilizers, zeolites, antioxidants, fillers, plasticizers,
- additional additives such as, for example, primary stabilizers, co-stabilizers, zeolites, antioxidants, fillers, plasticizers,
- Stabilizers can be combined.
- Co-stabilizers are compounds which provide a further stabilizing contribution to halogen-containing polymers when used in the stabilizer composition according to the present invention.
- Possible co-stabilizers may be selected from the group consisting of 1,3-diketone compounds, dihydropyridines, polyols,
- Isocyanurates metal salts, natural or synthetic minerals such as hydrotalcites, hydrocalumites, zeolites, amino acid derivatives, organic esters of phosphorous acid, epoxy compounds, perchlorates and salts of superacids.
- 1,3-diketone compounds include, but are not limited to, dibenzoylmethane,
- Co-stabilizers from the group of polyols include, but are not limited to, glycerol, pentaerythritol, di- and tripentaerythritol, trismethylolpropane (TMP), di-TMP, sorbitol, mannitol, malititol, saccharides, disaccharides (especially sucrose, 4-O ⁇ -D-galactopyranosyl-D-glucose, 4-O-alpha-D-glucopyranosyl-D-glucose, 6-O- (6-deoxy-alpha-L-mannopyranosyl) -D-glucose, alpha-D-glucopyranosyl alpha-D-glucopyranoside, 6-0-alpha-D-glucopyranosyl-D-glucose, 4-O-beta-D-glucopyranosyl-D-glucose, 2-O-beta-D-glu
- Galactopyranosyl-D-glucitol 4-O-alpha-D-glucopyranosyl-D-glucitol, 6-O-alpha-D-galactopyranosyl-D-glucose, 3-O-alpha-D-galactopyranosyl-D-myo-inositol, 4-O- ⁇ -D-galactopyranosyl-D-fructose, 4-O- ⁇ -D-galactopyranosyl- ⁇ -D-glucopyranose, 6-O-alpha-D-glucopyranosyl-D-fructose, 4-O- ⁇ - D-galactopyranosyl-alpha-D-glucopyranose, 2-0- (6-deoxy-alpha-L-mannopyranosyl) -D-glucose, 4-O-alpha-D-glucopyranosyl-D-fructose, 2-O-ß- D-glucopy
- Glucopyranosyl-D-fructose 6-O-alpha-D-glucopyranosyl-alpha-D-fructofuranose, 6-O-alpha-D-glucopyranosyl-D-glucitol, 4-O-beta-D-galactopyranosyl-D-glucitol, 4-0-alpha-D- Glucopyranosyl-D-glucitol, 1-O-alpha-D-glucopyranosyl-D-mannitol), trisaccharides, polysaccharides, especially polyvinyl alcohols, starch, cellulose and theirs
- antioxidants include, but are not limited to, alkylphenols, hydroxyphenylpropionates, hydroxybenzyl compounds, alkylidenebisphenols, thiobisphenols, and aminophenols, especially, for example, 2,6-di-tert.
- co-stabilizers from the group of metal salts include, but are not limited to, hydroxides, oxides, carbonates, basic carbonates, and carboxylic acid salts of lithium, sodium, potassium, magnesium, calcium, aluminum, titanium, and the like.
- the metal salts may be used salts of carboxylic acids.
- Carboxylic acids are carboxylic acids which have 2-22, in particular 7-22 carbon atoms and can be aliphatic or aromatic, saturated or unsaturated, branched or unbranched.
- carboxylic anions include anions of mono and divalent carboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, enanthic acid, octanoic acid, neodecanoic acid, 2-ethylhexanoic acid,
- Sorbic acid anions of divalent carboxylic acids or their monoesters such as oxalic acid, malonic acid, maleic acid, fumaric acid, adipic acid, tartaric acid, cinnamic acid, mandelic acid, malic acid, glycolic acid, salicylic acid,
- Polyglykoldicarbon Acid having a degree of polymerization of about 10 to about 12, phthalic acid, isophthalic acid, terephthalic acid or hydroxyphthalic acid, anions of trioder tetravalent carboxylic acids or
- natural and synthetic minerals include, but are not limited to, A3, A4, A5 zeolites, mordenite zeolites, erionite, faujasite X. or Y-type and ZSM-5 zeolites, hydrotalcites (Alcamizer 1 and 4 type) and / or mixtures thereof.
- co-stabilizers from the group of amino acid derivatives include, but are not limited to, glycine, alanine, lysine, tryptophan,
- the alcohol components of these esters may include monohydric alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, i-propyl alcohol, butyl alcohol, ⁇ -ethylhexanol, octyl alcohol, i-octyl alcohol, lauryl alcohol, stearyl alcohol, and the like, as well as polyols such as ethylene glycol, Propylene glycol, 1, 3-butanediol, 1, 4-butanediol, glycerol, diglycerol, trismethylolpropane, pentaerythritol,
- co-stabilizers from the group of phosphorous acid esters include, but are not limited to, triaryl phosphites, such as
- Triphenyl phosphite tris (p-nonylphenyl) phosphite
- Alkylaryl phosphites such as
- Monoalkyldiphenylphosphites eg diphenylisooctylphosphite, diphenylisodecylphosphite; and dialkyl monophenyl phosphites such as phenyl diisooctyl phosphite, phenyl diisodecyl phosphite; and trialkyl phosphites such as triisooctyl phosphite, tristearyl phosphite and the like.
- co-stabilizers from the group of epoxy compounds include, but are not limited to, various animal or vegetable oils, such as epoxysoar oil, epoxy rapeseed oil, epoxidized carboxylic acid esters, such as epoxidized epoxy methyl oleate, epoxybutyl oleate, epoxidized alicyclic compounds, glycidyl ethers, such as For example, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether; Glycidic esters, such as glycidyl acrylate, glycidyl methacrylate, their polymers, copolymers; and epoxidized polymers such as epoxidized polybutadiene, epoxidized ABS, and the like.
- various animal or vegetable oils such as epoxysoar oil, epoxy rapeseed oil, epoxidized carboxylic acid esters, such as epoxidized epoxy methyl oleate, epoxybutyl oleate
- Exemplary isocyanurates include, but are not limited to,
- dihydropyridines include, but are not limited to,
- Exemplary perchlorates include, but are not limited to, NaC104, Ca (C104) 2, g (C104) 2, or A1 (C104) 3. Further exemplary compounds of this group are Alcamizer 5 and Alcamizer 5-2 from Kyowa.
- chalk or coated chalk may also be named as fillers, the fillers being not restricted thereto.
- Stabilizer composition of the invention can be added is titanium dioxide. Titanium dioxide occurs essentially in nature in three modifications: anatase, brookite, and rutile.
- a stabilizer composition of the invention may further include lubricants such as montan wax, fatty acid esters, purified or hydrogenated natural or synthetic triglycerides or partial esters, polyethylene waxes, amide waxes, chloroparaffins, glycerol esters or
- lubricants Contain alkaline earth soap.
- Useful lubricants are moreover also described in "Plastics Additives Handbook", H. Zweifel / RD Maier / M. Schiller, Carl Hanser Verlag, 6th edition, 2009, pp. 539-579.
- lubricants are, for example, fatty ketones as described in DE 4204887 and silicone-based lubricants, as mentioned for example in EP-A 0 259 783, or combinations thereof, as mentioned in EP-A 0 259 783.
- the documents cited are hereby incorporated by reference, the disclosure of which relates to lubricants being considered part of the disclosure of the present text.
- the stabilizer composition according to the invention has at least the following component:
- Zinc, calcium and / or magnesium salts of at least one C7-C22 carboxylic acid which may be aliphatic or aromatic, saturated or unsaturated, branched or unbranched, such as. of technical stearic, lauric, C8-10 carboxylic and / or benzoic acid,
- Zn-content of such a composition is between 0.5 to 1.5 wt.% With a starting amount of 1 to 4.5 phr.
- the stabilizer composition preferably contains an isocyanurate compound.
- the stabilizer composition according to the invention is preferably solid and preferably contains no solvent.
- Stabilizer composition to process the methods known in the art can be used. Examples of such methods include, but are not limited to, extruding and the like.
- the present invention accordingly provides a remarkable and novel contribution to the development of the prior art, in particular for the processing and stabilization of PVC profiles and other halogen-containing thermoplastic polymers, preferably rigid PVC.
- Paraffin wax (1 10 ° C) 0.20 0.20 0.20 0.20 oxidized PE wax 0.10 0.10 0.10 0.10 0.10
- Zinc benzoate (21.3% Zn) 0.20 0.10
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- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to stabilizer compositions for halogen-containing polymers having a zinc content ranging from approximately 0.5 to approximately 1.5% zinc (based on the total quantity of the stabilizer composition) at an input quantity of the stabilizer ranging from approximately 1 to 4.5 per 100 parts of resin.
Description
STABILISATORZUSAMMENSETZUNGEN MIT NIEDRIGEN ZINKGEHALT FÜR FENSTERPROFILE STABILIZER COMPOSITIONS WITH LOW ZINC CONTENT FOR WINDOW PROFILES
Die Erfindung betrifft eine zinkarme Zusammensetzung zur Stabilisierung von halogenhaltigen Polymere, insbesondere Polyvinylchlorid ( PVC) . - Profilanwendungen, die die besagte SatbilisatorZusammensetzung beinhalten . The invention relates to a low-zinc composition for the stabilization of halogen-containing polymers, in particular polyvinyl chloride (PVC) . Profile applications involving said satellizer composition.
Halogenhaltige Polymere bzw. Kunststoffe oder daraus hergestellte Formkörper neigen zu substantiellen Veränderungen während ihres Herstellungsverfahrens und aufgrund der Einwirkung von Umwelteinflüssen. Zum Beispiel kann sich diese Art von Kunststoffen unter Einfluss von Wärme und/oder Licht zersetzen oder verfärben. Zur Stabilisierung von halogenhaltigen Polymeren sind daher bereits verschiedenste Stoffe oder Stoffgemische verwendet worden . Halogen-containing polymers or plastics or molded articles produced therefrom tend to undergo substantial changes during their production process and due to the effect of environmental influences. For example, these types of plastics may decompose or discolor under the influence of heat and / or light. To stabilize halogen-containing polymers, therefore, a very wide variety of substances or mixtures have already been used.
Ein halogenhaltiges Polymer, wie z.B. Polyvinylchlorid (PVC) , geht beim Schmelzverformen in eine Polyenstruktur über, wobei Salzsäure eliminiert und das Polymer verfärbt wird. Um die Thermostabilität des Polymers zu verbessern, ist es üblich, Metallcarboxylate als Stabilisatoren in das Harz einzuarbeiten. Da jedoch die Einarbeitung der Stabilisatoren allein bei einem längerenA halogen-containing polymer, e.g. Polyvinyl chloride (PVC), when melt-formed, transforms into a polyene structure, eliminating hydrochloric acid and discoloring the polymer. In order to improve the thermostability of the polymer, it is common to incorporate metal carboxylates as stabilizers in the resin. However, since the incorporation of the stabilizers alone in a longer
Schmelzformverfahren eine Schwärzung des Polymeren hervorruft, ist es allgemeine Praxis, einen Co-Stabilisator zuzusetzen. Es sind eine Vielzahl von Kombinationen aus anorganischen und organischen Verbindungen als Stabilisatoren für halogenhaltige Polymere bekannt. Melt-molding process causes blackening of the polymer, it is common practice to add a co-stabilizer. There are a variety of combinations of inorganic and organic compounds known as stabilizers for halogen-containing polymers.
Die Basis bildet in fast allen Fällen das Calciumsalz einer organischen Säure (z.B. technische Stearinsäure, The basis in almost all cases is the calcium salt of an organic acid (e.g., technical stearic acid,
BESTÄTIGUNGSKOPIE
Laurinsäure, 2-Ethylhexansäure, Octansäure oderCONFIRMATION COPY Lauric acid, 2-ethylhexanoic acid, octanoic acid or
Benzoesäure) . Das Calciumsalz bewirkt eine grundlegende Stabilisierung des halogenhaltigen Polymers durch die Bindung der freiwerdenden Salzsäure als Calciumchlorid. Das Calciumsalz wird gelegentlich auch mit einem Magnesiumsalz auf o.g. Basis kombiniert" ""oder durch ein Magnesiumsalz ersetzt . Benzoic acid). The calcium salt causes a fundamental stabilization of the halogen-containing polymer by the binding of the liberated hydrochloric acid as calcium chloride. The calcium salt is occasionally combined with a magnesium salt to the above base """or replaced by a magnesium salt.
Das Calcium- bzw. Magnesiumsalz kann aber in Kombination mit Zinksalzen basierend auf o.g. organischen Säuren eingesetzt werden. Einerseits geben die Zinksalze mit der anstehenden abgebildeten Formel 1 dem halogenhaltigen Polymer eine gute Farbe, weil sie die labilen Chloratome am halogenhaltigen Polymer (PVC) substituieren können. Es entsteht während dieser Reaktion Zinkchlorid. Dieses Chlorid ist dem Chemiker als Lewis-Säuren bekannt. Es ist in der Lage, mehr als zwei Chloridionen zu binden wie in der Formel 2 dargestellt. Dadurch katalysiert das Chlorid die Zersetzung des halogenhaltigen Polymers und verringert die Stabilität. However, the calcium or magnesium salt may be used in combination with zinc salts based on o.o. organic acids are used. On the one hand, the zinc salts having the formula 1 depicted above give the halogen-containing polymer a good color because they can substitute the labile chlorine atoms on the halogen-containing polymer (PVC). Zinc chloride is formed during this reaction. This chloride is known to the chemist as Lewis acids. It is capable of binding more than two chloride ions as shown in Formula 2. As a result, the chloride catalyzes the decomposition of the halogen-containing polymer and reduces the stability.
Formel 2: Formula 2:
ZnCl2 + 2 HCl -» H2[ZnCl4]
Eine weitere Reaktion der Erdalkaliseifen besteht in der Verdrängung der Fettsäure durch Salzsäure aus dem Salz wie in der Formel 3 dargestellt. ZnCl 2 + 2 HCl - »H 2 [ZnCl 4 ] Another reaction of the alkaline earth metal soaps is the displacement of the fatty acid by hydrochloric acid from the salt as shown in Formula 3.
Formel 3: Formula 3:
O O ZnCI2 + Ca(O^R)2 * Zn(O^R)2 + CaCI2 OOZ nCl 2 + Ca (O-R) 2 * Zn (O-R) 2 + CaCl 2
Mit verschiedenen Verhältnissen von Erdalkali- zu Zinksalzen lassen sich prinzipiell alle Stabilitäten und Anfangsfarben einstellen. Überwiegt die Erdalkaliseife, so erreicht man gute Stabilitäten bei eher bescheidener Anfangsfarbe. Überwiegen Zinksalze, umso besser ist die Farbe bei wahrscheinlich akzeptabler Stabilität. Aus der Bildung des Zinkchlorids gemäß Formel 1 bzw. Formel 2, die Zersetzung des halogenhaltigen Polymers fördert, ergibt sich die Notwendigkeit Costabilisatoren einzusetzen. Diese Costabilisatoren binden entweder Salzsäure, oder sie komplexieren die Lewissäuren sprich das Zinkchlorid in diesem Falle. Typische Costabilisatoren sind Hydrotalcite, Zeolithe, Metall (hydr) oxide, Polyole, ß-Diketone, organische Phosphite, Antioxidantien, Epoxide, Perchlorate etc . With different ratios of alkaline earth to zinc salts, all stabilities and initial colors can be adjusted in principle. If the alkaline-earth soap dominates, good stabilities can be achieved with a rather modest initial color. If zinc salts predominate, the color is better, with probably acceptable stability. From the formation of the zinc chloride according to formula 1 or formula 2, which promotes decomposition of the halogen-containing polymer, there is the need to use costabilizers. These costabilizers either bind hydrochloric acid or they complex the Lewis acids ie the zinc chloride in this case. Typical costabilizers are hydrotalcites, zeolites, metal (hydr) oxides, polyols, β-diketones, organic phosphites, antioxidants, epoxides, perchlorates, etc.
Kommerziell verfügbare Fensterprofilstabilisatoren enthalten zwischen 2.0 und 6.0% Zink bei einer Einsatzmenge des Stabilisators von ca. 3.5 bis 4.5 pro 100 Teile Harz (phr = per hundred resin) . In der Patentliteratur sind vergleichbare Zinkgehalte für Stabilisatorkombinationen für PVC-Profile bei vergleichbarer Einsatzmenge zu finden wie
in der Tab. 1 dargestellt. Nur bei deutlich höherer Einsatzmenge sind Zinkgehalte <2.0% zu finden, die die deutlichen Kostennachteile für den Anwender aufweisen. Derartige Stabilisatorkombinationen ermöglichen die Herstellung von Kunststoffprofilen mit guter Thermo- und Lichtstabilität " in Kombination mit einer guten Anfangsfarbe. Die gute Licht- und Bewitterungsstabilität wird vom Fachmann u.a. auf die Gegenwart von Zinkverbindungen zurückgeführt. Allerdings wird Zink ebenso wie Blei, Zinn und Schwefel als Element in der Literatur als nicht nachhaltig betrachtet (C. Azar, J. Holmberg, K. Lindgren; "Socio-ecological indicators for sustainability" Ecological Economics 18 (1996) 89; K.E. Lunde, J. Leadbitter, M. Schiller; "Sustainability assessment of stabiliser Systems for use in PVC pipes", PVC '05, Brighton, U.K., 2005; Mark Everard; "PVC: Reaching for Sustainability" IOM3 and The Natural Step, 2008) . Commercially available window profile stabilizers contain between 2.0 and 6.0% zinc at a stabilizer use level of about 3.5 to 4.5 per 100 parts resin (phr = per hundred resin). In the patent literature comparable zinc contents for stabilizer combinations for PVC profiles can be found at a comparable amount as shown in Tab. 1. Zinc contents <2.0% can be found only at a significantly higher input quantity, which has significant cost disadvantages for the user. Such stabilizer combinations make it possible to produce plastic profiles with good thermal and light stability " in combination with a good initial color." The light and weathering stability is attributed, among other things, to the presence of zinc compounds by the person skilled in the art, but zinc as well as lead, tin and sulfur become an element considered unsustainable in the literature (C. Azar, J. Holmberg, K. Lindgren, "Socio-ecological indicators for sustainability" Ecological Economics 18 (1996) 89; KE Lunde, J. Leadbitter, M. Schiller; "Sustainability assessment of stable systems for use in PVC pipes ", PVC '05, Brighton, UK, 2005; Mark Everard;" PVC: Reaching for Sustainability "IOM3 and The Natural Step, 2008).
Es würde überraschenderweise festgestellt, dass eine PVC- Stabilisatorzusammensetzung vorteilhafte Eigenschaften aufweist, insbesondere bei der Verwendung der Zusammensetzung für die Kunststoffprofile, wenn der Zn- Gehalt in einem ganz engen Bereich begrenzt ist. Deshalb besteht die Notwendigkeit Stabilisatorkombinationen bereitzustellen, die die besseren Eigenschaften als die üblichen Stabilisatorzusammensetzungen aufweisen. It would surprisingly be found that a PVC stabilizer composition has advantageous properties, particularly when using the composition for the plastic profiles, when the Zn content is limited within a very narrow range. Therefore, there is a need to provide stabilizer combinations that have the better properties than the usual stabilizer compositions.
Diese Aufgabe wurde durch die Merkmale der Zusammensetzung gemäß Anspruch 1 gelöst. This object has been achieved by the features of the composition according to claim 1.
Tab. 1 zeigt Übersicht über Zinkgehalte von (Fenster) Profilstabilisatorkombinationen in der
Patentliteratur (Patentnummer, Beispiel, Einsatzmenge der Stabilisatorkombination in phr, Zinkgehalt in %, Anwendung) Tab. 1 shows an overview of zinc contents of (window) profile stabilizer combinations in the Patent literature (patent number, example, amount of stabilizer combination used in phr, zinc content in%, application)
Patentnr . Beispiel Einsatzmenge %Zn Anwendung Patent no. Example use amount% Zn application
EP1692220 1 4.40 2.48 FensterprofilEP1692220 1 4.40 2.48 Window profile
EP1692220 6 4.19 2.61 FensterprofilEP1692220 6 4.19 2.61 Window profile
EP1692220 12 3.92 2.79 FensterprofilEP1692220 12 3.92 2.79 Window profile
EP1692220 13 3.55 3.08 FensterprofilEP1692220 13 3.55 3.08 Window profile
EP1641872 B3 4.35 1.96 FensterprofilEP1641872 B3 4.35 1.96 Window profile
EP1613696 VI 2.85 4.75 technisches ProfilEP1613696 VI 2.85 4.75 Technical profile
EP1613696 V2 2.85 4.75 technisches ProfilEP1613696 V2 2.85 4.75 technical profile
EP1613696 V3 2.85 4.75 technisches ProfilEP1613696 V3 2.85 4.75 Technical profile
EP1613696 AI 2.85 4.75 technisches ProfilEP1613696 AI 2.85 4.75 Technical profile
EP1088032 A6 4.39 2.91 FensterprofilEP1088032 A6 4.39 2.91 Window profile
EP1088032 AI 4.40 4.85 FensterprofilEP1088032 AI 4.40 4.85 Window profile
EP1088032 A2 4.40 3.40 FensterprofilEP1088032 A2 4.40 3.40 Window profile
EP1088032 A3 4.40 1.95 FensterprofilEP1088032 A3 4.40 1.95 Window profile
EP1088032 A4 4.40 3.40 FensterprofilEP1088032 A4 4.40 3.40 Window profile
EP1088032 A5 4.40 1.95 FensterprofilEP1088032 A5 4.40 1.95 Window profile
EP1088032 Bl 4.90 1.75 FensterprofilEP1088032 Bl 4.90 1.75 Window profile
EP1088032 B4 4.90 1.75 FensterprofilEP1088032 B4 4.90 1.75 Window profile
EP1088032 B7 4.90 1.75 FensterprofilEP1088032 B7 4.90 1.75 Window profile
EP1088032 B2 5.30 1.62 FensterprofilEP1088032 B2 5.30 1.62 Window profile
EP1088032 B5 5.30 1.62 FensterprofilEP1088032 B5 5.30 1.62 Window profile
EP1088032 B8 5.30 1.62 FensterprofilEP1088032 B8 5.30 1.62 Window profile
EP1088032 B3 6.10 1.40 FensterprofilEP1088032 B3 6.10 1.40 Window profile
EP1088032 B6 6.10 1.40 FensterprofilEP1088032 B6 6.10 1.40 Window profile
EP1088032 B9 6.10 1.40 Fensterprofil EP1088032 B9 6.10 1.40 Window profile
Der vorliegenden Erfindung liegt daher die Aufgabe zugrunde, neue zinkarme Stabilisatorzusammensetzungen bei einer Einsatzmenge <4.5 phr bereitzustellen, die sich insbesondere für PVC-Profile eignen, ohne die oben erwähnten Nachteile der bekannten Stabilisatoren aufzuweisen . The present invention is therefore based on the object of providing new low-zinc stabilizer compositions at a use amount <4.5 phr, which are particularly suitable for PVC profiles, without having the above-mentioned disadvantages of the known stabilizers.
Diese Aufgabe wird erfindungsgemäß gelöst durch die Bereitstellung einer Stabilisatorzusammensetzung mit
Zinkgehalten von 0.5 bis 1.5% bei einer Einsatzmenge <4.5 phr für PVC-Profile. This object is achieved by providing a stabilizer composition with Zinc contents of 0.5 to 1.5% at a use rate <4.5 phr for PVC profiles.
Überraschenderweise hat sich gezeigt, dass die erfindungsgemäßen Stabilisatorzusammensetzungen PVC-Surprisingly, it has been found that the stabilizer compositions according to the invention
_ Profilen und" den daraus hergestellten Teilen und Produkten eine sehr gute Anfangsfarbe, eine ausgezeichnete Farbhaltung sowie eine erhöhte Stabilität gegenüber der Einwirkung von Sonnen- und Kunstlicht und ein besseres Nachhaitigkeitspotential verleihen . _ And "give profiles the parts and products made from it a very good initial color, excellent color retention and increased stability to the action of sunlight and artificial light and a better Nachhaitigkeitspotential.
Insbesondere kann die Anfangsfarbe und die Farbhaltung des halogenhaltigen Materials deutlich im Vergleich zu anderen organischen und anorganischen Costabilisatoren verbessert werden, wenn es in Applikationen, die im freien verwendet werden, zum Beispiel in Profilen, eingesetzt wird. Zudem hat sich gezeigt, dass sich durch Verwendung der erfindungsgemäßen Stabilisatorzusammensetzungen problemlos Formkörper aus halogenhaltigen Polymeren herstellen lassen, die eine optimale Performance im Gebrauch ermöglichen und die mit den Commodities zur PVC-Stabilisierung auf der Basis von Stabilisatorzusammensetzungen für PVC-Profile vergleichbar sind. Dieser stabilisierende Effekt tritt auch auf, wenn das PVC weitere Stabilisatoren, Co-Stabilisatoren oder Hilfsmittel enthält. In particular, the initial color and the color retention of the halogen-containing material can be significantly improved compared to other organic and inorganic costabilizers when used in applications that are used outdoors, for example in profiles. In addition, it has been found that by using the stabilizer compositions according to the invention moldings of halogen-containing polymers can easily be produced which enable optimum performance in use and which are comparable to PVC stabilization commodities based on stabilizer compositions for PVC profiles. This stabilizing effect also occurs when the PVC contains further stabilizers, co-stabilizers or adjuvants.
Gegenstand der vorliegenden Erfindung ist ebenfalls die Verwendung der erfindungsgemäßenThe present invention also relates to the use of the invention
Stabilisatorzusammensetzung zur Stabilisierung von PVC- Profilen, sowie die PVC-Profile, die eineStabilizer composition for the stabilization of PVC profiles, as well as the PVC profiles, the one
Stabilisatorzusammensetzung gemäß der Erfindung enthalten.
Die zinkarme Stabilisatorzusammensetzung der vorliegenden Erfindung kann für halogenhaltige Polymere verwendet werden. Beispiele für solche halogenhaltigen Polymere können thermoplastische halogenhaltige Polymere sein, beispielsweise, ohne darauf beschränkt zu sein, Polyvinylchlorid (PVC) , Polyvinylidenchlorid, chloriertes oder chlorsulfoniertes Polyethylen, chloriertesStabilizer composition according to the invention included. The low-zinc stabilizer composition of the present invention can be used for halogen-containing polymers. Examples of such halogen-containing polymers may be thermoplastic halogen-containing polymers, for example, but not limited to, polyvinyl chloride (PVC), polyvinylidene chloride, chlorinated or chlorosulfonated polyethylene, chlorinated
Polypropylen oder chloriertes Ethylen/Vinylacetat-Copolymer oder ähnliche Verbindungen. Besonders vorteilhaft sind Polymere vom PVC-Typ, d.h. Vinylchlorid-Homopolymere und Copolymere von Vinylchlorid mit anderen Monomeren. Polypropylene or chlorinated ethylene / vinyl acetate copolymer or similar compounds. Particularly advantageous are polymers of the PVC type, i. Vinyl chloride homopolymers and copolymers of vinyl chloride with other monomers.
Die Stabilisatorzusammensetzungen für halogenhaltige Polymere gemäß der vorliegenden Erfindung enthalten mindestens eine Zinkverbindung. DieThe stabilizer compositions for halogen-containing polymers according to the present invention contain at least one zinc compound. The
Stabilisatorzusammensetzung gemäß der vorliegenden Erfindung kann insgesamt in einer Menge von ungefähr 1 bis 4.5 Teile pro 100 Teile Harz (phr) hinzugegeben werden. Stabilizer composition according to the present invention may be added in total in an amount of about 1 to 4.5 parts per 100 parts of resin (phr).
In einer Ausführungsform wird dieIn one embodiment, the
Stabilisatorzusammensetzung in einer Menge von ungefähr 2.0 bis 4.3 phr hinzugegeben, beispielsweise in einer Menge von ungefähr 2.5 bis ungefähr 3.8. Stabilizer composition in an amount of about 2.0 to 4.3 phr added, for example in an amount of about 2.5 to about 3.8.
Die erfindungsgemäß verwendete Stabilisatorzusammensetzung kann einzeln zum Polymer oder zur Polymermischung hinzugegeben werden. Es ist aber auch möglich, die erfindungsgemäße Kombination zusammen mit anderen (Co)- Stabilisatoren oder den unten aufgeführten Hilfsstoffen zum dem Polymer oder einem Polymergemisch hinzuzugeben. Zum Beispiel ist eine Dosierung im Extruder, z.B. in der
Vakuumzone, ebenfalls von der vorliegenden Erfindung umfasst . The stabilizer composition used according to the invention can be added individually to the polymer or to the polymer mixture. However, it is also possible to add the combination according to the invention together with other (co) stabilizers or the auxiliaries listed below to the polymer or a polymer mixture. For example, a dosage in the extruder, for example in the Vacuum zone, also encompassed by the present invention.
Die erfindungsgemäße Stabilisatorzusammensetzung kann weiterhin mit einem oder mehreren zusätzlichen Additiven, wie zum Beispiel Primärstabilisatoren, Co-Stabilisatoren, Zeolithe, Antioxidantien, Füllstoffe, Weichmacher,The stabilizer composition according to the invention may further comprise one or more additional additives, such as, for example, primary stabilizers, co-stabilizers, zeolites, antioxidants, fillers, plasticizers,
Farbstoffe, Pigmente, Antistatica, oberflächenaktive Agenzien, Treibmittel, Schlagzähmodifizierer, UV-Dyes, pigments, antistatic agents, surface active agents, blowing agents, impact modifiers, UV
Stabilisatoren, Gleitmittel, Verarbeitungsmittel oder dergleichen, kombiniert werden. Stabilizers, lubricants, processing agents or the like can be combined.
Co-Stabilisatoren sind Verbindungen die einen weiteren stabilisierenden Beitrag für halogenhaltige Polymere liefern, wenn in der Stabilisatorzusammensetzung gemäß der vorliegenden Erfindung verwendet. Mögliche Co- Stabilisatoren können aus der Gruppe, die aus 1,3- Diketonverbindungen, Dihydropyridine, Polyolen,Co-stabilizers are compounds which provide a further stabilizing contribution to halogen-containing polymers when used in the stabilizer composition according to the present invention. Possible co-stabilizers may be selected from the group consisting of 1,3-diketone compounds, dihydropyridines, polyols,
Isocyanurate, Metallsalzen, natürlichen oder synthetischen Mineralien wie Hydrotalcite, Hydrocalumite, Zeolite, Aminosäurederivaten, organischen Estern der phosphorigen Säure, Epoxyverbindungen, Perchloraten und Salzen von Superacids besteht, ausgewählt werden. Isocyanurates, metal salts, natural or synthetic minerals such as hydrotalcites, hydrocalumites, zeolites, amino acid derivatives, organic esters of phosphorous acid, epoxy compounds, perchlorates and salts of superacids.
Beispiele für 1 , 3-Diketonverbindungen beinhalten, sind aber nicht darauf beschränkt, Dibenzoylmethan,Examples of 1,3-diketone compounds include, but are not limited to, dibenzoylmethane,
Stearoylbenzoylmethan, Palmitoylbenzoylmethan, Myristoylbenzoylmethan, Lauroylbenzoylmethan,Stearoylbenzoylmethane, palmitoylbenzoylmethane, myristoylbenzoylmethane, lauroylbenzoylmethane,
Benzoylaceton, Acetylaceton, Tribenzoylmethan,Benzoylacetone, acetylacetone, tribenzoylmethane,
Diacetylacetobenzol, p-Methoxystearoylacetophenon, Acetoessigsäureester und Acetylaceton sowie deren
Metallsalze, insbesondere die des Zn, Li, Na, K, Ca, Mg, Ti und/oder AI . Diacetylacetobenzene, p-Methoxystearoylacetophenon, acetoacetic acid esters and acetylacetone and their Metal salts, in particular those of Zn, Li, Na, K, Ca, Mg, Ti and / or Al.
Co-Stabilisatoren aus der Gruppe der Polyole beinhalten, sind aber nicht darauf beschränkt, Glycerin, Pentaerythrit , Di- und Tripentaerythrit, Trismethylolpropan (TMP) , Di-TMP, Sorbitol, Mannitol, Malititol, Saccharide, Disacchariden (insbesondere Saccharose, 4-O-ß-D-Galactopyranosyl-D- glucose, 4-O-alpha-D-Glucopyranosyl-D-glucose, 6-0- (6- deoxy-alpha-L-Mannopyranosyl) -D-glucose, alpha-D- Glucopyranosyl-alpha-D-glucopyranosid, 6-0-alpha-D- Glucopyranosyl-D-glucose, 4-O-ß-D-Glucopyranosyl-D-glucose, 2-O-ß-D-Glucopyranosyl-D-glucose, 6-0-alpha-D- Glucopyranosyl-D-glucitol, 3-0-alpha-D-Glucopyranosyl-D- fructose, 6-0-ß-D-Glucopyranosyl-D-glucose, 4-O-ß-D-Co-stabilizers from the group of polyols include, but are not limited to, glycerol, pentaerythritol, di- and tripentaerythritol, trismethylolpropane (TMP), di-TMP, sorbitol, mannitol, malititol, saccharides, disaccharides (especially sucrose, 4-O β-D-galactopyranosyl-D-glucose, 4-O-alpha-D-glucopyranosyl-D-glucose, 6-O- (6-deoxy-alpha-L-mannopyranosyl) -D-glucose, alpha-D-glucopyranosyl alpha-D-glucopyranoside, 6-0-alpha-D-glucopyranosyl-D-glucose, 4-O-beta-D-glucopyranosyl-D-glucose, 2-O-beta-D-glucopyranosyl-D-glucose, 6 -0-alpha-D-glucopyranosyl-D-glucitol, 3-O-alpha-D-glucopyranosyl-D-fructose, 6-O-beta-D-glucopyranosyl-D-glucose, 4-O-beta-D-
Galactopyranosyl-D-glucitol, 4-0-alpha-D-Glucopyranosyl-D- glucitol, 6-0-alpha-D-Galactopyranosyl-D-glucose, 3-0- alpha-D-Galactopyranosyl-D-myo-inositol, 4-0-ß-D- Galactopyranosyl-D-fructose, 4-O-ß-D-Galactopyranosyl-ß-D- glucopyranose, 6-0-alpha-D-Glucopyranosyl-D-fructose, 4-0- ß-D-Galactopyranosyl-alpha-D-glucopyranose, 2-0- (6-Deoxy- alpha-L-mannopyranosyl ) -D-glucose, 4-0-alpha-D- Glucopyranosyl-D-fructose, 2-O-ß-D-Glucopyranosyl-alpha-D- glucopyranose, 1-O-alpha-D-Glucopyranosyl-D-mannitol, 6-0- ( 6-Deoxy-alpha-L-mannopyranosyl) -ß-D-glucopyranose, 2-0-ß- D-Glucopyranosyl-ß-D-glucopyranose, 6-0-alpha-D- Glucopyranosyl-alpha-D-glucopyranose, 2-0-alpha-D- Glucopyranosyl-alpha-D-glucopyranose, 2-0-alpha-D-Galactopyranosyl-D-glucitol, 4-O-alpha-D-glucopyranosyl-D-glucitol, 6-O-alpha-D-galactopyranosyl-D-glucose, 3-O-alpha-D-galactopyranosyl-D-myo-inositol, 4-O-β-D-galactopyranosyl-D-fructose, 4-O-β-D-galactopyranosyl-β-D-glucopyranose, 6-O-alpha-D-glucopyranosyl-D-fructose, 4-O-β- D-galactopyranosyl-alpha-D-glucopyranose, 2-0- (6-deoxy-alpha-L-mannopyranosyl) -D-glucose, 4-O-alpha-D-glucopyranosyl-D-fructose, 2-O-ß- D-glucopyranosyl-alpha-D-glucopyranose, 1-O-alpha-D-glucopyranosyl-D-mannitol, 6-O- (6-deoxy-alpha-L-mannopyranosyl) -β-D-glucopyranose, 2-0- β-D-glucopyranosyl-β-D-glucopyranose, 6-0-alpha-D-glucopyranosyl-alpha-D-glucopyranose, 2-0-alpha-D-glucopyranosyl-alpha-D-glucopyranose, 2-0-alpha D-
Glucopyranosyl-ß-D-glucopyranose, 1-0-alpha-D-Glucopyranosyl-β-D-glucopyranose, 1-0-alpha-D-
Glucopyranosyl-D-fructose, 6-0-alpha-D-Glucopyranosyl- alpha-D-fructofuranose, 6-0-alpha-D-Glucopyranosyl-D- glucitol, 4-0-ß-D-Galactopyranosyl-D-glucitol, 4-0-alpha-D-
Glucopyranosyl-D-glucitol, 1-O-alpha-D-Glucopyranosyl-D- mannitol), Trisaccharide, Polysaccharide, insbesondere Polyvinylalkohole, Stärke, Cellulose und derenGlucopyranosyl-D-fructose, 6-O-alpha-D-glucopyranosyl-alpha-D-fructofuranose, 6-O-alpha-D-glucopyranosyl-D-glucitol, 4-O-beta-D-galactopyranosyl-D-glucitol, 4-0-alpha-D- Glucopyranosyl-D-glucitol, 1-O-alpha-D-glucopyranosyl-D-mannitol), trisaccharides, polysaccharides, especially polyvinyl alcohols, starch, cellulose and theirs
Partialester . Partialester.
Beispiele für Antioxidantien beinhalten, sind aber nicht darauf beschränkt, Alkylphenole, Hydroxyphenylpropionate, HydroxybenzylVerbindungen, Alkylidenbisphenole, Thiobisphenole und Aminophenole, insbesondere z.B. 2, 6-Di- tert . -butyl-4-methyl-phenol , 2, 6-Di-benzyl-4-methyl-phenol, Stearyl-3- (31 -5 '-di-tert . -butyl- ' -hydroxy- phenyl ) propionat , 4,4' -Thiobis- ( 3-methyl-6-tert . -butyl- phenol) , 4-Nonylphenol, 2 , 2 ' -Methylenbis ( 4-methyl-6-tert . - butylphenol) , 2 , 5-Di-tert . -butylhydrochinon, 4,4',4''-(l- Methyl-l-propanyl-3-ylidene) tris [2- (1, 1-dimethylethyl ) -5- methyl-phenol, deren neutrale oder basischen Lithium-, Magnesium-, Calcium- und Aluminiumsalze, sowie sterisch gehinderte Amine und/oder Phosphonite sowie Mischungen davon . Examples of antioxidants include, but are not limited to, alkylphenols, hydroxyphenylpropionates, hydroxybenzyl compounds, alkylidenebisphenols, thiobisphenols, and aminophenols, especially, for example, 2,6-di-tert. -butyl-4-methyl-phenol, 2,6-di-benzyl-4-methyl-phenol, stearyl-3- (3 1 -5 '-di-tert-butyl-' -hydroxy-phenyl) -propionate, 4 '4'-thiobis (3-methyl-6-tert-butylphenol), 4-nonylphenol, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,5-diol tert. -butylhydroquinone, 4,4 ', 4''- (1-methyl-1-propanyl-3-ylidenes) tris [2- (1, 1-dimethyl-ethyl) -5-methylphenol, the neutral or basic lithium thereof, Magnesium, calcium and aluminum salts, and hindered amines and / or phosphonites and mixtures thereof.
Beispiele für Co-Stabilisatoren aus der Gruppe der Metallsalze beinhalten, sind aber nicht darauf beschränkt, Hydroxide, Oxide, Carbonate, basische Carbonate und Carbonsäuresalze von Lithium, Natrium, Kalium, Magnesium, Calcium, Aluminium, Titanium und ähnliche. In einer Ausführungsform der vorliegenden Erfindung können die Metallsalze Salze von Carbonsäuren verwendet werden. Als Carbonsäuren werden Carbonsäuren bezeichnet, die 2-22, insbesondere 7-22 Kohlenstoffatomen aufweisen und aliphatisch oder aromatisch, gesättigt oder ungesättigt, verzweigt oder unverzweigt sein können. Beispiele für geeignete Carbonsäureanionen umfassen Anionen von mono-und
divalenten Carbonsäuren wie Essigsäure, Propionsäure, Buttersäure, Valeriansäure, Hexansäure, Önanthsäure, Octansäure, Neodecansäure, 2-Ethylhexansäure,Examples of co-stabilizers from the group of metal salts include, but are not limited to, hydroxides, oxides, carbonates, basic carbonates, and carboxylic acid salts of lithium, sodium, potassium, magnesium, calcium, aluminum, titanium, and the like. In one embodiment of the present invention, the metal salts may be used salts of carboxylic acids. Carboxylic acids are carboxylic acids which have 2-22, in particular 7-22 carbon atoms and can be aliphatic or aromatic, saturated or unsaturated, branched or unbranched. Examples of suitable carboxylic anions include anions of mono and divalent carboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, enanthic acid, octanoic acid, neodecanoic acid, 2-ethylhexanoic acid,
Pelargonsäure, Decansäure, Undecansäure, Dodecansäure, Tridecansäure, Myristinsäure, Palmitinsäure, Laurinsäure, Isostearinsäure, Stearinsäure, 12-Hydroxystearinsäure, 9, 10-Dihydroxystearinsäure, Ölsäure, 3 , 6-Dioxaheptansäure, 3, 6, 9-Trioxadecansäure, Behensäure, Benzoesäure, p-tert- Butylbenzoesäure, Dimethylhydroxy-benzoesäure, 3,5-Di-tert- butyl-4-hydroxybenzoesäure, Tolylsäure,Pelargonic, decanoic, undecanoic, dodecanoic, tridecanoic, myristic, palmitic, lauric, isostearic, stearic, 12-hydroxystearic, 9,10-dihydroxystearic, oleic, 3,6-dioxaheptanoic, 3,6,9-trioxadecanoic, behenic, benzoic, p-tert-butylbenzoic acid, dimethylhydroxybenzoic acid, 3,5-di-tert-butyl-4-hydroxybenzoic acid, toluic acid,
Dimethylbenzoesäure, Ethylbenzoesäure, n-Propyl- benzoesäure, Salicylsäure, p-tert-Octylsalicylsäure,Dimethylbenzoic acid, ethylbenzoic acid, n-propylbenzoic acid, salicylic acid, p-tert-octylsalicylic acid,
Sorbinsäure, Anionen von divalenten Carbonsäuren bzw. deren Monoestern wie Oxalsäure, Malonsäure, Maleinsäure, Fumarsäure, Adipinsäure, Weinsäure, Zimtsäure, Mandelsäure, Äpfelsäure, Glykolsäure, Salicylsäure,Sorbic acid, anions of divalent carboxylic acids or their monoesters such as oxalic acid, malonic acid, maleic acid, fumaric acid, adipic acid, tartaric acid, cinnamic acid, mandelic acid, malic acid, glycolic acid, salicylic acid,
Polyglykoldicarbonsäuren mit einem Polymerisationsgrad von etwa 10 bis etwa 12, Phthalsäure, Isophthalsäure, Terephthalsäure oder Hydroxyphthalsäure , Anionen von trioder tetravalenten Carbonsäuren bzw. Polyglykoldicarbonsäuren having a degree of polymerization of about 10 to about 12, phthalic acid, isophthalic acid, terephthalic acid or hydroxyphthalic acid, anions of trioder tetravalent carboxylic acids or
deren Mono-, Di- oder Triestern wie sie in Hemimellithsäure, Trimellithsäure, Pyromellithsäure oder Zitronensäure sowie ferner sogenannte überbasische Carboxylate, wie sie beispielsweise in der DED4106404 oder der DEA 4002988 beschrieben werden, wobei die Offenbarung der letztgenannten Dokumente als Bestandteil der Offenbarung des vorliegenden Textes betrachtet wird. their mono-, di- or triesters such as those in hemimellitic acid, trimellitic acid, pyromellitic acid or citric acid and also so-called overbased carboxylates, as described, for example, in DED4106404 or DEA 4002988, the disclosure of the latter documents being part of the disclosure of the present text is looked at.
Beispiel für natürliche und synthetische Mineralien beinhalten, sind aber nicht darauf beschränkt, A3-, A4-, A5-Zeolithe, Zeolithe vom Mordenit, Erionit-, Faujasit X-
oder Y-Typ sowie ZSM-5-Zeolithe, Hydrotalcite (vom Alcamizer 1- und 4-Typ) und/oder Gemische davon. Examples of natural and synthetic minerals include, but are not limited to, A3, A4, A5 zeolites, mordenite zeolites, erionite, faujasite X. or Y-type and ZSM-5 zeolites, hydrotalcites (Alcamizer 1 and 4 type) and / or mixtures thereof.
Beispiele für Co-Stabilisatoren aus der Gruppe der Aminosäurederivate beinhalten, sind aber nicht darauf beschränkt, Glycin, Alanin, Lysin, Tryptophan,Examples of co-stabilizers from the group of amino acid derivatives include, but are not limited to, glycine, alanine, lysine, tryptophan,
Acetylmethionin, Pyrrolidoncarbonsäure, a-Aminocrotonsäure, a-Aminoacrylsäure, α-Aminoadipinsäure und ähnliche, sowie die entsprechenden Ester davon. Die Alkoholkomponenten dieser Ester können einwertige Alkohole, wie zum Beispiel Methylalkohol, Ethylalkohol, Propylalkohol, i-Prop- ylalkohol, Butylalkohol , α-Ethylhexanol , Oktylalkohol, i- Oktylalkohol, Laurylalkohol , Stearylalkohol und ähnliche umfassen, sowie Polyole, wie zum Beispiel Ethylenglycol, Propylenglycol, 1 , 3-Butandiol , 1, 4-Butandiol, Glycerol, Diglycerol, Trismethylolpropan, Pentaerythritol,Acetylmethionine, pyrrolidonecarboxylic acid, α-aminocrotonic acid, α-aminoacrylic acid, α-aminoadipic acid and the like, and the corresponding esters thereof. The alcohol components of these esters may include monohydric alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, i-propyl alcohol, butyl alcohol, α-ethylhexanol, octyl alcohol, i-octyl alcohol, lauryl alcohol, stearyl alcohol, and the like, as well as polyols such as ethylene glycol, Propylene glycol, 1, 3-butanediol, 1, 4-butanediol, glycerol, diglycerol, trismethylolpropane, pentaerythritol,
Dipentaerythritol , Erythrithol, Sorbitol, Mannitol und ähnliche . Dipentaerythritol, erythritol, sorbitol, mannitol and the like.
Beispiele für Co-Stabilisatoren aus der Gruppe der Ester der phosphorigen Säure beinhalten, sind aber nicht darauf beschränkt, Triarylphosphite, wie zum BeispielExamples of co-stabilizers from the group of phosphorous acid esters include, but are not limited to, triaryl phosphites, such as
Triphenylphosphit , Tris (p-nonylphenyl ) phosphit;Triphenyl phosphite, tris (p-nonylphenyl) phosphite;
Alkylarylphosphite, wie zum BeispielAlkylaryl phosphites, such as
Monoalkyldiphenylphosphite, z.B. Diphenylisooctylphosphit, Diphenylisodecylphosphit ; und Dialkylmonophenylphosphite, wie zum Beispiel Phenyldiisooctylphosphit, Phenyl- diisodecylphosphit ; und Trialkylphosphite, wie Triisooctyl- phosphit, Tristearylphosphit und ähnliche.
Beispiele für Co-Stabilisatoren aus der Gruppe der Epoxyverbindungen beinhalten, sind aber nicht darauf beschränkt, verschiedene tierische oder pflanzliche öle, wie zum Beispiel Epoxysojaöl, Epoxyrapsöl, epoxidierte Carbonsäureester, wie zum Beispiel epoxidiertes Epoxymethyloleat, Epoxybutyloleat , epoxidierte alicyclische Verbindungen, Glycidether, wie zum Beispiel Bisphenol-A- diglycidether, Bisphenol-F-diglycidether; Glycidester, wie Glycidylacrylat , Glycidylmethacrylat, deren Polymere, Copolymere; und epoxidierte Polymere, wie epoxidiertes Polybutadien, epoxidiertes ABS, und ähnliche. Monoalkyldiphenylphosphites, eg diphenylisooctylphosphite, diphenylisodecylphosphite; and dialkyl monophenyl phosphites such as phenyl diisooctyl phosphite, phenyl diisodecyl phosphite; and trialkyl phosphites such as triisooctyl phosphite, tristearyl phosphite and the like. Examples of co-stabilizers from the group of epoxy compounds include, but are not limited to, various animal or vegetable oils, such as epoxysoar oil, epoxy rapeseed oil, epoxidized carboxylic acid esters, such as epoxidized epoxy methyl oleate, epoxybutyl oleate, epoxidized alicyclic compounds, glycidyl ethers, such as For example, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether; Glycidic esters, such as glycidyl acrylate, glycidyl methacrylate, their polymers, copolymers; and epoxidized polymers such as epoxidized polybutadiene, epoxidized ABS, and the like.
Beispielhafte Isocyanurate sind, ohne darauf beschränkt zu sein, Exemplary isocyanurates include, but are not limited to,
und
Beispielhafte Dihydropyridine sind, ohne darauf beschränkt zu sein,and Exemplary dihydropyridines include, but are not limited to,
Beispielhafte Perchlorate sind, ohne darauf beschränkt zu sein, NaC104, Ca(C104)2, g(C104)2 oder A1(C104)3. Weitere Beispielhafte Verbindungen dieser Gruppe sind Alcamizer 5 und Alcamizer 5-2 der Firma Kyowa. Exemplary perchlorates include, but are not limited to, NaC104, Ca (C104) 2, g (C104) 2, or A1 (C104) 3. Further exemplary compounds of this group are Alcamizer 5 and Alcamizer 5-2 from Kyowa.
Beispielhaft sei zudem Kreide oder gecoatete Kreide als Füllstoffe benannt, wobei die Füllstoffe nicht darauf beschränkt sind. By way of example, chalk or coated chalk may also be named as fillers, the fillers being not restricted thereto.
Eine weitere Komponente, die derAnother component of the
Stabilisatorzusammensetzung der Erfindung hinzugegeben werden kann ist Titandioxid. Titandioxid tritt im Wesentlichen in der Natur in drei Modifikationen auf: Anatas, Brookit und Rutil. Stabilizer composition of the invention can be added is titanium dioxide. Titanium dioxide occurs essentially in nature in three modifications: anatase, brookite, and rutile.
Eine erfindungsgemäße Stabilisatorzusammensetzung kann weiterhin Gleitmittel wie Montanwachs, Fettsäureester, gereinigte oder hydrierte natürliche oder synthetische Triglyceride oder Partialester, Polyethylenwachse, Amidwachse, Chlorparaffine, Glyzerinester oderA stabilizer composition of the invention may further include lubricants such as montan wax, fatty acid esters, purified or hydrogenated natural or synthetic triglycerides or partial esters, polyethylene waxes, amide waxes, chloroparaffins, glycerol esters or
Erdalkaliseifen enthalten. Verwendbare Gleitmittel werden darüber hinaus auch in "Plastics Additives Handbook", H. Zweifel/R. D. Maier/M. Schiller, Carl Hanser Verlag, 6. Auflage, 2009, S. 539 - 579 beschrieben.
Weiterhin als Gleitmittel geeignet sind beispielsweise Fettketone wie sie in der DE 4204887 beschrieben werden sowie Gleitmittel auf Silikonbasis, wie sie beispielsweise die EP-A 0 259 783 nennt, oder Kombinationen davon, wie sie in der EP-A 0 259 783 genannt werden. Auf die genannten Dokumente wird hiermit ausdrücklich Bezug genommen, deren Gleitmittel betreffende Offenbarung wird als Bestandteil der Offenbarung des vorliegenden Textes betrachtet. Contain alkaline earth soap. Useful lubricants are moreover also described in "Plastics Additives Handbook", H. Zweifel / RD Maier / M. Schiller, Carl Hanser Verlag, 6th edition, 2009, pp. 539-579. Also suitable as lubricants are, for example, fatty ketones as described in DE 4204887 and silicone-based lubricants, as mentioned for example in EP-A 0 259 783, or combinations thereof, as mentioned in EP-A 0 259 783. The documents cited are hereby incorporated by reference, the disclosure of which relates to lubricants being considered part of the disclosure of the present text.
Vorzugsweise weist die Stabilisatorzusammensetzung gemäß der Erfindung wenigstens folgende Komponente auf: Preferably, the stabilizer composition according to the invention has at least the following component:
Zink-, Calcium- und/oder Magnesiumsalze einer mindestens einer C7-C22 Carbonsäure, die aliphatisch oder aromatisch, gesättigt oder ungesättigt, verzweigt oder unverzweigt sein kann wie z.B. von technische Stearin-, Laurin-, C8-10-Carbon- und/oder Benzoesäure, Zinc, calcium and / or magnesium salts of at least one C7-C22 carboxylic acid, which may be aliphatic or aromatic, saturated or unsaturated, branched or unbranched, such as. of technical stearic, lauric, C8-10 carboxylic and / or benzoic acid,
- ein 1,3-Diketon oder ein Calcium-, und/oder ein Mg und/oder ein Zn-Salz eines 1 , 3-Diketons , a 1,3-diketone or a calcium, and / or a Mg and / or a Zn salt of a 1, 3-diketone,
wobei der Zn-Gehalz einer solchen Zusammensetzung zwischen 0,5 bis 1,5 Gew.% liegt bei einer Einsatzmenge von 1 bis 4,5 phr . wherein the Zn-content of such a composition is between 0.5 to 1.5 wt.% With a starting amount of 1 to 4.5 phr.
Des Weiteren enthält die Stabilisatorzusammensetzung vorzugsweise eine Isocyanuratverbindung . Furthermore, the stabilizer composition preferably contains an isocyanurate compound.
Die Stabilisatorzusammensetzung gemäß der Erfindung ist vorzugsweise fest und enthält vorzugsweise kein Lösungsmittel . The stabilizer composition according to the invention is preferably solid and preferably contains no solvent.
Um PVC-Profile mit der erfindungsgemäßenTo PVC profiles with the invention
Stabilisatorzusammensetzung zu verarbeiten, können die im Stand der Technik bekannten Verfahren verwendet werden. Beispiele für derartige Verfahren beinhalten, sind aber nicht darauf beschränkt, Extrudieren und ähnliche.
Die vorliegende Erfindung liefert demzufolge einen bemerkenswerten und neuen Beitrag zur Entwicklung des Standes der Technik, insbesondere für die Verarbeitung und Stabilisierung von PVC-Profilen und anderen halogenhaltigen thermoplastischen Polymeren, vorzugsweise Hart-PVC. Stabilizer composition to process, the methods known in the art can be used. Examples of such methods include, but are not limited to, extruding and the like. The present invention accordingly provides a remarkable and novel contribution to the development of the prior art, in particular for the processing and stabilization of PVC profiles and other halogen-containing thermoplastic polymers, preferably rigid PVC.
Die Erfindung wird durch die nachfolgenden Beispiele näher veranschaulicht, ohne jedoch darauf beschränkt zu sein. The invention is further illustrated by, but not limited to, the following examples.
In den nachfolgenden Beispielen werden verschiedene Zusammensetzungen von PVC-Fensterprofilen beschrieben. Zu deren Herstellung wurden neben S-PVC, Kreide mit Oberflächenbehandlung, Titandioxide und Impactmodifier auf Acrylatbasis die in den Beispielen genannten Bestandteile eingewogen. (Wenn in Tab. 1 nicht explizit ein Zinkgehalt angegeben ist, so enthält das entsprechende Additiv kein Zink oder nur im Spurenbereich.) Alle Komponenten wurden in einem Heißmischer innerhalb von 5 min. auf 120°C erhitzt, in 5 min. auf 40°C abgekühlt, danach 24 h gelagert und anschließend 90 min. auf einem parallelenIn the following examples, various compositions of PVC window profiles are described. In addition to S-PVC, chalks with surface treatment, titanium dioxides and acrylate impact modifiers, the components mentioned in the examples were weighed for their preparation. (If in Tab. 1 not explicitly a zinc content is indicated, then the corresponding additive contains no zinc or only in the trace range.) All components were in a hot mixer within 5 min. heated to 120 ° C, in 5 min. cooled to 40 ° C, then stored for 24 h and then 90 min. on a parallel
Doppelschneckenextruder der Firma Brabender extrudiert. Die einzelnen Zusammensetzungen sind in der folgenden Tabelle 1 wiedergegeben . Twin screw extruder from Brabender extruded. The individual compositions are given in Table 1 below.
Die Rheologie (Drehmoment und Massedruck) der erfindungsgemäßen Kombination stimmen mit dem The rheology (torque and mass pressure) of the combination of the invention agree with the
Vergleichsbeispiel, einem handelsüblichen Produkts der Fa. Akdeniz Kimya überein. Es wird ebenso eine vergleichbare und zum Teil bessere Anfangsfarbe (L a b-Werte) und ein vergleichbarer Glanz erzielt. Die statitischeComparative example, a commercial product of the Fa. Akdeniz Kimya match. It also achieves a comparable and in some cases better initial color (L a b values) and a comparable gloss. The statical
Thermostabilität (DHC = Dehydrochlorierung) liegt je nach dem gewählten Costabilisator im vergleichbaren Bereich oder
deutlich über dem DHC-Wert des Vergleichsbeispiels. Thermostability (DHC = dehydrochlorination) is, depending on the chosen costabilizer in the comparable range or significantly above the DHC value of the comparative example.
Vergleichs Beispiel Beispiel Beispiel Beispiel beispiel 1 2 3 4 Comparative Example Example Example Example Example 1 2 3 4
PVC (k = 68) 100 100 100 100 100PVC (k = 68) 100 100 100 100 100
Kreide mit Oberflächenbehandlung 10 10 10 10 10Chalk with surface treatment 10 10 10 10 10
Schlagzähmodifier auf Acrylatbasis 6 6 6 6 6Acrylic Based Impact Modifier 6 6 6 6 6
Titaniumdioxid (Rutil) 4 4 4 4 4Titanium dioxide (rutile) 4 4 4 4 4
Fließhilfe 0.50 0.50 0.50 0.50Flow aid 0.50 0.50 0.50 0.50
Distearylphthalat 0.50 0.50 0.50 0.50Distearyl phthalate 0.50 0.50 0.50 0.50
PE-Wachs 0.20 0.20 0.20 0.20PE wax 0.20 0.20 0.20 0.20
Paraffinwachs (1 10°C) 0.20 0.20 0.20 0.20 oxidiertes PE-Wachs 0.10 0.10 0.10 0.10Paraffin wax (1 10 ° C) 0.20 0.20 0.20 0.20 oxidized PE wax 0.10 0.10 0.10 0.10
Calciumacetylacetonat 0.30 0.30 0.30 0.30Calcium acetylacetonate 0.30 0.30 0.30 0.30
Dibenzoylmethan 0.30 0.30 0.30 0.30Dibenzoylmethane 0.30 0.30 0.30 0.30
Irganox 1076 0.20 0.20 0.20 0.20Irganox 1076 0.20 0.20 0.20 0.20
Calciumstearat 0.50 0.50 0.50 0.50Calcium Stearate 0.50 0.50 0.50 0.50
Actilox CAHC (Fa. Nabaltec) 1.20 Actilox CAHC (Nabaltec) 1.20
Sorbacid 91 1 (Fa. Südchemie) 1.00 Sorbacid 91 1 (Südchemie) 1.00
Dipentaerythrithol 0.75 Dipentaerythritol 0.75
2-Phenylindol 0.50 2-phenylindole 0.50
Zinkbenzoat (21.3% Zn) 0.20 0.10Zinc benzoate (21.3% Zn) 0.20 0.10
Zinklaurat (14.1% Zn) 0.25 Zinc laurate (14.1% Zn) 0.25
Zinkstearat (10.7% Zn) 0.30 0.10 Zinc stearate (10.7% Zn) 0.30 0.10
Akropan 7535-1 GX 4.50 Akropan 7535-1 GX 4.50
Summe der Stabilisatorkombination 4.50 4.30 4.05 3.75 3.50Sum of the stabilizer combination 4.50 4.30 4.05 3.75 3.50
Zinkgehalt in der Zinc content in the
Stab i 1 isatorkomb ination 2.63% 0.75% 0.87% 1.14% 0.91% Stab i 1 isator combination 2.63% 0.75% 0.87% 1.14% 0.91%
Extruderdrehmoment (Nm) 151 156 147 156 147Extruder torque (Nm) 151 156 147 156 147
Massedruck (bar) 148 159 151 163 154Melt pressure (bar) 148 159 151 163 154
L 92.2 92.1 92.2 92.4 92.3 a -1.3 -1.5 -1.3 -0.8 -0.6 b 4.3 4.2 4.4 2.8 3.5L 92.2 92.1 92.2 92.4 92.3 a -1.3 -1.5 -1.3 -0.8 -0.6 b 4.3 4.2 4.4 2.8 3.5
Glanz (oben) 48 47 51 48 53Gloss (above) 48 47 51 48 53
Glanz (unten) 26 31 35 34 38Gloss (below) 26 31 35 34 38
DHC 62 67 74 95 57
DHC 62 67 74 95 57
Claims
1. Stabilisatorzusammensetzung für halogenhaltige Polymere gekennzeichnet durch einen Zn-Gehalt von ca. 0.5 bis ca. 1.5 Gew.%, vorzugsweise 0.75 bis 1.15 Gew% Zink (bezogen auf die Gesamtmenge des Stabilisatorzusammensetzung) bei einer Einsatzmenge des Stabilisators von ca. 1 bis 4.5 pro 100 Teile Harz (phr) . 1. stabilizer composition for halogen-containing polymers characterized by a Zn content of about 0.5 to about 1.5 wt.%, Preferably 0.75 to 1.15 wt% zinc (based on the total amount of the stabilizer composition) at an amount of the stabilizer of about 1 to 4.5 per 100 parts resin (phr).
2. Stabilisatorzusammensetzung für halogenhaltige Polymere gemäß Anspruch 1 enthaltend eine Metallseife. 2. stabilizer composition for halogen-containing polymers according to claim 1 containing a metal soap.
3. Stabilisatorzusammensetzung für halogenhaltige Polymere nach einem der vorhergehenden Ansprüche enthaltend zusätzlich ein Antioxidans. 3. stabilizer composition for halogen-containing polymers according to any one of the preceding claims additionally containing an antioxidant.
4. Stabilisatorzusammensetzung für halogenhaltige Polymere nach einem der vorhergehenden Ansprüche enthaltend zusätzlich ein ß-Diketon und/oder eine Metallverbindung eines ß-Diketons. 4. stabilizer composition for halogen-containing polymers according to any one of the preceding claims additionally containing a ß-diketone and / or a metal compound of a ß-diketone.
5. Stabilisatorzusammensetzung für halogenhaltige Polymere nach einem der vorhergehenden Ansprüche enthaltend zusätzlich ein Isocyanurat. 5. stabilizer composition for halogen-containing polymers according to any one of the preceding claims additionally containing an isocyanurate.
6. Stabilisatorzusammensetzung für halogenhaltige Polymere nach einem der vorhergehenden Ansprüche enthaltend zusätzlich ein Polyol . 6. stabilizer composition for halogen-containing polymers according to any one of the preceding claims additionally containing a polyol.
7. Stabilisatorzusammensetzung für halogenhaltige Polymere nach einem der vorhergehenden Ansprüche enthaltend zusätzlich eine Perchloratverbindung . 7. stabilizer composition for halogen-containing polymers according to any one of the preceding claims additionally containing a perchlorate compound.
8. Stabilisatorzusammensetzung für halogenhaltige Polymere nach einem der vorhergehenden Ansprüche enthaltend zusätzlich ein Gleitmittel. 8. stabilizer composition for halogen-containing polymers according to any one of the preceding claims additionally containing a lubricant.
9. Stabilisatorzusammensetzung für halogenhaltige Polymere nach einem der vorhergehenden Ansprüche enthaltend zusätzlich eine Metallverbindung vorzugsweise aus der Gruppe aus Hydrotalcite, Metalloxide und Metallhydroxide . 9. stabilizer composition for halogen-containing polymers according to any one of the preceding claims additionally containing a metal compound, preferably from the group of hydrotalcites, metal oxides and metal hydroxides.
10. Stabilisatorzusammensetzung für halogenhaltige Polymere nach einem der vorhergehenden Ansprüche enthaltend zusätzlich einen Füllstoff. 10. stabilizer composition for halogen-containing polymers according to any one of the preceding claims additionally containing a filler.
11. Stabilisatorzusammensetzung für halogenhaltige Polymere nach einem der vorhergehenden Ansprüche enthaltend zusätzlich ein Pigment. 11. stabilizer composition for halogen-containing polymers according to any one of the preceding claims additionally containing a pigment.
12. Stabilisatorzusammensetzung für halogenhaltige Polymere nach einem der vorhergehenden Ansprüche enthaltend zusätzlich einen UV-Stabilisator. 12. stabilizer composition for halogen-containing polymers according to any one of the preceding claims additionally containing a UV stabilizer.
13. Stabilisatorzusammensetzung für halogenhaltige Polymere nach einem der vorhergehenden Ansprüche enthaltend zusätzlich gemäß Anspruch 1 enthaltend einen ZinnStabilisator. 13. stabilizer composition for halogen-containing polymers according to any one of the preceding claims additionally containing according to claim 1 containing a tin stabilizer.
14. Stabilisatorzusammensetzung für halogenhaltige Polymere nach einem der vorhergehenden Ansprüche enthaltend zusätzlich ein Dihydropyridin . 14. stabilizer composition for halogen-containing polymers according to any one of the preceding claims additionally containing a dihydropyridine.
15. Stabilisatorzusammensetzung für halogenhaltige Polymere nach einem der vorhergehenden Ansprüche enthaltend zusätzlich eine Epoxidverbindung . 15. stabilizer composition for halogen-containing polymers according to any one of the preceding claims additionally containing an epoxy compound.
16. Stabilisatorzusammensetzung für halogenhaltige Polymere nach einem der vorhergehenden Ansprüche enthaltend zusätzlich ein organisches Phosphit. 16. stabilizer composition for halogen-containing polymers according to any one of the preceding claims additionally containing an organic phosphite.
17. Stabilisatorzusammensetzung für halogenhaltige Polymere nach einem der vorhergehenden Ansprüche enthaltend zusätzlich eine Uracil. 17. stabilizer composition for halogen-containing polymers according to any one of the preceding claims additionally containing a uracil.
18. Stabilisatorzusammensetzung für halogenhaltige Polymere nach einem der vorhergehenden Ansprüche enthaltend zusätzlich ein Melamin. 18. stabilizer composition for halogen-containing polymers according to any one of the preceding claims additionally containing a melamine.
19. Stabilisatorzusammensetzung für halogenhaltige Polymere nach einem der vorhergehenden Ansprüche enthaltend zusätzlich eine Aminosäure. 19. stabilizer composition for halogen-containing polymers according to any one of the preceding claims additionally containing an amino acid.
20. Stabilisatorzusammensetzung für halogenhaltige Polymere nach einem der vorhergehenden Ansprüche enthaltend zusätzlich eine hydroxygruppenhaltige Aminoverbindung. 20. A stabilizer composition for halogen-containing polymers according to any one of the preceding claims additionally containing a hydroxyl-containing amino compound.
21. Stabilisatorzusammensetzung für halogenhaltige Polymere nach einem der vorhergehenden Ansprüche enthaltend zusätzlich ein Treibmittel. 21. A stabilizer composition for halogen-containing polymers according to any one of the preceding claims additionally containing a blowing agent.
22. Stabilisatorzusammensetzung für halogenhaltige Polymere nach einem der vorhergehenden Ansprüche enthaltend zusätzlich einen Weichmacher. 22. A stabilizer composition for halogen-containing polymers according to any one of the preceding claims additionally containing a plasticizer.
23. Stabilisatorzusammensetzung für halogenhaltige Polymere nach einem der vorhergehenden Ansprüche als Schmelzprodukt . 23. stabilizer composition for halogen-containing polymers according to any one of the preceding claims as a melt product.
24. PVC-Compound (Granulat oder dryblend) enthaltend eine Stabilisatorzusammensetzung für halogenhaltige Polymere nach einem der vorhergehenden Ansprüche. 24. PVC compound (granule or dryblend) containing a stabilizer composition for halogen-containing polymers according to any one of the preceding claims.
25. PVC-Profil enthaltend eine Stabilisatorzusammensetzung für halogenhaltige Polymere nach einem der vorhergehenden Ansprüche. 25. PVC profile containing a stabilizer composition for halogen-containing polymers according to any one of the preceding claims.
Applications Claiming Priority (2)
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DE102009052206A DE102009052206A1 (en) | 2009-11-06 | 2009-11-06 | Low zinc stabilizer composition for window profiles |
DE102009052206.9 | 2009-11-06 |
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PCT/EP2010/006775 WO2011054536A1 (en) | 2009-11-06 | 2010-11-08 | Stabilizer compositions having low zinc content for window profiles |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102604295A (en) * | 2012-01-12 | 2012-07-25 | 河北大学 | Polymer calcium zinc complex soap heat stabilizer, preparation method thereof and application thereof |
US8633266B2 (en) | 2010-05-11 | 2014-01-21 | Akdeniz Kimya San. ve Tic. A.S. | Tin-free stabilizer composition |
CN104387616A (en) * | 2014-12-16 | 2015-03-04 | 天津中财型材有限责任公司 | Ca/Zn composite stabilizer, preparation method thereof and environment-friendly profile |
CN105585798A (en) * | 2016-02-22 | 2016-05-18 | 江苏爱特恩东台新材料科技有限公司 | Specific environment-friendly heat stabilizer prepared from waste polyester for PVC cables and preparation method thereof |
CN106478990A (en) * | 2016-09-26 | 2017-03-08 | 深圳市志海实业股份有限公司 | A kind of novel melting one-step method prepares hydroxy fatty acid calcium zinc PVC stabilizer |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN103122109A (en) * | 2013-01-16 | 2013-05-29 | 江苏爱特恩高分子材料有限公司 | PVC (polyvinyl chloride) composite heat stabilizer and application thereof |
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Cited By (6)
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US8633266B2 (en) | 2010-05-11 | 2014-01-21 | Akdeniz Kimya San. ve Tic. A.S. | Tin-free stabilizer composition |
CN102604295A (en) * | 2012-01-12 | 2012-07-25 | 河北大学 | Polymer calcium zinc complex soap heat stabilizer, preparation method thereof and application thereof |
CN104387616A (en) * | 2014-12-16 | 2015-03-04 | 天津中财型材有限责任公司 | Ca/Zn composite stabilizer, preparation method thereof and environment-friendly profile |
CN105585798A (en) * | 2016-02-22 | 2016-05-18 | 江苏爱特恩东台新材料科技有限公司 | Specific environment-friendly heat stabilizer prepared from waste polyester for PVC cables and preparation method thereof |
CN105585798B (en) * | 2016-02-22 | 2017-07-07 | 盐城科迈特新材料有限公司 | PVC cable special environment protection heat stabilizer prepared by Waste Polyester and preparation method thereof |
CN106478990A (en) * | 2016-09-26 | 2017-03-08 | 深圳市志海实业股份有限公司 | A kind of novel melting one-step method prepares hydroxy fatty acid calcium zinc PVC stabilizer |
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