NO764344L - - Google Patents
Info
- Publication number
- NO764344L NO764344L NO764344A NO764344A NO764344L NO 764344 L NO764344 L NO 764344L NO 764344 A NO764344 A NO 764344A NO 764344 A NO764344 A NO 764344A NO 764344 L NO764344 L NO 764344L
- Authority
- NO
- Norway
- Prior art keywords
- phosphite
- mol
- substituted
- mixtures
- phosphites
- Prior art date
Links
- 239000000203 mixture Substances 0.000 claims description 72
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 claims description 58
- 239000003381 stabilizer Substances 0.000 claims description 30
- 239000003054 catalyst Substances 0.000 claims description 27
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- 238000005809 transesterification reaction Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 15
- 239000003513 alkali Substances 0.000 claims description 13
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical class C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 12
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 11
- 150000001298 alcohols Chemical class 0.000 claims description 9
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 9
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 claims description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000006227 byproduct Substances 0.000 claims description 7
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 claims description 7
- 125000003342 alkenyl group Chemical group 0.000 claims description 6
- 229910052788 barium Inorganic materials 0.000 claims description 6
- 239000011133 lead Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000011368 organic material Substances 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- 150000001408 amides Chemical class 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052793 cadmium Inorganic materials 0.000 claims description 5
- 150000007942 carboxylates Chemical class 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 5
- 125000001316 cycloalkyl alkyl group Chemical group 0.000 claims description 5
- 125000003884 phenylalkyl group Chemical group 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- 229920001169 thermoplastic Polymers 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 230000015556 catabolic process Effects 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 229920003023 plastic Polymers 0.000 claims description 4
- 239000004033 plastic Substances 0.000 claims description 4
- 230000006641 stabilisation Effects 0.000 claims description 4
- 238000011105 stabilization Methods 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 238000006731 degradation reaction Methods 0.000 claims description 3
- 101000623895 Bos taurus Mucin-15 Proteins 0.000 claims description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 2
- 125000005346 substituted cycloalkyl group Chemical group 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims 8
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 claims 1
- 229940031826 phenolate Drugs 0.000 claims 1
- -1 phenylalkyl phosphites Chemical class 0.000 description 56
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 28
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000011888 foil Substances 0.000 description 15
- 239000004800 polyvinyl chloride Substances 0.000 description 15
- 229920000915 polyvinyl chloride Polymers 0.000 description 15
- 230000009965 odorless effect Effects 0.000 description 14
- 230000000694 effects Effects 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 13
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 10
- 150000002989 phenols Chemical class 0.000 description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
- 239000004743 Polypropylene Substances 0.000 description 7
- 239000000654 additive Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 229920001155 polypropylene Polymers 0.000 description 7
- 238000005096 rolling process Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- TXSWGTOCTHQLJU-UHFFFAOYSA-N CCCCCCCCCC(C=C1)=C(CCCCCCCCC)C(CCCCCCCCC)=C1P(O)(O)O Chemical compound CCCCCCCCCC(C=C1)=C(CCCCCCCCC)C(CCCCCCCCC)=C1P(O)(O)O TXSWGTOCTHQLJU-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- NMAKPIATXQEXBT-UHFFFAOYSA-N didecyl phenyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OC1=CC=CC=C1 NMAKPIATXQEXBT-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000003825 pressing Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- BLXLSQIOCCHAHJ-UHFFFAOYSA-N [2,3,4-tri(nonyl)phenyl] dihydrogen phosphite Chemical compound CCCCCCCCCC1=CC=C(OP(O)O)C(CCCCCCCCC)=C1CCCCCCCCC BLXLSQIOCCHAHJ-UHFFFAOYSA-N 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000005755 formation reaction Methods 0.000 description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 5
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 4
- 229920000877 Melamine resin Polymers 0.000 description 4
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 4
- GLOQRSIADGSLRX-UHFFFAOYSA-N decyl diphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OCCCCCCCCCC)OC1=CC=CC=C1 GLOQRSIADGSLRX-UHFFFAOYSA-N 0.000 description 4
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 150000004707 phenolate Chemical class 0.000 description 4
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 150000003512 tertiary amines Chemical class 0.000 description 4
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- 229920002292 Nylon 6 Polymers 0.000 description 3
- 229920002367 Polyisobutene Polymers 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000010348 incorporation Methods 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 229920001748 polybutylene Polymers 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 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
- 241001295925 Gegenes Species 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229920013623 Solprene Polymers 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 239000000370 acceptor Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- MGFRKBRDZIMZGO-UHFFFAOYSA-N barium cadmium Chemical compound [Cd].[Ba] MGFRKBRDZIMZGO-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical class OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 description 2
- KUMNEOGIHFCNQW-UHFFFAOYSA-N diphenyl phosphite Chemical compound C=1C=CC=CC=1OP([O-])OC1=CC=CC=C1 KUMNEOGIHFCNQW-UHFFFAOYSA-N 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910001510 metal chloride Inorganic materials 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 125000001802 myricyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 239000005033 polyvinylidene chloride Substances 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000011814 protection agent Substances 0.000 description 2
- 239000002516 radical scavenger Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000000126 substance 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
- 150000003672 ureas Chemical class 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 238000009489 vacuum treatment Methods 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- JXGDULVGMVMNRZ-UHFFFAOYSA-N (2,3,4-trioctylphenyl) dihydrogen phosphite Chemical compound CCCCCCCCC1=CC=C(OP(O)O)C(CCCCCCCC)=C1CCCCCCCC JXGDULVGMVMNRZ-UHFFFAOYSA-N 0.000 description 1
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- HBXWUCXDUUJDRB-UHFFFAOYSA-N 1-octadecoxyoctadecane Chemical compound CCCCCCCCCCCCCCCCCCOCCCCCCCCCCCCCCCCCC HBXWUCXDUUJDRB-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
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- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 description 1
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- 230000002378 acidificating effect Effects 0.000 description 1
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- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
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- 239000002216 antistatic agent Substances 0.000 description 1
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- ITQVEYJXZXMBTR-UHFFFAOYSA-L cadmium(2+);dodecanoate Chemical compound [Cd+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O ITQVEYJXZXMBTR-UHFFFAOYSA-L 0.000 description 1
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- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- DDZKWIFZXPCREI-UHFFFAOYSA-N cyclohexylmethanol;terephthalic acid Chemical compound OCC1CCCCC1.OC(=O)C1=CC=C(C(O)=O)C=C1 DDZKWIFZXPCREI-UHFFFAOYSA-N 0.000 description 1
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000000522 cyclooctenyl group Chemical group C1(=CCCCCCC1)* 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000004851 cyclopentylmethyl group Chemical group C1(CCCC1)C* 0.000 description 1
- 125000003493 decenyl group Chemical group [H]C([*])=C([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 150000001993 dienes Chemical class 0.000 description 1
- OPDJXTMPAYLJDY-UHFFFAOYSA-N dihydroxy-(6-methylheptoxy)-diphenyl-lambda5-phosphane Chemical compound C(CCCCC(C)C)OP(O)(O)(C1=CC=CC=C1)C1=CC=CC=C1 OPDJXTMPAYLJDY-UHFFFAOYSA-N 0.000 description 1
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- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 238000001704 evaporation Methods 0.000 description 1
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- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
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- 150000002314 glycerols Chemical class 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- AHAREKHAZNPPMI-UHFFFAOYSA-N hexa-1,3-diene Chemical compound CCC=CC=C AHAREKHAZNPPMI-UHFFFAOYSA-N 0.000 description 1
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- 239000004615 ingredient Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 235000021190 leftovers Nutrition 0.000 description 1
- PKMBLJNMKINMSK-UHFFFAOYSA-N magnesium;azanide Chemical compound [NH2-].[NH2-].[Mg+2] PKMBLJNMKINMSK-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 125000006178 methyl benzyl group Chemical group 0.000 description 1
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- 235000010981 methylcellulose Nutrition 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
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- 239000012170 montan wax Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002460 pentacosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229920001568 phenolic resin Polymers 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
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- ZDCHZHDOCCIZIY-UHFFFAOYSA-N phthalic acid;propane-1,2,3-triol Chemical compound OCC(O)CO.OC(=O)C1=CC=CC=C1C(O)=O ZDCHZHDOCCIZIY-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000006077 pvc stabilizer Substances 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- HSFQBFMEWSTNOW-UHFFFAOYSA-N sodium;carbanide Chemical group [CH3-].[Na+] HSFQBFMEWSTNOW-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- YWMYPVCADAAQCE-UHFFFAOYSA-N strontium;azanide Chemical compound [NH2-].[NH2-].[Sr+2] YWMYPVCADAAQCE-UHFFFAOYSA-N 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- KFUSEUYYWQURPO-OWOJBTEDSA-N trans-1,2-dichloroethene Chemical compound Cl\C=C\Cl KFUSEUYYWQURPO-OWOJBTEDSA-N 0.000 description 1
- 125000002469 tricosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- FEVFLQDDNUQKRY-UHFFFAOYSA-N tris(4-methylphenyl) phosphite Chemical group C1=CC(C)=CC=C1OP(OC=1C=CC(C)=CC=1)OC1=CC=C(C)C=C1 FEVFLQDDNUQKRY-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 235000019871 vegetable fat Nutrition 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/141—Esters of phosphorous 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
Description
Fosfitblandinger, fremgangsmåte til deres fremstilling og organiske materialer stabilisert dermed. Phosphite mixtures, process for their preparation and organic materials stabilized thereby.
Oppfinnelsen vedrører blandinger av forskjellige substituerte fosfiter som inneholder hydrokarbonrester av alifatisk, cykloalifatisk og aromatisk karakter, en fremgangsmåte til fremstilling av blandinger av forskjellige substituerte fosfiter samt dermed stabiliserte organiske materialer. The invention relates to mixtures of various substituted phosphites containing hydrocarbon residues of aliphatic, cycloaliphatic and aromatic character, a method for producing mixtures of various substituted phosphites and thus stabilized organic materials.
Estere av fosforsyrling er av betraktelig interesse som forarbeidelseshjelpemiddel for kunststoffer og gummi. De har spesiell betydning for PVC, dets blandingspolymerisater og-andre klorholdige polymere som klorholdige polyolefiner. Disse polymere spalter seg som bekjent under innvirkning av lys og varme. For ved de nødvendige forarbeidelsestemperaturer å unn-gå disse spaltningsforeteelser tilsettes til den polymere stabilisatorer. Utbredt anvendelse finner derved blant metall-holdige stabilisatorer på basis av karboksylater resp. fenolater av barium, kadmium, kalsium, sink og bly., Esters of phosphoric acid are of considerable interest as processing aids for plastics and rubber. They are of particular importance for PVC, its mixed polymers and other chlorine-containing polymers such as chlorine-containing polyolefins. As you know, these polymers split under the influence of light and heat. In order to avoid these splitting phenomena at the required processing temperatures, stabilizers are added to the polymer. Widespread use is thereby found among metal-containing stabilizers based on carboxylates or phenolates of barium, cadmium, calcium, zinc and lead.,
Disse primærstabilisatorer er ved anvendelse alene imidlertid bare begrenset virksomme. Etter generell oppfatning katalyserer de metallklorider som danner seg ved stabiliserings-prosessen nedbygningen av PVC. Denne destabiliserende virkning av metallkloridene kan imidlertid virksomt hindres ved samtidig anvendelse av fosfiter som såkalte kostabilisatorer. However, these primary stabilizers are only limitedly effective when used alone. According to general opinion, the metal chlorides that form during the stabilization process catalyze the breakdown of PVC. This destabilizing effect of the metal chlorides can, however, be effectively prevented by the simultaneous use of phosphites as so-called cost stabilisers.
Denne anvendelse av fosfiter i kombinasjon med metallstabilisatorer er kjent (sammenlign J. Voigt: "Die Stabilisierung der Kunststoffe gegen Licht und V/årme", Springer-Verlag, Berlin, 1. opplag 1966, side 316-326; K. Thinius: "Stabilisierung und Alterung von Plastwerkstoffen", Akademie-Verlag, Berlin, 1969, bind I, side 517-530). This use of phosphites in combination with metal stabilizers is known (compare J. Voigt: "Die Stabilisierung der Kunststoffe gegen Licht und V/årme", Springer-Verlag, Berlin, 1st edition 1966, pages 316-326; K. Thinius: " Stabilisierung und Alterung von Plastwerkstoffen", Akademie-Verlag, Berlin, 1969, volume I, pages 517-530).
De til teknikkens stand svarende fosfiter er triarylfosfiter, fenylalkylfosfiter eller alkylfenylalkylfosfiter samt polymere fosfiter av typen omforestringsprodukter av f.eks. trifenylfosfit med di- resp. polyhydroksyforbindelser. The phosphites corresponding to the state of the art are triaryl phosphites, phenylalkyl phosphites or alkylphenylalkyl phosphites as well as polymeric phosphites of the transesterification product type of e.g. triphenyl phosphite with di- resp. polyhydroxy compounds.
Por fremstilling av disse fosfiter var det kjent flere forskjellige fremgangsmåter (sammenlign Houben-Weyl, "Methoden der organischen Chemie", Thieme-Verlag, Stuttgart 1964, bind XII/2, side 59-78). For the preparation of these phosphites several different methods were known (compare Houben-Weyl, "Methoden der organischen Chemie", Thieme-Verlag, Stuttgart 1964, volume XII/2, pages 59-78).
Således syntetiseres triarylfosfiter f.eks. ved direkte omsetning av tilsvarende fenoler med fosfor-(III)-klorid i molforhold J>-' 1, idet omsetningens reaksjonstemperatur vanligvis utgjør 150°C og høyere. Fjerning av resterende hydrogenklorid kan foretas ved vakuumbehandling, innføring av inertgass eller ifølge US-patent nr. 2.170.833 også ved behand-ling med fast natriumkarbonat. Også anvendelsen av tertiære aminer, som f.eks. pyridin, som syreoppfanger er mulig. Thus, triaryl phosphites are synthesized e.g. by direct reaction of corresponding phenols with phosphorus (III) chloride in molar ratio J>-' 1, the reaction temperature of the reaction usually being 150°C and higher. Removal of residual hydrogen chloride can be carried out by vacuum treatment, introduction of inert gas or, according to US patent no. 2,170,833, also by treatment with solid sodium carbonate. Also the use of tertiary amines, such as e.g. pyridine, as an acid scavenger is possible.
Usymmetriske fosfiter, som ary1-dialkylfosfiter eller diarylalkylfosfiter f.eks. syntetiseres av de tilsvarende alkoksy(aryloksy)-dihalogenfosfiter resp. dialkoksy(aryloksy)-halogenfosfiter og alkoholer i nærvær av tertiære aminer, som f.eks. pyridin, N,N-dimetylanilin eller trietylamin eller syntetiseres også ved omforestring av trifenyl- resp. tritolylfos-fit, f.eks. med tilsvarende alkoholer i nærvær av katalytiske mengder alkali- eller jordalkalialkoholater eller -fenolater. Unsymmetrical phosphites, such as aryl1-dialkyl phosphites or diarylalkyl phosphites e.g. are synthesized from the corresponding alkoxy(aryloxy)-dihalophosphites resp. dialkoxy(aryloxy)-halophosphites and alcohols in the presence of tertiary amines, such as e.g. pyridine, N,N-dimethylaniline or triethylamine or is also synthesized by transesterification of triphenyl- or tritolylphos-fit, e.g. with corresponding alcohols in the presence of catalytic amounts of alkali or alkaline earth alcoholates or phenolates.
Således fåes ifølge US-patent nr. 3.056.824 diiso-okty1-monotolylfosfit resp. mono-isooktyl-difenylfosfit ved omforestring av tritolyl- resp. trifenylfosfit med isooktanol i nærvær av kalium- resp. natrium-isooktanolat. Thus, according to US patent no. 3,056,824, diiso-octyl-monotolyl phosphite or mono-isooctyl-diphenylphosphite by transesterification of tritolyl- or triphenylphosphite with isooctanol in the presence of potassium resp. sodium isooctanolate.
Ifølge britisk patent nr. 901.703 kan isooktyl-difenylfosfit f.eks. også fremstilles ved omforestring av trifenylfosfit med isooktanol i nærvær av 50#-ig, vandig natronlut. According to British patent no. 901,703, isooctyl-diphenyl phosphite can e.g. also produced by transesterification of triphenyl phosphite with isooctanol in the presence of 50% aqueous caustic soda.
Med alkaryl- og alkylgrupper substituerte fosfiter omtales i US-patent 2.968.670. Disse produkter kan enten fremstilles ved omsetning av mono- og dialkarylhalogenfosfiter med alkanoler i nærvær av aminbaser, som pyridin, ammoniakk, tertiære aminer eller alkalialkoholater, som natriummetylat, idet aminbasene resp. natriummetylat tjener som syreoppfanger. En ytterligere frems tillingsmulighet .er omforestringen av triarylfosfiter med alkoholer eller med i overskudd anvendt alkalialkoholater. Det nevnes i dette patent også at disse fosfiter kan inneholde mindre mengder av ■ tilsvarende triaryl- og trialkylfos-fiter, idet dette innhold altså erkarakterisertså lavt at en opprensning ikke var nødvendig. Phosphites substituted with alkaryl and alkyl groups are described in US patent 2,968,670. These products can either be prepared by reacting mono- and dialkylhalophosphites with alkanols in the presence of amine bases, such as pyridine, ammonia, tertiary amines or alkali alcoholates, such as sodium methylate, as the amine bases resp. sodium methylate serves as an acid scavenger. A further development possibility is the transesterification of triaryl phosphites with alcohols or with alkali alcoholates used in excess. It is also mentioned in this patent that these phosphites may contain smaller amounts of ■ corresponding triaryl and trialkyl phosphites, as this content is thus characterized as being so low that a purification was not necessary.
Fremgangsmåten i henhold til teknikkens stand resp. The procedure according to the state of the art or
de herved fremstilte fosfiter har følgende ulemper.the phosphites produced in this way have the following disadvantages.
Ved anvendelse av pyridin og tertiære aminer som halogenakseptorer kan disse såvel de dannede ammoniumsalter praktisk talt ikke fjernes fullstendig mer fra reaksjonspro-duktene, således at det til produktene etter en uheldig lukt som i industrihygienisk henseende medfører betraktelige ulemper. Lukten kan også henge ved stabiliserte sluttprodukter, hvilket begrenser deres anvendelsesområde. Ved anvendelsen av ammoniakk resp. mono- eller diaminer er det dessuten også i et visst omfang å regne med dannelsen av alkarylfosforamider som har til følge en nedsettelse av stabilisatorenes anvendelsestekniske egenskaper. When using pyridine and tertiary amines as halogen acceptors, these as well as the formed ammonium salts practically cannot be completely removed from the reaction products, so that the products leave an unpleasant smell which in terms of industrial hygiene entails considerable disadvantages. The smell can also linger in stabilized end products, which limits their area of application. When using ammonia or mono- or diamines, the formation of alkaryl phosphoramides can also be expected to a certain extent, which results in a reduction in the stabilisers' technical application properties.
Ved forsøk på å fjerne ammoniumsaltene ved ut-vaskning med vann, dannes ved hydrolytisk avbygning meget lett biprodukter, som likeledes betraktelig kan nedsette de dannede produkters stabiliseringsegenskaper. Sett samlet er disse fremgangsmåter dyre og uøkonomiske, spesielt også på grunn av de i større mengder dannede ammoniumsalter som må fjernes. When trying to remove the ammonium salts by washing out with water, by-products are very easily formed by hydrolytic decomposition, which can likewise considerably reduce the stabilization properties of the products formed. Taken together, these methods are expensive and uneconomical, especially also because of the ammonium salts formed in large quantities that must be removed.
Hvis alkalialkoholater anvendes som halogenhydrogen-akseptorer får man de ønskede fosfiter i lave utbytter og bare i sterkt forurenset form. If alkali alcoholates are used as halogen-hydrogen acceptors, the desired phosphites are obtained in low yields and only in heavily contaminated form.
Ved.omforestring av triarylfosfiter med alkoholer uten tilsetning av katalysatorer er det på grunn av den lille reaksjonshastighet nødvendig med en relativt høy reaksjonstemperatur. Ved disse temperaturer forløper imidlertid allerede i merkbart omfang bireaksjcner som f.eks. fosfonatdannelsen ved isomerisering. De således fremstilte fosfiter har derfor bare forminskede anvendelsestekniske egenskaper. In the transesterification of triaryl phosphites with alcohols without the addition of catalysts, a relatively high reaction temperature is necessary due to the low reaction rate. At these temperatures, however, secondary reactions such as e.g. the phosphonate formation by isomerization. The phosphites produced in this way therefore only have reduced technical application properties.
Ved omforestringen av triarylfosfiter med alkalialkoholater i overskudd kan de i reaksjonsblandingen opplaste alkalialkoholater resp. alkaliaryloater praktisk talt ikke fullstendig adskilles, således at fosfitene som er fremstillet således ved henstand tenderer til ofte flere ganger etterfellinger av faste produkter og derfor er å anse som ikke lagringsstabile. Heller ikke ved anvendelsen av katalytiske mengder av alkalialkoholater er denne ulempe å omgå. During the transesterification of triaryl phosphites with alkali alcoholates in excess, they can precipitate alkali alcoholates or alkali aryloates are practically not completely separated, so that the phosphites thus produced by standing tend to often precipitate several times solid products and are therefore to be regarded as not storage stable. Even when using catalytic amounts of alkali alcoholates, this disadvantage cannot be avoided.
Reaksjonen i nærvær av vandig natronlut har den ulempe at dannelsen av biprodukter, f.eks. mono- og difosfiter ikke kan hindres ved hydrolyse. Derved har de ønskede produkter ofte ikke noe tilstrekkelig anvendelsestekniske egenskaper. The reaction in the presence of aqueous caustic soda has the disadvantage that the formation of by-products, e.g. mono- and diphosphites cannot be prevented by hydrolysis. As a result, the desired products often do not have sufficient application technical properties.
Omforestringen av triarylfosfiter med alkanoler eller polyhydroksylalkaner kan foretas ifølge britisk patent nr. 1.204.141 også i nærvær av sure katalysatorer som f.eks. difenylfosfit. Denne fremgangsmåte har imidlertid to vesentlige ulemper: 1. Omforestringen gjennomføres vanligvis ved temperaturer over 200°C, idet allerede i merkbart omfang kan det forløpe bireaksjoner som de overnevnte fosfonatdannelser. 2. Den anvendte katalysator forblir i reaksjonsblandingen og kan ikke mere adskilles. Det er imidlertid kjent at difosfiter, spesielt difenylfosfit "på ingen måte har stabilitets-forbedrende virkning" (J. Voigt: "Die Stabilisierung der Kunststoffe gegen Licht und Wårme", Springer-Verlag, Berlin 1, første opplag, 1966, side 320-321), men derimot aksel-lerer avbygningen av PVC. The transesterification of triaryl phosphites with alkanols or polyhydroxyalkanes can be carried out according to British patent no. 1,204,141 also in the presence of acidic catalysts such as e.g. diphenyl phosphite. However, this method has two significant disadvantages: 1. The transesterification is usually carried out at temperatures above 200°C, as side reactions such as the above-mentioned phosphonate formations can already take place to a noticeable extent. 2. The used catalyst remains in the reaction mixture and can no longer be separated. It is known, however, that diphosphites, especially diphenyl phosphite "do not in any way have a stability-improving effect" (J. Voigt: "Die Stabilisierung der Kunststoffe gegen Licht und Wårme", Springer-Verlag, Berlin 1, first edition, 1966, page 320- 321), but on the other hand accelerates the degradation of PVC.
Dessuten endrer de i det nevnte patent omtalte polymere fosfiter under den hydrolytiske innvirkning av luft-fuktighet lett til harpikslignende, klebrige masser, som ved forarbeidelsen medfører vanskelig doserings- og fordelingspro-blemer. In addition, the polymeric phosphites mentioned in the aforementioned patent easily change under the hydrolytic effect of atmospheric moisture into resin-like, sticky masses, which during processing cause difficult dosing and distribution problems.
Oppfinnelsens oppgave er derfor å tilveiebringe blandinger av forskjellige substituerte fosfiter med forbedrede anvendelsestekniske egenskaper og som dessuten praktisk talt er katalysatorfri, luktfri, flytende og lagringsstabile. En ytterligere oppgave ifølge oppfinnelsen ligger i tilveiebringelsen av en enkel og økonomisk katalytisk omforestringsfremgangsmåte til fremstilling av disse blandinger, som med høye utbytter og korte reaksjonstider gir de ønskede produkter, idet de ovenfor omtalte ulemper unngås. The task of the invention is therefore to provide mixtures of various substituted phosphites with improved technical application properties and which are also practically catalyst-free, odorless, liquid and storage-stable. A further task according to the invention lies in the provision of a simple and economical catalytic transesterification method for the production of these mixtures, which with high yields and short reaction times gives the desired products, while avoiding the above-mentioned disadvantages.
En gjenstand ifølge oppfinnelsen er blandinger av forskjellige substituerte fosfiter, som inneholder hydrokarbonrester av alifatisk, cykloalifatisk og aromatisk karakter, idet blandingene består, referert til samlet fos forinnhold An object according to the invention is mixtures of various substituted phosphites, which contain hydrocarbon residues of aliphatic, cycloaliphatic and aromatic character, the mixtures consisting, referred to total phosphorus content
a) til 1 til 40 mol% av et fosfit med den generelle formel I a) to 1 to 40 mol% of a phosphite of the general formula I
1 5 3 . 1 5 3 .
hvori R , R" og R er like eller forskjellige og betyr en med wherein R, R" and R are the same or different and mean one with
lineært eller forgrenet alkyl, cykloalkyl, aryl eller aralkyl substituert fenylgruppe, idet karbontallet av de substituerte fenylgrupper minst utgjør 10, linear or branched alkyl, cycloalkyl, aryl or aralkyl substituted phenyl group, the carbon number of the substituted phenyl groups being at least 10,
b) til 1 til 40 mol% av et fosfit med den generelle formel II b) to 1 to 40 mol% of a phosphite of the general formula II
hvori R 4 , R3 5 og R 6er like eller forskjellige og betyr eventuelt med en eller flere oksygenatomer avbrutte lineære eller forgrenede alkyl eller alkenyl og usubstituert eller substituert cykloalkyl, cykloalkenyl, cykloalkylalkyl, cykloalkenylalkyl eller aralkyl, c) til 8 til 90 mol% av et fosfit med den generelle formel III hvori R"*" til R^ har den ovenfor angitte betydning og d) til 8 til 90 mol% av et fosfit med formel IV in which R 4 , R 3 5 and R 6 are the same or different and mean optionally with one or more oxygen atoms interrupted linear or branched alkyl or alkenyl and unsubstituted or substituted cycloalkyl, cycloalkenyl, cycloalkylalkyl, cycloalkenylalkyl or aralkyl, c) to 8 to 90 mol% of a phosphite of the general formula III in which R"*" to R^ has the meaning given above and d) to 8 to 90 mol% of a phosphite of the formula IV
hvori R"'" til R^ har' den ovenfor angitte betydning. in which R"'" to R^ have the meaning indicated above.
Molprosentangivelsene er å forstå således atThe mole percentage statements are to be understood as such that
summen av alle prosentuelle mengder av de fire komponenter I, II, III og IV kompletterer seg til 100. Videre kan disse blandinger inneholde mellom 0 og 5>fortrinnsvis mellom 0 og 3 vekt%, referert til samlet masse av et substituert fenol med formel R<1>OH,R<2>OH,R<3>OH eller blandinger herav, hvori R<1>til R^ har den tidligere angitte betydning. Fortrinnsvis fjernes imidlertid det ved fremstillingen dannede substituerte fenol ved destillering fullstendig eller til et lite restinnhold fra 0,005 til 0,5 vekt?. the sum of all percentage amounts of the four components I, II, III and IV add up to 100. Furthermore, these mixtures may contain between 0 and 5>preferably between 0 and 3% by weight, referred to the total mass of a substituted phenol of formula R <1>OH, R<2>OH, R<3>OH or mixtures thereof, in which R<1> to R^ have the previously stated meaning. Preferably, however, the substituted phenol formed during the preparation is removed by distillation completely or to a small residual content of 0.005 to 0.5% by weight.
Fortrinnsvis består blandingen til 1 til 30 mol%Preferably, the mixture consists of 1 to 30 mol%
av komponent I, til 1 til 25, spesielt 1 til 20 mol% av komponent II, til 18 til 80, spesielt 20 til 60 mol% av komponent III og til 18 til 80, spesielt 20 til 60 mol% av komponent IV. Videre inneholder den substituerte fenylgruppe fortrinnsvis minst 12, spesielt 12 til 30 og spesielt 12 til 24 karbonatomer. of component I, to 1 to 25, especially 1 to 20 mol% of component II, to 18 to 80, especially 20 to 60 mol% of component III and to 18 to 80, especially 20 to 60 mol% of component IV. Furthermore, the substituted phenyl group preferably contains at least 12, especially 12 to 30 and especially 12 to 24 carbon atoms.
Videre betyr fortrinnsvis i fosfitene med formel I til IVFurthermore, preferably means in the phosphites of formula I to IV
<4><6>rester.<4><6>leftovers.
R til R-^ samt restene R til R samme rester.R to R-^ and the residues R to R the same residues.
Substituentene i de substituerte fenylgrupper kan være bundet i ønskelig stilling, fortrinnsvis imidlertid i 2,4- eller 6-stillingene og 2,4- eller 4,6-stillingene. Det er foretrukket fenylgrupper med ikke mer enn to substituenter, spesielt imidlertid de med en substituent, som fortrinnsvis er bundet i parastilling. Fortrinnsvis er substituentene lineære eller forgrenede alkyl, cykloalkyl, fenyl eller fenylalkyl. En foretrukket undergruppe av restene R<1>til R^ i formlene I, III og IV er fenylgrupper substituert med ltil 18, spesielt 4 til 12 karbonatomer, cykloalkyl med 5 til 12 karbonatomer, fenyl eller fenylalkyl med 7 til 9 karbonatomer. The substituents in the substituted phenyl groups can be attached in the desired position, preferably, however, in the 2,4- or 6-positions and the 2,4- or 4,6-positions. Phenyl groups with no more than two substituents are preferred, especially those with one substituent, which is preferably attached in the para position. Preferably, the substituents are linear or branched alkyl, cycloalkyl, phenyl or phenylalkyl. A preferred subgroup of the radicals R<1> to R^ in formulas I, III and IV are phenyl groups substituted with 1 to 18, especially 4 to 12 carbon atoms, cycloalkyl with 5 to 12 carbon atoms, phenyl or phenylalkyl with 7 to 9 carbon atoms.
Eksempler på alkylgrupper er metyl,, etyl, propyl, i-propyl, butyl, i-butyl, t-butyl, pentyl, heksyl, oktyl, nonyl, dodecyl, pentadecyl, oktadecyl, eikosyl, pentacosyl, triakontyl. Spesielt foretrukkede rester er oktyl, nonyl, decyl og dodecyl. Examples of alkyl groups are methyl,, ethyl, propyl, i-propyl, butyl, i-butyl, t-butyl, pentyl, hexyl, octyl, nonyl, dodecyl, pentadecyl, octadecyl, eicosyl, pentacosyl, triacontyl. Particularly preferred residues are octyl, nonyl, decyl and dodecyl.
Eksempler for cykloalkyl er cyklopentyl, metyl-cyklopentyl, metyIcykloheksyl, trimetylcykloheksy1, cyklododecyl, cyklodecyl, cyklododecyl og spesielt cykloheksyl. Examples of cycloalkyl are cyclopentyl, methylcyclopentyl, methylcyclohexyl, trimethylcyclohexyl, cyclododecyl, cyclodecyl, cyclododecyl and especially cyclohexyl.
Eksempler for fenylalkyl er benzyl, a- eller 8-fenyletyl, a-,'B- eller y-fenylpropyl. Examples of phenylalkyl are benzyl, a- or 8-phenylethyl, a-,'B- or y-phenylpropyl.
4.6. 4.6.
R til R 1 fosfitene med formel II til IV kan eventuelt være med en eller flere oksygenatomer avbrutt, forgrenet eller lineært alkyl eller alkenyl. The R to R 1 phosphites of formulas II to IV may optionally have one or more oxygen atoms interrupted, branched or linear alkyl or alkenyl.
Fortrinnsvis inneholder alkyl eller alkenyl minstPreferably, alkyl or alkenyl contains at least
4 karbonatomer. Eksempler hertil er: Metyl, etyl, propyl, butyl ,. iso-butyl , n-oktyl, iso-oktyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, heksadecyl, heptadecyl, oktadecyl, eikosyl, trikosyl, triakontyl, butenyl, oktenyl, decenyl, dode-cenyl, heksadecenyl, oleyl. 4 carbon atoms. Examples of this are: Methyl, ethyl, propyl, butyl,. iso-butyl, n-octyl, iso-octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl, heptadecyl, octadecyl, eicosyl, tricosyl, triacontyl, butenyl, octenyl, decenyl, dodecenyl, hexadecenyl, oleyl.
Eksempler for med en eller flere oksygenatomer substituert alkyl er: Monoetere av glykoler som metoksyetyl, oktoksyetyl, dodecyloksyetyl, i-oktoksyety1, oktadecyloksyety1, 2-butoksy-propyl, 3-oktoksypropy1, 2-metoksybutyl, 1-butoksybuty1. Examples of alkyl substituted with one or more oxygen atoms are: Monoethers of glycols such as methoxyethyl, octoxyethyl, dodecyloxyethyl, i-octoxyethyl1, octadecyloxyethyl1, 2-butoxy-propyl, 3-octoxypropyl1, 2-methoxybutyl, 1-butoxybutyl1.
Monoetere av polyglykoler, som fortrinnsvis inneholder 2 til 15, spesielt 2 til 10 alkylenoksyenheter som metyl-, etyl-, propyl-, butyl-, heksyl-, oktyl-, i-oktyl-, decyl-, dodecyl-, oktadecyleter av polyetylen-, polypropylen og polybutylen- oksyder. Polypropylen- og polybutylenoksydenhetene kan være 1,2-, 1,3- eller 1,4-sammenknyttet. Monoethers of polyglycols, which preferably contain 2 to 15, especially 2 to 10 alkyleneoxy units such as methyl, ethyl, propyl, butyl, hexyl, octyl, i-octyl, decyl, dodecyl, octadecyl ether of polyethylene , polypropylene and polybutylene oxides. The polypropylene and polybutylene oxide units may be 1,2-, 1,3- or 1,4-linked.
Med cykloalkyl, cykloalkenyl, cykloalkylalkyl og cykloalkenylalkyl for R til R^ forstås også polycykliske rester. Foretrukket er cykloheksyl og trimetylcykloheksyl. Aralkyl betyr spesielt fenylalkyl. Disse rester kan også være substituert, fortrinnsvis med alkyl med 1 til 18, spesielt 1 Cycloalkyl, cycloalkenyl, cycloalkylalkyl and cycloalkenylalkyl for R to R^ also mean polycyclic residues. Cyclohexyl and trimethylcyclohexyl are preferred. Aralkyl means in particular phenylalkyl. These residues can also be substituted, preferably with alkyl with 1 to 18, especially 1
til 12 karbonatomer. Aralkylet kan også være substituert med cykloalkyl, fortrinnsvis cykloheksyl. Alkylenkjeden av cykloalkyl- og cykloalkenylalkyl og aralkyl inneholder fortrinnsvis 1 til 3 karbonatomer. to 12 carbon atoms. The aralkyl can also be substituted with cycloalkyl, preferably cyclohexyl. The alkylene chain of cycloalkyl and cycloalkenylalkyl and aralkyl preferably contains 1 to 3 carbon atoms.
I en foretrukket undergruppe er de usubstituerteIn a preferred subgroup, they are unsubstituted
og substituerte rester R^<1>til R^ i formlene II til IV alkyl eller alkenyl med 4 til 30, fortrinnsvis 8 til 24, spesielt 10 til 18 karbonatomer, cykloalkyl med 5 til 12 karbonatomer, and substituted residues R^<1>to R^ in the formulas II to IV alkyl or alkenyl with 4 to 30, preferably 8 to 24, especially 10 to 18 carbon atoms, cycloalkyl with 5 to 12 carbon atoms,
cykloalkylalkyl, cykloalkenyl og cykloalkenylalkyl med 6 tilcycloalkylalkyl, cycloalkenyl and cycloalkenylalkyl with 6 to
12 karbonatomer og aralkyl med 7 til 25, fortrinnsvis 7 til 19 karbonatomer. 12 carbon atoms and aralkyl with 7 to 25, preferably 7 to 19 carbon atoms.
4.6 Eksempler for R til R er: cyklopentyl, metyl-cyklopentyl, cykloheksyl, cykloheksenyl, metylcykloheksyl, etylcykloheksyl, 3,3,5_trimetylcykloheksyl, 4-t-butylcykloheksyl, oktylcykloheksy1, nonylcykloheksy1, dodecylcykloheksyl, okta-decy lcyklbheksyl , metylcykloheksenyl, oktylcyklohekseny1, cyklopentyl, cyklooktyl, cyklooktenyl, cyklodecyl, norbornyl, tricyklo-1,4<1->5,9°-decylmetyl, bicyklo-2,2,1-heptyl, bicyklo-2,2,2-oktyl, cyklododecy1, cyklopentylmetyl, metylcyklopenty1-etyl, cykloheksylmetyl, cykloheksenylmety1, etylcykloheksyletyl, oktylcykloheksyImety1, dodecylcykloheksylmety1, (bicyklo-2,2,1-hepten-2,3-yl)-6-metyl, tricyklo-1,4 -5,9°-decylmety1, benzyl, a- og 6-fenyletyl, 3~fenylpropyl, 2-fenyIpropylideny1, naftyl-.metyl, metylbenzyl, etylbenzyl, isopropylbenzy1, butylbenzyl, t-'butylbenzy1, oktylbenzyl, dodecylbenzyl, metylfenyletyl, B-metylfenylpropyl. 4.6 Examples for R to R are: cyclopentyl, methylcyclopentyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, ethylcyclohexyl, 3,3,5_trimethylcyclohexyl, 4-t-butylcyclohexyl, octylcyclohexy1, nonylcyclohexy1, dodecylcyclohexyl, octadecylcyclohexyl, methylcyclohexenyl, octylcyclohexeny1, cyclopentyl , cyclooctyl, cyclooctenyl, cyclodecyl, norbornyl, tricyclo-1,4<1->5,9°-decylmethyl, bicyclo-2,2,1-heptyl, bicyclo-2,2,2-octyl, cyclododecy1, cyclopentylmethyl, methylcyclopenty1 -ethyl, cyclohexylmethyl, cyclohexenylmethyl, ethylcyclohexylethyl, octylcyclohexylmethyl, dodecylcyclohexylmethyl, (bicyclo-2,2,1-hepten-2,3-yl)-6-methyl, tricyclo-1,4 -5,9°-decylmethyl, benzyl, a- and 6-phenylethyl, 3~phenylpropyl, 2-phenylIpropylideny1, naphthyl-.methyl, methylbenzyl, ethylbenzyl, isopropylbenzy1, butylbenzyl, t-'butylbenzy1, octylbenzyl, dodecylbenzyl, methylphenylethyl, B-methylphenylpropyl.
Blandingene ifølge oppfinnelsen fåes ved hjelp av en ny fremgangsmåte ved omforestring av triarylfosfiter med alkoholer i nærvær av en basisk katalysator. En ytterligere gjenstand for oppfinnelsen er følgelig en fremgangsmåte til fremstilling av blandingen ifølge oppfinnelsen ved omforestring av substituerte trifenylfosfiter med formel I eller blandinger herav med en eller flere alkoholer med formlene R 4 OH, R-<S>^O<H>eller The mixtures according to the invention are obtained by means of a new method by transesterification of triaryl phosphites with alcohols in the presence of a basic catalyst. A further object of the invention is consequently a method for producing the mixture according to the invention by transesterification of substituted triphenylphosphites of formula I or mixtures thereof with one or more alcohols of the formulas R 4 OH, R-<S>^O<H>or
6 . i) t-n D6 ..6. i) t-n D6 ..
R OHj hvori R til a har samme betydning som tidligere angittR OHj in which R to a have the same meaning as previously indicated
i nærvær av en basisk katalysator ved temperaturer over 50°Cin the presence of a basic catalyst at temperatures above 50°C
og fjerning av det eller de dannede fenoler ved destillering, idet fremgangsmåten erkarakterisert vedat det som katalysator anvendes 0,001 til 5 mo 15?, referert til det substituerte trifenylfosfit av et alkali- eller jordalkaliamid, idet katalysatoren eller dets følgeprodukter frafiltreres før eller etter destilleringen samt de ved denne fremgangsmåte fremstilte blandinger. and removal of the phenol or phenols formed by distillation, the method being characterized by using as catalyst 0.001 to 5 mo 15?, referred to the substituted triphenyl phosphite of an alkali or alkaline earth amide, the catalyst or its by-products being filtered off before or after the distillation as well as the mixtures produced by this method.
Egnede katalysatorer er litiumamid, natriumamid, kaliumamid, rubidiumamid, magnesiumamid-, kalsiumamid, strontium-amid, bariumamid. Foretrukket er alkaliamidene, spesielt natriumamid og spesielt litiumamid. Fortrinnsvis anvendes 0,01 til 3 mol% katalysator. Suitable catalysts are lithium amide, sodium amide, potassium amide, rubidium amide, magnesium amide, calcium amide, strontium amide, barium amide. Preferred are the alkali amides, especially sodium amide and especially lithium amide. Preferably, 0.01 to 3 mol% catalyst is used.
De som utgangsprodukter anvendte substituerte fenylfosfiter fåes på kjent måte ved omsetning av de tilsvarende fenoler med fosfortriklorid under fjerning' av det dannede hydrogenklorid. Hvis det herved anvendes en blanding av fenoler får man fosfiter med forskjellige substituerte fenylgrupper som utgangsprodukter. Alkoholene med formel R OH er enten opp-nåelige i handelen eller fremstillbare etter kjente fremgangsmåter.. The substituted phenylphosphites used as starting products are obtained in a known manner by reacting the corresponding phenols with phosphorus trichloride while removing the hydrogen chloride formed. If a mixture of phenols is used in this way, phosphites with different substituted phenyl groups are obtained as starting products. The alcohols with the formula R OH are either commercially available or can be prepared according to known methods.
I detalj kan fremgangsmåten ifølge oppfinnelsen utføres således at man i de hertil vanlige innretninger blander et substituert fosfit med formel I med minst en alkohol med formel R^OH, R<5>0H eller R<6>0H og et alkali- eller jordalkaliamid som katalysator og deretter omforestrer ved temperaturer fra 50 til 200°C, fortrinnsvis 100 til l60oc. Reaksjonen kan gjennomføres i vakuum ved normalt- eller overtrykk eller med eller uten inerte oppløsningsmidler. Det resp. de dannede substituerte fenoler med formlene R 1 OH, R POH og R^OH kan avdestilleres løpende under reaksjonen fra reaksjonsblandingen eller først etter avslutning av reaksjonen. Fortrinnsvis fjernes det dannede fenol fullstendig eller inntil et restinnhold fra 0,005 til 0,5 vekt/?, referert til den samlede blanding. Det kan imidlertid også bli tilbake mellom 0 til 5 vekt/? av fenolet i den samlede blanding. Reaksjonstidene er på grunn av den overraskende høye katalytiske aktivitet av alkali- og jord-alkaliamidene relativt lav og utgjør vanligvis mellom 1 til 10 timer.. Ved omforestringsreaksjonen fåes prinsippielle bland inger. Mengdeforholdene av de to utgangskomnonenter fosfit med formel I og alkohol med formel R OH retter seg derfor i det vesentlige etter den ønskede sammensetning i sluttproduktet. Hvis det pr. mol fosfit anvendes omtrent 1 mol alkohol vil fosfitene med formel IV mengdemessig overveie og når det pr. mol fosfit omtrent anvendes 2 mol alkohol vil fosfitene med formel III mengdemessig overveie. Fortrinnsvis anvendes pr. mol fosfit 0,5 til 2,5, spesielt 1 til 2 mol alkohol. In detail, the method according to the invention can be carried out such that, in the usual devices for this, a substituted phosphite of formula I is mixed with at least one alcohol of formula R^OH, R<5>0H or R<6>0H and an alkali or alkaline earth amide which catalyst and then transesterifies at temperatures from 50 to 200°C, preferably 100 to 160°C. The reaction can be carried out in vacuum at normal or positive pressure or with or without inert solvents. That resp. the formed substituted phenols with the formulas R 1 OH, R POH and R^OH can be distilled off continuously during the reaction from the reaction mixture or only after completion of the reaction. Preferably, the phenol formed is removed completely or up to a residual content of from 0.005 to 0.5 wt%, referred to the overall mixture. However, it can also remain between 0 and 5 weight/? of the phenol in the overall mixture. Due to the surprisingly high catalytic activity of the alkali and alkaline earth amides, the reaction times are relatively low and usually amount to between 1 and 10 hours. In the transesterification reaction, basic mixtures are obtained. The quantity ratios of the two starting components phosphite with formula I and alcohol with formula R OH are therefore essentially based on the desired composition in the final product. If it per mol of phosphite is used approximately 1 mol of alcohol, the phosphites with formula IV will predominate in terms of quantity and when there is per moles of phosphite approximately 2 moles of alcohol are used, the phosphites of formula III will predominate in terms of quantity. Preferably used per moles of phosphite 0.5 to 2.5, especially 1 to 2 moles of alcohol.
De faste katalysatorresiduer, hvor det også kan dreie seg om følgeprodukter av reaksjonen av katalysatoren med de tilstedeværende reaksjonsdeltagere fjernes vanligvis etter destillasjonen av det under tiden som oppløsningsmiddel virkende dannede fenol med formel R<1>OH ved filtrering praktisk talt fullstendig. Fortrinnsvis medanvendes herved filtreringshjelpe-midler som aktivkull og blekjord. The solid catalyst residues, which may also be by-products of the reaction of the catalyst with the reaction participants present, are usually removed after the distillation of the phenol of formula R<1>OH formed in the meantime acting as a solvent by practically complete filtration. Filtering aids such as activated charcoal and bleached earth are preferably also used here.
På grunn av den overraskende høye og spesifikke katalysatorvirkning av de ifølge oppfinnelsen ved omforestrings-fremgangsmåten anbragte katalysatorer fåes i løpet av korte reaksjonstider i høye utbytter de .ønskede rene f osf itblandinger, da den samlede reaksjon er fri for bireaksjoner som kunne føre til forurensede og dermed til ikke luktløse sluttprodukter. I mange tilfeller betinger nettopp slike biprodukter en merkelig lukt. En overraskende og vesentlig fordel er at den anvendte katalysator resp. dens følgeprodukt praktisk talt igjen fullstendig kan fjernes på enkel måte fra de ønskede produkter. Sluttproduktene er derfor lagringsstabile og viser ingen vanske-lige filtrerbare etterutfellinger og uklarheter som eksempelvis ethvert produkt som fremstilles med natriumalkoholater som katalysator. Due to the surprisingly high and specific catalyst effect of the catalysts placed according to the invention in the transesterification process, the desired pure phosphite mixtures are obtained in high yields within short reaction times, as the overall reaction is free of side reactions that could lead to contaminated and thus to non-odorless end products. In many cases, precisely such by-products cause a strange smell. A surprising and significant advantage is that the used catalyst resp. its by-product practically again completely can be easily removed from the desired products. The end products are therefore storage-stable and show no difficult-to-filter after-precipitations and turbidities like, for example, any product produced with sodium alcoholates as a catalyst.
Fosfitblandingene ifølge oppfinnelsen er klare, delvis viskose væsker. De er praktisk talt katalysatorfrie, lagringsstabile og luktløse, hvilket medfører betraktelige fordeler, såvel i anvendelsesteknisk som industrihygienisk henseende. Videre har de en fremragende stabiliserende virkning i organiske substrater som overraskende overtreffer virkningen av mange kjente og sammenlignbare fosfiter. Videre viser blandingen ifølge oppfinnelsen på tross av et lite fosforinnhold overraskende i PVC en jevn og forbedret kostabiliseren.de virkning sammenlignet til kjente fenylalkylfosfiter. The phosphite mixtures according to the invention are clear, partly viscous liquids. They are practically catalyst-free, storage-stable and odorless, which entails considerable advantages, both in terms of application technology and industrial hygiene. Furthermore, they have an outstanding stabilizing effect in organic substrates which surprisingly surpasses the effect of many known and comparable phosphites. Furthermore, despite a small phosphorus content in PVC, the mixture according to the invention surprisingly shows a uniform and improved cost-stabilizing effect compared to known phenylalkyl phosphites.
Som substrater som skal stabiliseres kommer det eksempelvis på tale: 1. Polymerejsom avleder seg fra enkle eller dobbelt umettede hydrokarboner, som polyolefiner, som f.eks. polyetylen, som eventuelt kan være nettdannet, polypropylen, polyisobutylen, polymetylbuten-1, polyme£ylpenten-l, polybuten-1, polyisopren, polybutadien, polystyren, polyisobutylen, kopolymere av de til de nevnte homopolymere til grunn liggende monomere, som etylen-propylen-kopolymere, propylen-buten-l-kopolymere, propylen-isobutylen-kopolymere, styren-butadien-kopolymere samt terpolymere av etylen og propylen med et dien, som f.eks. heksadien, dicyklopentadien eller etylidennorbornen, blandinger av de overnevnte homopolymere, som eksempelvis blandinger av polypropylen og polyetylen, polypropylen og poly-buten-1.polypropylen og polyisobutylen. 2. Halogenholdige vinylpolymere, som polyvinylklorid, polyvinylidenklorid, polyvinylfluorid, men også polykloropren• og klorkautsjuker. 3. Polymere, som avleder seg fra a,8-umettéde syrer og deres derivater, som polyakrylater og polymetakrylater, polyakrylamider og polyakrylnitriler samt deres kopolymere med andre vinylf orbinde.lser, som akrylnitril/butadien/styren, akryl-nitrii/styren og akrylnitril/styren/akrylester-kopolymerisater. 4. Polymere,.som avleder seg fra umettede alkoholer og aminer resp. deres acylderivater eller acetaler, som poly-vinylalkohol, polyvinylacetat-, -stearat, -benzoat, -maleat, polyvinylbutyral, polyallylftalat, polyallylmelamin og deres kopolymere med andre vinylforbindelser som etylen/vinylacetat-kopolymere. Substrates to be stabilized include, for example: 1. Polymers derived from simple or doubly unsaturated hydrocarbons, such as polyolefins, such as e.g. polyethylene, which may optionally be cross-linked, polypropylene, polyisobutylene, polymethylbutene-1, polymethylpentene-1, polybutene-1, polyisoprene, polybutadiene, polystyrene, polyisobutylene, copolymers of the monomers underlying the aforementioned homopolymers, such as ethylene-propylene -copolymers, propylene-butene-1-copolymers, propylene-isobutylene copolymers, styrene-butadiene copolymers and terpolymers of ethylene and propylene with a diene, such as e.g. hexadiene, dicyclopentadiene or ethylidene norbornene, mixtures of the above-mentioned homopolymers, such as, for example, mixtures of polypropylene and polyethylene, polypropylene and poly-butene-1.polypropylene and polyisobutylene. 2. Halogen-containing vinyl polymers, such as polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, but also polychloroprene• and chlorinated rubbers. 3. Polymers derived from α,8-unsaturated acids and their derivatives, such as polyacrylates and polymethacrylates, polyacrylamides and polyacrylonitriles as well as their copolymers with other vinyl compounds, such as acrylonitrile/butadiene/styrene, acrylonitrile/styrene and acrylonitrile /styrene/acrylic ester copolymers. 4. Polymers, which are derived from unsaturated alcohols and amines or their acyl derivatives or acetals, such as polyvinyl alcohol, polyvinyl acetate, stearate, benzoate, maleate, polyvinyl butyral, polyallyl phthalate, polyallyl melamine and their copolymers with other vinyl compounds such as ethylene/vinyl acetate copolymers.
5. Polyfenylenoksyder.5. Polyphenylene oxides.
6. Polyuretaner og polyurinstoffer.6. Polyurethanes and polyureas.
7. Polykarbonater.7. Polycarbonates.
8. Polysulfoner.8. Polysulfones.
9. Polyamider og kopolyamider, som avleder seg fra diaminer og dikarboksylsyrer og/eller fra aminokarboksylsyrer eller de tilsvarende laktamer, som polyamid 6, polyamid 6/6, polyamid 6/10, polyamid 11, polyamid 12. 10. Polyestere, som avleder seg fra dikarboksylsyrer og dialkoholer og/eller fra hydroksykarboksylsyrer eller de tilsvarende laktoner som polyetylenglykoltereftalat, poly-1,4-di- 9. Polyamides and copolyamides, which derive from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, such as polyamide 6, polyamide 6/6, polyamide 6/10, polyamide 11, polyamide 12. 10. Polyesters, which derive from dicarboxylic acids and dialcohols and/or from hydroxycarboxylic acids or the corresponding lactones such as polyethylene glycol terephthalate, poly-1,4-di-
metylol-cykloheksantereftalat, poly-1,4-butylentereftalat.methylol cyclohexane terephthalate, poly-1,4-butylene terephthalate.
11. Nettdannede polymerisater som avleder seg fra al-dehydet på den ene side og fenoler, urinstoffer og melaminer på den annen side, som fenol-formaldehyd-, urinstoff-formaldehyd- og melamin-formaldehydharpikser. 12. Alkylharpikser, som glycerol-ftalsyre-harpikser og deres blandinger med melamin-formaldehydharpikser. 13- Umettede polyesterharpikser, som avleder seg fra kopolyestere av mettede- og umettede dikarboksylsyrer med fler-verdige alkoholer, samt vinylforbindelser som nettdannelses-midler, som også deres halogenholdige, tungt brennbare modifi-kasjoner. 14. Naturlige polymere, som cellulose, gummi, samt deres polymerhomologt kjemisk modifiserte derivater, som cellu-loseacetater, -propionater og -butyrater resp. celluloseetrene som metylcellulose. 11. Network-formed polymers deriving from the aldehyde on the one hand and phenols, ureas and melamines on the other, such as phenol-formaldehyde, urea-formaldehyde and melamine-formaldehyde resins. 12. Alkyl resins, such as glycerol-phthalic acid resins and their mixtures with melamine-formaldehyde resins. 13- Unsaturated polyester resins, which derive from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols, as well as vinyl compounds as network-forming agents, as well as their halogen-containing, highly flammable modifications. 14. Natural polymers, such as cellulose, rubber, as well as their polymer-homologously chemically modified derivatives, such as cellulose acetates, -propionates and -butyrates resp. the cellulose ethers such as methyl cellulose.
±5- ■ Naturlige og syntetiske organiske stoffer, som danner rene monomere forbindelser eller blandinger av slike, eksempelvis mineralolje, dyrisk fett og plantefett, olje og voks, eller olje, voks og fett på basis av syntetiske estere, samt blandinger av syntetiske estere med mineraloljer i ønskelig vektsforhold. ±5- ■ Natural and synthetic organic substances, which form pure monomeric compounds or mixtures of such, for example mineral oil, animal fat and vegetable fat, oil and wax, or oil, wax and fat based on synthetic esters, as well as mixtures of synthetic esters with mineral oils in the desired weight ratio.
Foretrukket er gruppene 1, 2, 9 og 10. Groups 1, 2, 9 and 10 are preferred.
Blandingene ifølge oppfinnelsen innforlives i substratene i en konsentrasjon på 0,005 til 5 vekti, beregnet på materialet som skal stabiliseres. The mixtures according to the invention are incorporated into the substrates in a concentration of 0.005 to 5 by weight, calculated on the material to be stabilized.
Fortrinnsvis innarbeides 0,01 til 1,0 spesielt foretrukket 0,02 til 0,5 vekt% av forbindelsene, beregnet på materialet som skal stabiliseres i dette. Innarbeidelsen kan eksempelvis foregå ved innblanding av blandingen ifølge oppfinnelsen og eventuelt ytterligere additiver etter de i teknikken vanlige metoder før eller under formgivning eller også ved på-føring av de oppløste eller dispergerte forbindelser på den polymere, eventuelt under etterfølgende fordampning av oppløs-ningsmidlet. Preferably, 0.01 to 1.0, particularly preferably 0.02 to 0.5% by weight of the compounds are incorporated, calculated on the material to be stabilized therein. The incorporation can, for example, take place by mixing in the mixture according to the invention and possibly further additives according to the methods common in the art before or during shaping or also by applying the dissolved or dispersed compounds to the polymer, possibly during subsequent evaporation of the solvent.
I tilfellet av nettdannet polyetylen tils'ettes blandingene før nettdannelsen. In the case of crosslinked polyethylene, the mixtures are added prior to crosslinking.
Blandingene ifølge oppfinnelsen kan også tilsettes før eller under polymerisasjonen, idet det ved en mulig innbyg-ning i polymerkjeden kan fåes stabiliserte substrater, hvori The mixtures according to the invention can also be added before or during the polymerisation, since a possible incorporation into the polymer chain can result in stabilized substrates, in which
stabilisatoren ikke er flyktig- eller ekstraherbar.the stabilizer is not volatile or extractable.
De ifølge oppfinnelsen stabiliserte organiske materialer kan også inneholde ytterligere tilsetninger. Som eksempler på ytterligere additiver, hvormed sammen stabilisa-torene kan anvendes er å nevne: Antioksydanter, lysbeskyttel-lsesmidler, metalldesaktivatorer, peroksydødeleggende forbindelser, polyamidstabilisatorer, basiske kostabilisatorer, PVC-stabilisatorer, nukleringsmidler og urinstoffderivater som er omtalt i DOS 2.427.853, side 15 til 25. Ytterligere mulige tilsetninger er mykningsmidler, glidemidler, emulgatorer, fy 11-stoffer som sot, asbest, kaolin, talkum-og glassfibre, pigmenter, optiske lysgjørere, flammebeskyttelsesmidler, anti-statika. The organic materials stabilized according to the invention can also contain further additives. Examples of further additives with which the stabilizers can be used are: Antioxidants, light protection agents, metal deactivators, peroxide-destroying compounds, polyamide stabilizers, basic co-stabilizers, PVC stabilizers, nucleating agents and urea derivatives, which are mentioned in DOS 2,427,853, page 15 to 25. Further possible additives are emollients, lubricants, emulsifiers, fy 11 substances such as soot, asbestos, kaolin, talc and glass fibres, pigments, optical brighteners, flame retardants, anti-static agents.
Posfitblandingen ifølge oppfinnelsen egner seg spesielt fremragende til beskyttelse mot nedbrytning med. varme-eller lysinnvirkning av klorholdige termoplaster, som inneholder barium-, kadmium-, kalsium-, sink- eller blykarboksylater eller -fenolater eller blandinger herav som primærstabilisatorer. Vanligvis innblandes blandingen ifølge oppfinnelsen til de tidligere nevnte kunststoffer i mengder fra 0,05 til 3, fortrinnsvis 0,1 til 1,5 vekt/?, referert til samlet masse. En ytterligere- gjenstand i henhold til oppfinnelsen er denne kunststoff-blanding. Primærstabilisatoren innblandes vanligvis i mengder på 0,05 til 5, fortrinnsvis 0,2 til 3 vekt$, referert til den samlede masse. Karboksylatgruppen inneholder fortrinnsvis 6-22 karbonatomer og fenolatgruppen 8 til 24 karbonatomer. The posfit mixture according to the invention is particularly well suited for protection against degradation with. heat or light exposure of chlorine-containing thermoplastics, which contain barium, cadmium, calcium, zinc or lead carboxylates or phenolates or mixtures thereof as primary stabilizers. Usually, the mixture according to the invention is mixed into the previously mentioned plastics in amounts of from 0.05 to 3, preferably 0.1 to 1.5, by weight, referred to total mass. A further object according to the invention is this synthetic material mixture. The primary stabilizer is usually incorporated in amounts of 0.05 to 5, preferably 0.2 to 3, by weight, referred to the total mass. The carboxylate group preferably contains 6-22 carbon atoms and the phenolate group 8 to 24 carbon atoms.
Som klorholdige termoplaster skal det nevnes: Polyvinylidenklorid og fortrinnsvis polymere av eller på grunnlag av vinylklorid. Som slike kommer det på tale E-, S- og M-PVC, idet polyvinylkloridet også kan være mykningsmiddelholdig eller etterklorert. Et ytterligere eksempel er klorerte polyolefiner som av polyetylen og polypropylen. Som komonomere for termoplaster på grunnlag av vinylklorid skal det nevnes: Vinyli-denklorid, transdikloreten, etylen, propylen, butylen, malein-syre, akrylsyre, fumarsyre, itakonsyre resp. deres alkylester eller vinylacetat. Også blandinger av polymere som PVC/MBS/ABS eller PVC/vinylacetat kan stabiliseres. Chlorine-containing thermoplastics include: Polyvinylidene chloride and preferably polymers of or based on vinyl chloride. As such, we are talking about E-, S- and M-PVC, as the polyvinyl chloride can also contain plasticizer or post-chlorination. A further example is chlorinated polyolefins such as polyethylene and polypropylene. As comonomers for thermoplastics based on vinyl chloride, the following should be mentioned: Vinylidene chloride, transdichloroethene, ethylene, propylene, butylene, maleic acid, acrylic acid, fumaric acid, itaconic acid or their alkyl ester or vinyl acetate. Mixtures of polymers such as PVC/MBS/ABS or PVC/vinyl acetate can also be stabilized.
Før, under eller etter tilsetning av stabilisatoren ifølge oppfinnelsen kan det alt etter formmassens anvendelses-formål 'tilsettes ytterligere tilsetninger som glidemiddel, for trinnsvis montanvoks, epoksyderte oljer eller glycerolestere, fyllstoffer, forsterkende fyllstoffer som glassfibre, modifika-torer som f.eks. slagseigtilsetninger, lysbeskyttelsesmidler, antioksydanter og/eller pigmenter. Innforlevningen av alle tilsetninger og forarbeidelsen av de termoplastiske kunststoff-masser foregår med de i teknikken vanlige metoder. Before, during or after the addition of the stabilizer according to the invention, depending on the intended use of the molding compound, additional additives such as lubricants, for stages montan wax, epoxidized oils or glycerol esters, fillers, reinforcing fillers such as glass fibers, modifiers such as e.g. impact strength additives, light protection agents, antioxidants and/or pigments. The incorporation of all additives and the processing of the thermoplastic plastic masses takes place using the methods common in the art.
Fosfiten ifølge oppfinnelsen er fremragende egnet direkte å tilblandes ønskelige flytende stabilisatorer på basis av f.eks. barium-, k&dmium-, sink- eller bly-karboksylater og/eller -fenolater som ko-stabilisator. The phosphite according to the invention is eminently suitable to be mixed directly with desirable liquid stabilizers on the basis of e.g. barium, potassium, zinc or lead carboxylates and/or phenolates as co-stabilizer.
Slike stabilisator-kombinasjoner er praktisk talt luktfrie og derfor i anvendelse mere fordelaktig enn stabili-satorsystemer som fremstilles med de handelsvanlige luktintensive fosfiter.. Such stabilizer combinations are practically odorless and therefore in use more advantageous than stabilizer systems which are produced with the commercially available odor-intensive phosphites.
Oppfinnelsen skal forklares nærmere ved hjelp av noen eksempler. Prosenter er her vektprosenter og deler vektdeler, hvis intet annet er bemerket. De prosentuelle mengder, av elementene karbon, hydrogen og fosfor bestemmes ved elemen-tæranalyse. The invention will be explained in more detail with the help of some examples. Percentages here are percentages by weight and parts by weight, if nothing else is noted. The percentage amounts of the elements carbon, hydrogen and phosphorus are determined by elemental analysis.
Eksempel 1.Example 1.
689 g (1 mol) tris-nonylfenylfosfit, som på kjent måte ble fremstillet av 1 mol fosfortriklorid og 3 mol nonylfenol,'biandes etter fjerning av dannet hydrogenklorid i den med nitrogen spylte reaksjonsapparatur bestående av en trehalset kolbe med rører, termometer, destillasjonsbro og forlagskolbe med 214 g (1 mol) tetradekanol og 0,7 g (0,03 mol) litiumamid og oppvarmes under omrøring i løpet av 1 time ved 120-130°C. Reaksjonsblandingen omrøres 5 timer ved denne temperatur og deretter fjernes det ved omforestringen frigjorte nonylfenol ved vakuumdestillering (Tg maks. 190°C/p under eller lik 1 mm Hg) fra reaks j onsblandingen. Det. gjenblivende residu blandes med litt aktivkull og blekjord og filtreres etter avkjøling. Utbytte: 656 g (96$ av det teoretiske) av en lysegul klar 689 g (1 mol) of tris-nonylphenylphosphite, which was prepared in a known manner from 1 mol of phosphorus trichloride and 3 mol of nonylphenol, is combined after removal of formed hydrogen chloride in the nitrogen-flushed reaction apparatus consisting of a three-necked flask with stirrer, thermometer, distillation bridge and flask with 214 g (1 mol) tetradecanol and 0.7 g (0.03 mol) lithium amide and heated with stirring during 1 hour at 120-130°C. The reaction mixture is stirred for 5 hours at this temperature and then the nonylphenol released during the transesterification is removed by vacuum distillation (Tg max. 190°C/p below or equal to 1 mm Hg) from the reaction mixture. The. the remaining residue is mixed with a little activated carbon and bleached earth and filtered after cooling. Yield: 656 g ($96 of the theoretical) of a pale yellow clear
væske: n^ P 1,5036.liquid: n^ P 1.5036.
Eksempel 2. (Sammenligningseksempel). Example 2. (Comparison example).
I en med nitrogen spylt reaksjonsapparatur (sammenlign eksempel 1) oppvarmes 689 g (1 mol) tris-nonylfenylfosfit, 429 g (2 mol) tetradecylalkohol og 3 g (0,06 mol) natriummetylat som katalysator i løpet av 1 time ved 120-130°C, om-røres 5 timer ved denne temperatur og deretter underkastes en vakuumdestillering (Tg maks. 190°C/p under eller lik 1 mm Hg) for å fjerne nonylfenol. Residuet blandes med aktivkull og blekjord og filtreres etter avkjøling. Det dannede filtrat viser etter lengere henstand igjen sterke uklarhetsforeteelser, som bare vanskelig er å fjerne ved ytterligere filtreringer. In a nitrogen-flushed reaction apparatus (compare example 1), 689 g (1 mol) of tris-nonylphenyl phosphite, 429 g (2 mol) of tetradecyl alcohol and 3 g (0.06 mol) of sodium methylate as catalyst are heated during 1 hour at 120-130 °C, stirred for 5 hours at this temperature and then subjected to a vacuum distillation (Tg max. 190°C/p below or equal to 1 mm Hg) to remove nonylphenol. The residue is mixed with activated charcoal and bleached earth and filtered after cooling. After a longer period of time, the formed filtrate again shows strong turbidity phenomena, which are only difficult to remove by further filtrations.
Utbytte: 609 g ( 90% av det teoretiske) av en lysegul væske: Yield: 609 g (90% of theoretical) of a pale yellow liquid:
N<20>1,4836. N<20>1.4836.
Eksempel 3- Example 3-
619 g (3 mol) oktylfenol blandes i en reaksjonsapparatur bestående av 4-halset kolbe,.rører, termometer, dryppe-trakt og tilbakeløpskjøler under nitrogen med 137,5 g (1 mol) f osf ortriklorid og oppvarmes under omrøring langsomt til 55°C.. Etter avslutning av hydrogenkloridutviklingen omrøres reaksjonsblandingen 1 time ved 100°C og 11 timer ved l60°C. Ved etterfølgende v.akuumbehandling ved 150-l60°C70 ,15 mm Hg fjernes resterende hydrogenklorid og ikke omsatt oktylfenol (53 g tilsvarende 8,5$ av den anvendte mengde). Det dannede tris-oktyl-fenylfosfit 592 g (0,9 mol) blandes etter utveksling av til-bakeløpskjøleren med en destillasjonsbro med forlagskolben med 195 g (0,9 mol) tetradecylalkohol og 1,1 g (0,05 mol) litiumamid som katalysator, oppvarmes i løpet av en time til l60°C og omrøres-8 timer ved denne temperatur. Det ved omforestringen dannede oktylfenol destilleres deretter av i vakuum (Tg maks. l80°C/p er lik eller under 1 mm Hg). Residuet filtreres etter tilsetning av aktivkull og blekjord. 619 g (3 mol) of octylphenol are mixed in a reaction apparatus consisting of a 4-necked flask, stirrer, thermometer, dropping funnel and reflux condenser under nitrogen with 137.5 g (1 mol) of phosphorus trichloride and heated while stirring slowly to 55° C.. After completion of hydrogen chloride evolution, the reaction mixture is stirred for 1 hour at 100°C and 11 hours at 160°C. During subsequent vacuum treatment at 150-160°C70.15 mm Hg, residual hydrogen chloride and unreacted octylphenol are removed (53 g corresponding to 8.5% of the amount used). The formed tris-octyl-phenyl phosphite 592 g (0.9 mol) is mixed after exchanging the reflux condenser with a distillation bridge with the original flask with 195 g (0.9 mol) of tetradecyl alcohol and 1.1 g (0.05 mol) of lithium amide as catalyst, is heated during one hour to 160°C and stirred for 8 hours at this temperature. The octylphenol formed during the transesterification is then distilled off in vacuum (Tg max. 180°C/p is equal to or below 1 mm Hg). The residue is filtered after adding activated charcoal and bleached earth.
Utbytte: 58l g ( 97% av det teoretiske referert til tris-oktyl-fenylfosfit) av en lysegul viskos væske: nn<20>1,5077. Yield: 58l g (97% of theoretical referred to tris-octyl-phenylphosphite) of a pale yellow viscous liquid: nn<20>1.5077.
Eksempel ' 4 - 30. Example ' 4 - 30.
Ytterligere aryl-alkylfosfitblandinger, som er opp-■ stillet i tabell 1 ble fremstillet analogt eksempel 1 eller ek sempel 3j idet. destillasjonstemperaturene alt etter de anvendte fenoler ligger mellom 176 og 190°C. Further aryl-alkyl phosphite mixtures, which are set out in Table 1, were prepared analogously to Example 1 or Example 3j. the distillation temperatures, depending on the phenols used, are between 176 and 190°C.
Eksempel 42. Example 42.
En blanding av tris-nonylfenylfosfit og tetradekanol (molforhold 1 : 1) oppvarmes etter tilsetning av 3 mol f-katalysator under omrøring i løpet av 1 time ved 120°C, avkjøles deretter og filtreres under tilsetning av aktivkull og blekjord. A mixture of tris-nonylphenylphosphite and tetradecanol (molar ratio 1:1) is heated after adding 3 mol of f-catalyst while stirring for 1 hour at 120°C, then cooled and filtered while adding activated carbon and bleaching earth.
Som katalysatorer anvendes litiumamid, natriumamid og natriummetylat. Lithium amide, sodium amide and sodium methylate are used as catalysts.
I de dannede omforestringsblandinger ble deretter ^"'".P-NMR-spektroskopisk bestemt innholdet av bis-nonylfenyl-tetradecylfosfit (128,5 ppm i CDCl^referert til H^PO^). Resultatene er oppstillet i tabell 2. Man ser at litiumamid har den største katalysatoraktivitet, mens virkningen av natriumamid og natriummetylat er sammenlignbar. In the transesterification mixtures formed, the content of bis-nonylphenyl-tetradecyl phosphite (128.5 ppm in CDCl^ referred to H^PO^) was then determined ^"'".P-NMR spectroscopically. The results are listed in table 2. It can be seen that lithium amide has the greatest catalyst activity, while the effect of sodium amide and sodium methylate is comparable.
Eksempel 43. Example 43.
Tris-nonylfenylfosfit blandes med tetradekanol i molforhold 1 : 1 og oppvarmes etter tilsetning av 3 mol?? katalysator under omrøring i løpet av 1 time til 120°C og omrøres 5 timer ved denne temperatur. Deretter avdestilleres det ved omforestringen dannede nonylfenol ved T ^s l80°C i oljepumpe-vakuum og residuet filtreres etter tilsetning av aktivkull og blekj ord. Tris-nonylphenylphosphite is mixed with tetradecanol in a molar ratio of 1:1 and heated after adding 3 mol?? catalyst with stirring during 1 hour at 120°C and stirred for 5 hours at this temperature. The nonylphenol formed by the transesterification is then distilled off at T ^s 180°C in an oil pump vacuum and the residue is filtered after adding activated carbon and bleach.
Som katalysatorer anvendes litiumamid, natriumamid og natriummetylat. Lithium amide, sodium amide and sodium methylate are used as catalysts.
Mens de ved litiumamid- og natriumamid-katalysen dannede omforestringsprodukter heller ikke etter lengere henstand viser noen etteruklarhet vil ved det over natriummetylkatalyse dannede lett uklare produkt allerede etter kort standtid ved værelsestemperatur iakttas en sterk etterutfelling. While the transesterification products formed by lithium amide and sodium amide catalysis do not show any after-cloudiness even after a longer delay, with the slightly cloudy product formed over sodium-methyl catalysis a strong after-precipitation is already observed after a short standing time at room temperature.
De følgende eksempler viser de anvendelsestekniske egenskaper av de ifølge oppfinnelsen luktløse fosfiter sammenlignet med handelsvanlige luktintensive resp. de til teknikkens stand svarende luktfattige fosfiter som ko-stabilisatorer i praksisnære stabilisatorkombinasjoner og resepturer. The following examples show the technical application properties of the odorless phosphites according to the invention compared to commercially available odor-intensive resp. the low-odor phosphites corresponding to the state of the art as co-stabilizers in practical stabilizer combinations and recipes.
Eksempel 44.Example 44.
Følgende reseptur på basis av en kalsium-sink-stabilisator-kombinasjon egner seg f.eks. til fremstilling av folier og flasker for innpakning av næringsmidler. The following recipe based on a calcium-zinc-stabilizer combination is suitable, for example. for the production of foils and bottles for food packaging.
For undersøkelse på termostabilitet blandes be-standdelene til en pulverformet sammensetning og av blandingen fremstilles på et valseverk ved 170°C i løpet av 5 minutter en folie (forsøk 1, tabell 4). For testing thermostability, the ingredients are mixed into a powdery composition and a foil is produced from the mixture on a rolling mill at 170°C within 5 minutes (experiment 1, table 4).
I et annet forsøk settes til denne sammensetning i tillegg 1 vektdel tris-nonylfenylfosfit (I) (forsøk 2, tabell 4), som er tillatt for fremstilling av emballasje for næringsmidler i tallrike industriland. In another trial, 1 part by weight of tris-nonylphenylphosphite (I) (trial 2, table 4), which is permitted for the production of packaging for foodstuffs in numerous industrialized countries, is additionally added to this composition.
I ytterligere forsøk tilblandes til sammensetningen 1 vektdel av et fra eksemplene uttatt fosfit ifølge oppfinnelsen. In further tests, 1 part by weight of a phosphite taken from the examples according to the invention is mixed into the composition.
De dannede folier forarbeides i en platepresse ved l80°C og et sluttrykk på 200 ato til plater av 2,5 mm tykkelse. Som presstid velges 5 minutter, 20 minutter og 40 minutter. For å sikre like prøvebetingelser sammensetter sammenligningsfoliene og de med fosfitene ifølge oppfinnelsen fremstilte folier i en pressprosess til en eneste pressplate av ved siden av hverandre liggende avsnitt. De i avhengighet av resepturen og presstiden opptredende misfarvninger av avsnittene av pressplatene sees ved måling av "YELLONESS-INDEX" ifølge ASTM D 1925-70. Verdiene er oppstillet i tabell 4. The formed foils are processed in a plate press at 180°C and a final pressure of 200 ato into plates of 2.5 mm thickness. 5 minutes, 20 minutes and 40 minutes are selected as pressing time. In order to ensure the same test conditions, the comparison foils and the foils produced with the phosphites according to the invention are combined in a pressing process into a single pressing plate of adjacent sections. Depending on the recipe and the pressing time, the discolouration of the sections of the pressing plates can be seen by measuring the "YELLOWNESS-INDEX" according to ASTM D 1925-70. The values are listed in table 4.
Av. disse måleverdier sees at med det til teknikkens stand svarende tris-nonylfenylfosfit forbedres begynnelsesfarven (presstid 5 minutter) bare lite, mens de ifølge oppfinnelsen luktfrie fosfiter tydelig forbedrer denne for lysheten av den ferdige artikkel avgjørende egenskap. Videre viser resultatene også etter lengere presstider av den utpregede kostabiliserende effekt av fosfitene ifølge oppfinnelsen også kan fastslås ved den såkalte langtidsstabilitet. Of. these measured values show that with the state-of-the-art tris-nonylphenyl phosphite, the initial color (press time 5 minutes) is only slightly improved, while the odorless phosphites according to the invention clearly improve this crucial property for the brightness of the finished article. Furthermore, the results also show after longer pressing times that the pronounced co-stabilizing effect of the phosphites according to the invention can also be determined by the so-called long-term stability.
E ksempel 45.Example 45.
Tekniske artikler av PVC utrustes ofte med stabilisatorer på basis av barium- og kadmium-karboksylater, hvortil det spesielt til forbedring av begynnelsesstabiliteten settes fosfiter. Følgende eksempel viser virkning av de ifølge oppfinnelsen luktfrie fosfiter sammenlignet med handelsvanlige fosfiter i en praksisnær reseptur. Technical articles made of PVC are often equipped with stabilizers based on barium and cadmium carboxylates, to which phosphites are added especially to improve the initial stability. The following example shows the effect of the odorless phosphites according to the invention compared to commercially available phosphites in a practical recipe.
100 vektdeler PVC (K-verdi 70) blandes med en handelsvanlig grunnstabilisator av 0,8 vektdeler kadmiumstearat, 0,3 vektdeler kadmiumlaurat, 0,5 vektdeler bariumlaurat, 0,2 vektdeler pentaerytrit og 0,2 vektdeler bisfenol-A. Av blandingen 100 parts by weight PVC (K-value 70) is mixed with a commercially available basic stabilizer of 0.8 parts by weight cadmium stearate, 0.3 parts by weight cadmium laurate, 0.5 parts by weight barium laurate, 0.2 parts by weight pentaerythritol and 0.2 parts by weight bisphenol-A. Of the mixture
fremstilles på et valseverk ved l80°C i løpet av 5 minutter en folie. produced on a rolling mill at 180°C within 5 minutes a foil.
I ytterligere forsøk tilsettes til den angitte sammensetning hver gang 1 vektdel av det handelsvanlige luktintense fosfit deayl-difenylfosfit (II) resp. tris-nonylfenylfosfit (I) resp. de av eksemplene uttatte luktfrie fosfiter ifølge oppfinnelsen. In further experiments, 1 part by weight of the commercially available phosphite deayl-diphenyl phosphite (II) or tris-nonylphenylphosphite (I) resp. the odorless phosphites selected from the examples according to the invention.
Foliene forarbeides på overnevnte måte til 2,5 mm tykke pressplater som belastes ved l80°C. I tabell 5 er det angitt den ved prøvemønstrene fastslåtte "YELLONESS-INDEX", som muliggjør en vurdering av den kostabiliserende virkning av de anvendte fosfiter. The foils are processed in the above-mentioned manner into 2.5 mm thick press plates which are loaded at 180°C. Table 5 shows the "YELLOWNESS INDEX" determined by the sample patterns, which enables an assessment of the co-stabilizing effect of the phosphites used.
En sammenligning av misfarvningsverdien i tabell 5 viser at med de ifølge oppfinnelsen luktfrie fosfiter oppnås verdier som er overlegen eller i det minste sammenlignbare med begynnelsesstabiliteten av handelsvanlige luktintense fosfiter. Måleresultatene for tris-nonylfenylfosfit viser at det med et til teknikkens stand svarende luktnøytralt fosfit er det ikke å oppnå1i praksis en forbedring av begynnelsesfarven. Ved lang-tidsstabiliteten viser de ifølge oppfinnelsen luktfrie fosfiter resultater som er sammenlignbare med de luktintense fosfiter. Overfor tris-nonylfenylfosfit er fosfitene ifølge oppfinnelsen tydelig overlegne. A comparison of the discoloration value in table 5 shows that with the odorless phosphites according to the invention, values are obtained which are superior or at least comparable to the initial stability of commercially available odor-intense phosphites. The measurement results for tris-nonylphenyl phosphite show that with an odor-neutral phosphite corresponding to the state of the art, it is not possible to achieve1 in practice an improvement in the initial colour. In terms of long-term stability, the odorless phosphites according to the invention show results that are comparable to the odor-intense phosphites. Compared to tris-nonylphenyl phosphite, the phosphites according to the invention are clearly superior.
Eksempel 46.Example 46.
I en ytterligere forsøksserie blandes 100 vektdeler S-PVC (K-verdi 70) med 2 vektdeler av en handelsvanlig pulverformet barium-kadmium-stabilisator med 356% Ba- og 16,4$ Cd-innhold og av blandingen fremstilles ved l80°C i løpet av 5 minutter en folie (forsøk 1, tabell 6). I ytterligere forsøk tilblandes til den angitte sammensetning i tillegg hver gang 1 vektdel decyl-difenylfosfit (II) resp. 1 vektdel av et ifølge oppfinnelsen luktfritt fosfit. Prøvefoliene forarbeides på den angitte måte til 2,5 mm tykke pressplater' som belastes ved l80°C. De ved hjelp av "YELLONESS-INDEX" målte farvninger fremgår av tabell 7- In a further series of experiments, 100 parts by weight of S-PVC (K-value 70) are mixed with 2 parts by weight of a commercially available powdered barium-cadmium stabilizer with 356% Ba and 16.4% Cd content and the mixture is prepared at 180°C in during 5 minutes a foil (experiment 1, table 6). In further experiments, 1 part by weight of decyl-diphenylphosphite (II) or 1 part by weight of an odorless phosphite according to the invention. The sample foils are processed in the specified manner into 2.5 mm thick press plates' which are loaded at 180°C. The colors measured using the "YELLONESS-INDEX" appear in table 7-
Som en sammenligning av farvemålingsverdiene viser, blir de ved det valgte stabiliseringssystem betingede høye be-gyrinelsesstabilitet ytterligere betraktelig forbedret ved det ifølge oppfinnelsen luktfrie fosfit. I forhold til handelsvanlig luktintensivt decyl-difenylfosfit (II) viser fosfitene ifølge oppfinnelsen en tydelig forbedring av virkningen som kostabilisator. As a comparison of the color measurement values shows, the high gyration stability due to the selected stabilization system is further considerably improved by the odorless phosphite according to the invention. In relation to commercial odor-intensive decyl-diphenyl phosphite (II), the phosphites according to the invention show a clear improvement in their effect as a cost stabilizer.
Eksempel 47.Example 47.
100 vektdeler av en S-PVC (K-verdi 70) blandes med 48 vektdeler DOP, 2 vektdeler epoksydert soyaolje og 2 vektdeler 100 parts by weight of an S-PVC (K-value 70) is mixed with 48 parts by weight DOP, 2 parts by weight epoxidized soybean oil and 2 parts by weight
av en for stabilisering av myk-PVC egnet pulverformet handelsvanlig barium-kadmium-stabilisator med 7,4$ Ba- og 9,6$ Cd-innhold og ved l65°C fremstilles på et valseverk en prøvefolie. of a commercially available barium-cadmium stabilizer in powdered form suitable for stabilizing soft PVC with 7.4$ Ba and 9.6$ Cd content and at 165°C, a test foil is produced on a rolling mill.
I ytterligere forsøk settes til blandingen i tillegg hver gangIn further trials, more is added to the mixture each time
1 vektdel av det handelsvanlige luktintensive fenyl-didecylfos-fit (III) resp. tris-nonylfenylfosfit (I) resp. et ifølge oppfinnelsen luktfritt fosfit. Prøvefoliene forarbeides på vanlig måte ved l80°C i 2,5 mm tykke pressplater. De derved opptredende farvninger av pressplatene er oppstillet i tabell 8 som måleverdier av "YELLONESS-INDEX". 1 part by weight of the commercial odor-intensive phenyl didecyl phosphite (III) resp. tris-nonylphenylphosphite (I) resp. an odorless phosphite according to the invention. The sample foils are processed in the usual way at 180°C in 2.5 mm thick press plates. The resulting coloring of the press plates is listed in table 8 as measured values of the "YELLONESS-INDEX".
Farvningsmålingene viser at den kostabiliserende virkning av det handelsvanlige fosfit I er helt utilstrekkelig. Derimot fører de ifølge oppfinnelsen luktfrie fosfiter til en tydelig forbedring av begynnelsesfarven og bevirker en betraktelig forsinkelse av misfarvningsforeteelser ved økende belastning av pressplaten. Som det fremgår av sammenligningen av langtids-stabiliteten overtreffer de i disse egenskaper også handelsvanlige . luktintensive fosfiter. The staining measurements show that the co-stabilizing effect of the commercially available phosphite I is completely insufficient. In contrast, the odorless phosphites according to the invention lead to a clear improvement of the initial color and cause a considerable delay in discoloration phenomena with increasing load on the press plate. As can be seen from the comparison of the long-term stability, in these properties they also surpass commercial ones. odor intensive phosphites.
Eksempel 48.Example 48.
10 vektdeler S-PVC (K-verdi 70) blandes med 2 vektdeler av en handelsvanlig pastaformet kalsium-sink-stabilisator med 0,4$ Ca- og 1,0$ Zn-innhold og med 0,6 vektdeler glidemiddel. 10 parts by weight of S-PVC (K value 70) are mixed with 2 parts by weight of a commercially available paste-shaped calcium-zinc stabilizer with 0.4$ Ca and 1.0$ Zn content and with 0.6 parts by weight of lubricant.
Som kostabilisator tilblandes hver gang 0,5 vektdelerAs a cost stabilizer, 0.5 parts by weight are added each time
I tris-nonylfenylfosfit,In tris-nonylphenyl phosphite,
IV nonylfeny1-didodecylfosfit (fremstillet ifølge eksemplene 1 og 2 ifølge US-patent nr. 2.877.259), IV nonylpheny1-didodecyl phosphite (prepared according to Examples 1 and 2 of US Patent No. 2,877,259),
V oktylfenyl-dioktadecylfosfit (fremstillet ifølge eksemplene.IV og XV i US-patent nr. 2.968.670) resp. fosfit ifølge oppfinnelsen, eksempel 10. V octylphenyl-dioctadecyl phosphite (prepared according to examples IV and XV in US patent no. 2,968,670) resp. phosphite according to the invention, example 10.
Blandingene forarbeides ved 190°C på et valseverk til folier av 0,3 mm tykkelse og disse belastes i permanent-valseprøven. Hver gang etter 5 minutter uttas en prøve av fol-ien og dens farvning fastslås som måleverdi av Yellowness-indeksen. Resultatene er sammenstillet i tabell 95hvorav det fremgår overlegenheten av forbindelsene ifølge oppfinnelsen. Fosfit VI og VII har dessuten en tydelig delvis uheldig lukt. The mixtures are processed at 190°C on a rolling mill into foils of 0.3 mm thickness and these are loaded in the permanent rolling test. Every time after 5 minutes, a sample is taken from the foil and its coloring is determined as a measurement value of the Yellowness index. The results are compiled in table 95, from which the superiority of the compounds according to the invention is evident. Phosphite VI and VII also have a distinct partly unpleasant smell.
Eksempel 49. Example 49.
En høymolekylær Ziegler-hdpe ("Lupolen 5260 Z") 'ble undersøkt alene samt sammen med 0,05$ av et handelsvanlig antioksydans og hver gang 0,1$ av et handelsvanlig fosfit eller en av fosfitblandingene ifølge oppfinnelsen i Brabander-knaer ved 220°C og 50 omdreininger pr. minutt på forarbeidelsesstabili-serende virkning. A high molecular weight Ziegler hdpe ("Lupolen 5260 Z") was tested alone as well as together with 0.05$ of a commercial antioxidant and each time 0.1$ of a commercial phosphite or one of the phosphite mixtures according to the invention in Brabander furnaces at 220 °C and 50 revolutions per minute on the processing stabilizing effect.
Virkningen av fosfitblandingen ifølge oppfinnelsen fremgår av den tydelige forlengelse av knatiden inntil begyn-nende nettdannelse av den polymere (økning av kraftopptak). The effect of the phosphite mixture according to the invention can be seen from the clear extension of the kneading time until the starting network formation of the polymer (increase in power absorption).
Eksempel 50» Example 50»
I forstabilisert polybutadien ("Solprene 250")In pre-stabilized polybutadiene ("Solprene 250")
ble fosfitblandinger ifølge oppfinnelsen innarbeidet i Brabander-Plastic-order og samtidig aldret ved 150°C og 60 omdreininger pr. minutt i 30 minutter. phosphite mixtures according to the invention were incorporated into Brabander-Plastic orders and simultaneously aged at 150°C and 60 rpm. minute for 30 minutes.
Dessuten ble det i "Solprene 250" også innarbeidet handelsvanlige fosfiter, handelsvanlige antioksydanter, fosfitene ifølge oppfinnelsen samt fosfit-/antioksydans-blandinger og aldret ved 150°C og 60 omdreininger pr. minutt i 30 minutter. In addition, commercially available phosphites, commercially available antioxidants, the phosphites according to the invention as well as phosphite/antioxidant mixtures were also incorporated in "Solprene 250" and aged at 150°C and 60 revolutions per minute. minute for 30 minutes.
Virkningen av fos fitblandingene ifølge oppfinnelsen fremgår av den tydelige nedsettelse av dreiemomentmaksimum (Dj^) samt kvotienten D^/T^ av dreiemomentet (D^) og tiden (T^) fra begynnelse til oppnåelse av D... The effect of the phosphate mixtures according to the invention can be seen from the clear reduction of the torque maximum (Dj^) as well as the quotient D^/T^ of the torque (D^) and the time (T^) from the beginning to the achievement of D...
Eksempel 51» Example 51»
Følgende resepturer fremstilles ifølge eksempel 48 og blandingen belastes ved 190°C i permanentvalseprøve. Resultatene er å utlede fra tabell 11. The following recipes are prepared according to example 48 and the mixture is loaded at 190°C in a permanent rolling test. The results are to be derived from table 11.
Eksempel 52. Example 52.
Følgende resepturer fremstilles ifølge eksempel 48. The following recipes are prepared according to example 48.
Blandingene forarbeides til 0,3 mm tykke prøve-foler ved en valsevarighet på 5 minutter ved l65°C og foliene underkastes i sirkulasjonstørkeskap ved l80°C en varmeprøve, idet hvert 15. minutt uttas en prøve og dens farvning bestemmes. Resultatene fremgår av tabell 12. The mixtures are processed into 0.3 mm thick sample foils with a rolling duration of 5 minutes at 165°C and the foils are subjected to a heat test in a circulation drying cabinet at 180°C, with a sample taken every 15 minutes and its coloring determined. The results appear in table 12.
Claims (16)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH1670275 | 1975-12-23 |
Publications (1)
Publication Number | Publication Date |
---|---|
NO764344L true NO764344L (en) | 1977-06-24 |
Family
ID=4419514
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
NO764344A NO764344L (en) | 1975-12-23 | 1976-12-22 |
Country Status (9)
Country | Link |
---|---|
AT (1) | AT344731B (en) |
BE (1) | BE849725A (en) |
DE (1) | DE2656748C2 (en) |
DK (1) | DK580576A (en) |
FR (1) | FR2336409A1 (en) |
GB (1) | GB1557266A (en) |
NL (1) | NL7614216A (en) |
NO (1) | NO764344L (en) |
SE (1) | SE433749B (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2509740B1 (en) * | 1981-07-17 | 1986-10-17 | Ugine Kuhlmann | PROCESS FOR THE STABILIZATION OF VINYL CHLORIDE POLYMERS AND COPOLYMERS AND PLASTIC MATERIALS OBTAINED BY THE IMPLEMENTATION OF THIS PROCESS |
US5254610A (en) * | 1991-08-02 | 1993-10-19 | Eastman Kodak Company | Polyester/polycarbonate blends containing phosphites |
CN110551004A (en) * | 2019-08-16 | 2019-12-10 | 广东新华粤石化集团股份公司 | high-performance antioxidant and preparation method thereof |
-
1976
- 1976-12-15 DE DE2656748A patent/DE2656748C2/en not_active Expired
- 1976-12-21 NL NL7614216A patent/NL7614216A/en not_active Application Discontinuation
- 1976-12-21 GB GB53308/76A patent/GB1557266A/en not_active Expired
- 1976-12-22 AT AT954076A patent/AT344731B/en not_active IP Right Cessation
- 1976-12-22 BE BE173525A patent/BE849725A/en not_active IP Right Cessation
- 1976-12-22 DK DK580576A patent/DK580576A/en not_active Application Discontinuation
- 1976-12-22 SE SE7614451A patent/SE433749B/en not_active IP Right Cessation
- 1976-12-22 NO NO764344A patent/NO764344L/no unknown
- 1976-12-23 FR FR7638853A patent/FR2336409A1/en active Granted
Also Published As
Publication number | Publication date |
---|---|
FR2336409B1 (en) | 1980-10-03 |
BE849725A (en) | 1977-06-22 |
FR2336409A1 (en) | 1977-07-22 |
AT344731B (en) | 1978-08-10 |
SE433749B (en) | 1984-06-12 |
DK580576A (en) | 1977-06-24 |
SE7614451L (en) | 1977-06-24 |
DE2656748A1 (en) | 1977-07-14 |
GB1557266A (en) | 1979-12-05 |
NL7614216A (en) | 1977-06-27 |
DE2656748C2 (en) | 1985-11-28 |
ATA954076A (en) | 1977-12-15 |
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