AU621630B2 - Process for the stabilization of polyolefins - Google Patents
Process for the stabilization of polyolefins Download PDFInfo
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- AU621630B2 AU621630B2 AU36690/89A AU3669089A AU621630B2 AU 621630 B2 AU621630 B2 AU 621630B2 AU 36690/89 A AU36690/89 A AU 36690/89A AU 3669089 A AU3669089 A AU 3669089A AU 621630 B2 AU621630 B2 AU 621630B2
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- 238000000034 method Methods 0.000 title claims description 35
- 230000006641 stabilisation Effects 0.000 title claims description 11
- 238000011105 stabilization Methods 0.000 title claims description 11
- 229920000098 polyolefin Polymers 0.000 title description 6
- -1 piperidin compound Chemical class 0.000 claims description 38
- 238000006116 polymerization reaction Methods 0.000 claims description 31
- 229920000642 polymer Polymers 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 239000011777 magnesium Substances 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 8
- 150000003053 piperidines Chemical class 0.000 claims description 8
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 8
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 8
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 150000003609 titanium compounds Chemical class 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 239000011949 solid catalyst Substances 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 3
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 125000004956 cyclohexylene group Chemical group 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims 2
- SLRMQYXOBQWXCR-UHFFFAOYSA-N 2154-56-5 Chemical group [CH2]C1=CC=CC=C1 SLRMQYXOBQWXCR-UHFFFAOYSA-N 0.000 claims 1
- 230000003078 antioxidant effect Effects 0.000 claims 1
- 235000006708 antioxidants Nutrition 0.000 claims 1
- VEQOALNAAJBPNY-UHFFFAOYSA-N antipyrine Chemical compound CN1C(C)=CC(=O)N1C1=CC=CC=C1 VEQOALNAAJBPNY-UHFFFAOYSA-N 0.000 claims 1
- 229910001629 magnesium chloride Inorganic materials 0.000 claims 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims 1
- 229960005222 phenazone Drugs 0.000 claims 1
- 239000011541 reaction mixture Substances 0.000 claims 1
- 239000003381 stabilizer Substances 0.000 description 17
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 14
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 11
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- 150000001336 alkenes Chemical class 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 230000032683 aging Effects 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 239000007983 Tris buffer Substances 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Substances CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 3
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical group C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 2
- BVUXDWXKPROUDO-UHFFFAOYSA-N 2,6-di-tert-butyl-4-ethylphenol Chemical compound CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 BVUXDWXKPROUDO-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- YIKSCQDJHCMVMK-UHFFFAOYSA-N Oxamide Chemical compound NC(=O)C(N)=O YIKSCQDJHCMVMK-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 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
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 description 1
- 125000004343 1-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C([H])([H])[H] 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
- GXURZKWLMYOCDX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.OCC(CO)(CO)CO GXURZKWLMYOCDX-UHFFFAOYSA-N 0.000 description 1
- UUAIOYWXCDLHKT-UHFFFAOYSA-N 2,4,6-tricyclohexylphenol Chemical compound OC1=C(C2CCCCC2)C=C(C2CCCCC2)C=C1C1CCCCC1 UUAIOYWXCDLHKT-UHFFFAOYSA-N 0.000 description 1
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- JBYWTKPHBLYYFJ-UHFFFAOYSA-N 2,6-ditert-butyl-4-(2-methylpropyl)phenol Chemical compound CC(C)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 JBYWTKPHBLYYFJ-UHFFFAOYSA-N 0.000 description 1
- 125000003006 2-dimethylaminoethyl group Chemical group [H]C([H])([H])N(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- AIBRSVLEQRWAEG-UHFFFAOYSA-N 3,9-bis(2,4-ditert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP1OCC2(COP(OC=3C(=CC(=CC=3)C(C)(C)C)C(C)(C)C)OC2)CO1 AIBRSVLEQRWAEG-UHFFFAOYSA-N 0.000 description 1
- YLUZWKKWWSCRSR-UHFFFAOYSA-N 3,9-bis(8-methylnonoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCC(C)C)OCC21COP(OCCCCCCCC(C)C)OC2 YLUZWKKWWSCRSR-UHFFFAOYSA-N 0.000 description 1
- HCILJBJJZALOAL-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)-n'-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyl]propanehydrazide Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 HCILJBJJZALOAL-UHFFFAOYSA-N 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- SAKJVQIASONOAF-UHFFFAOYSA-N 4-(azepan-1-yl)morpholine Chemical compound C1COCCN1N1CCCCCC1 SAKJVQIASONOAF-UHFFFAOYSA-N 0.000 description 1
- OVARTXYXUGDZHU-UHFFFAOYSA-N 4-hydroxy-n-phenyldodecanamide Chemical compound CCCCCCCCC(O)CCC(=O)NC1=CC=CC=C1 OVARTXYXUGDZHU-UHFFFAOYSA-N 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- LZAIWKMQABZIDI-UHFFFAOYSA-N 4-methyl-2,6-dioctadecylphenol Chemical compound CCCCCCCCCCCCCCCCCCC1=CC(C)=CC(CCCCCCCCCCCCCCCCCC)=C1O LZAIWKMQABZIDI-UHFFFAOYSA-N 0.000 description 1
- ZVEWFTICTSQBDM-UHFFFAOYSA-N 4-methylphenol Chemical compound [CH2]C1=CC=C(O)C=C1 ZVEWFTICTSQBDM-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- BPTDMYLGVQDCNW-UHFFFAOYSA-N C[Si](OCC)(OCC)OCC.C1(=CC=CC=C1)[Si](OC)(OC)C1=CC=CC=C1 Chemical compound C[Si](OCC)(OCC)OCC.C1(=CC=CC=C1)[Si](OC)(OC)C1=CC=CC=C1 BPTDMYLGVQDCNW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- ODRWJRFALQTLOR-UHFFFAOYSA-N OP(O)OP(O)O.C(CCCCCCCCCCCCCCCCC)C(O)(C(CO)(CO)CO)CCCCCCCCCCCCCCCCCC.P(O)(O)O Chemical compound OP(O)OP(O)O.C(CCCCCCCCCCCCCCCCC)C(O)(C(CO)(CO)CO)CCCCCCCCCCCCCCCCCC.P(O)(O)O ODRWJRFALQTLOR-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical class P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910010066 TiC14 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003081 coactivator Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000002993 cycloalkylene group Chemical group 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
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- GLOQRSIADGSLRX-UHFFFAOYSA-N decyl diphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OCCCCCCCCCC)OC1=CC=CC=C1 GLOQRSIADGSLRX-UHFFFAOYSA-N 0.000 description 1
- NMAKPIATXQEXBT-UHFFFAOYSA-N didecyl phenyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OC1=CC=CC=C1 NMAKPIATXQEXBT-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 1
- 229910001623 magnesium bromide Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- UUEVFMOUBSLVJW-UHFFFAOYSA-N oxo-[[1-[2-[2-[2-[4-(oxoazaniumylmethylidene)pyridin-1-yl]ethoxy]ethoxy]ethyl]pyridin-4-ylidene]methyl]azanium;dibromide Chemical compound [Br-].[Br-].C1=CC(=C[NH+]=O)C=CN1CCOCCOCCN1C=CC(=C[NH+]=O)C=C1 UUEVFMOUBSLVJW-UHFFFAOYSA-N 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N para-hydroxytoluene Natural products CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000003884 phenylalkyl group Chemical group 0.000 description 1
- 125000005538 phosphinite group Chemical group 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical class OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000009747 press moulding Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000725 suspension Substances 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
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- IVIIAEVMQHEPAY-UHFFFAOYSA-N tridodecyl phosphite Chemical compound CCCCCCCCCCCCOP(OCCCCCCCCCCCC)OCCCCCCCCCCCC IVIIAEVMQHEPAY-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34926—Triazines also containing heterocyclic groups other than triazine groups
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
ik I -1 1 1, 1 Cur Ref: 280340
AUSTRALIA
Patents Act COMPLETE SPECIFICATION
(ORIGINAL)
FORM B<L2 630 Application Number: Lodged: Complete Specification Lodged: r Accepted: a Published: ft 0 Priority: I Related Art: t ft( #0 t 0SS 0 S Applicant(s): Ciba-Gigy AG Klybeckstrasse 141 4002 BASLE
SWITZERLAND
ARTHUR S. CAVE CO.
Patent Trade Mark Attovnerys Level 10, 10 Barrack Straet SYDNEY NSW 2000 Address for Service: Complete specification for the invention entitled "Process for the stabilizat.on of polyolefins".
Thk following statement is a full description of this invention, icluding the best mjthod of performing it known to met- -1-I 5020 JA Process for the stabilization of polyolefins The invention relates to a process for the stabilization or polyolefins and olefin copolymers by the addition of certain stabilizers to the polymerization, the polymerization occurring by a certain process. The invention also relates to the olefin polymers stabilized in this way.
The low pressure polymerization of olefins using organometallic ccmplex catalysts (for example Ziegler-Natta catalysts) normally leads to a fine polymer powder, which has to be granulated in an extruder before the S shaping processing. Stabilizers and other additives are added during this granulation.
Success has recently been achieved in preparing spherically granular S polymers which no longer have to be granulated, but can be directly t ti S" t processed, by the use of solid supported catalysts. Spherical magnesium halides of a certain particle size, as, for example, described in US-A 4,111,835 have in particular proved suitable as supports for these S" solid catalysts. The anhydrous magnesium halide forms insoluble complexes
I
with TiC14 and electron donors, which are then activated with aluminium S alkyls. The stereospecificity and activity are enhanced by the co-use of electron donors, for example carboxylic acid esters or compounds with Si-O-C bonds, described for example in EP-A 45 977.
S Furthermore it has recently been found (EP-A 192 987) that in this kind ,of olefin polymerization, stabilizers of the sterically hindered piperidine type can be added to the polymerization without the polymerization process thereby being impaired.
In this case neither the polymerization yield nor the quality of the polymer are reduced and a stabilizatipn against thermal, oxidative and photochemical ageing is achieved which is at least equal to the effect in i I 2 the case of subsequent edition of a stabilizer of this type to the finished polymer. The advantage is the saving of an operative procedure, namely mixing and granulation.
This stabilization process is described in EP-A, 192 987 and a large number of compounds are described there which are suitable as stabilizers for this process, including also those sterically hindered piperidine derivatives which contain a s-triazine group in their molecule.
In further work in this area it has been found that certain piperidine derivatives which contain at least one s-triazine group in their molecule are particularly suitable for the stabilization of olefins by addition to the polymerization.
c r
S
C a S. t In detail, the invention relates to a process for the stabilization of polyolefins and olefin copolymers, which are prepared by low pressure polymerization on a solid catalyst, which is prepared by the reaction of an aluminium alkyl with a solid product of a magnesium dihalide in active form and a titanium compound, the stabilization being carried out by the addition of a sterically hindered piperidine derivative to the polymerization, wherein a piperidine derivative of the formula I is used, a.
St *4 Si l~i~ ~ir i) in which n is 1-4, R I is C 1 -C4alkyl, allyl, benzyl or acetyl, and is also hydrogen in the case of n 2, R 2 is Ci-Cisalkyl, Os-C12cycloalky C phlkyl,C2penylakyl, C3-Clzalkyl interrupted by or or is a group of the formula II, R' -C CRN (I)
C,\H
_.ir I -3-
R
3 is a group -OR 5
-SR
5 or -N /R6 RI has-one of the meanings given for R3 when n 1, is one of the groups -X-R 8 113 -Nf i-0-o -0or in which q is 2-6, when n 2, is one of the groups -N-k(R -C)H2 3-N or -0CHCH 6 3 6CH2CHZQ- SO CH 2 CH 2
CH
2
O-
when n 3, and is a group c* -N(RG )CH2CH2,--CHC2--CHCH-N(P, or -N(R )-(C11 2 3
(CH
2 (CHZ)3-N(R6)- when n 4,
R
5 is Cl-Ciealkylt C 3
-C
1 Zalkenyl, Cs-Clzcycloakyl, C 7 -Clzphenylalkyl, phenyl or phenyl substituted by CI-C4alkyL, Cl-Ctalkoxy or halogen, R 6 and R 7 are independently of one another hydrogen, CI'Ci$41kyl, Cs-C12cycloa),kyl, C7-Cl2phenylalkyl or a group of the formula II, or R 6 and R 7 are together C4-Cioa1,ylene or CS-Coxa- or azaalkylene, RI is C2zC 1 2 alkylene, C4-Cizalkyleoee interupted by or Cs-Ci,2cycLOalkylene or phenylene, R 9 is hydrogen or methyl, X and Y are independently of one another or m is 2 or 3 and p is 2-10.
The radical R' as C 1 -C4 can, for example, be methyl, ethyl, propyl or butyl and preferably RI is miethyl.
-4- R1, R 5 R' and R 7 as Cl-Claalkyl may be an unbranched or branched alkyl.
Examples thereof are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, sec-pentyl, n-hexyl, 2-ethylbutyl, n-octyl, 2-ethyihexyl, n-decyl, isodecyl, n-dodecyl, 2,2,4,4-tetramethylbutyl, n-tetradecyl, n-hexadecyl or n-octadecyl. RI as al~kyl interrupted by 0 or
N(R
6 may, for example, be 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, 3-methoxypropyl, 2 -dime thylamino ethyl or 3-diethylaminopropyl.
R
2 R R 6 and IR as CS-Cizcycloalkyl may, for example, be cyclopentyl, cyclohexyl, cyclooctyl or cyclododecyl. A radical of this type is preferably cyclohexyl.
R
2
R
5
R
6 and R 7 as C 7 -Cl 2 phenylalkyl may, for example, be benzyl, 2-phenylethyl, 1-phenylethyl or c,c-dimethylbenzyl. A radical of this *type is preferably benzyl.
R5 as C 3 -Cl 2 alkenyl may, for example, be allyl, methqllyl, but-2- S enyli but-3-enyl, hex-2-enyl, hex-5--enyl, oct-7-enyl or dec-9-enyl.
Compounds with unsaturated substituents of this type p~an copolymerize in o*the react~ n medium.
R
5 as phenyl substituted with alkyl, alkoxy or halogen may, for O o:example, be p-tolyl, m-tolyl, 4-tert--butylphenyl, 4-methoxyphenyl, 03-ethoxyphenyl o'r 4"chlorophpnyl.
R
8 as 02-Cl 2 alkylene may be unbranched or branched alkylene. Examples thereof are di-, tri-, tetra-, hexa-, octa-, deca- and do de came thylene, 1,2-propylene or 2,2-dimethyl-1,3-propylene, If the alkylene radical is interrupted, by 0 or N(R6), this may, for example, be 3-oxapenta- .:methylene, 4-oxaheptamethy].ene, 3, 6-dioxaoc tamnethylene or 3-aza- or 3-methylazapentamethylene.
R
8 as cycloalkylene may in particular be cyclohexylene.
When R' and R' together are alkylene, oxa- or azaalkylene, they form, together with the N atom to which they are bonded, a heterocyclic ring, for example a pyrrolidine, piperidine, hexamethyleneimino, morpholine or piperazine ring. These rings may be alkyl-substituted.
Those compounds of the formula I are preferably used in which n is 1-4, R' is Ci-Cz 4 alkyl, and is also hydrogen in the case of n 2, R 2 is CI-Cizalkyl, cyclohexyl, benzyl or a group of the formula II, R 3 is a group -OR 5 or -N(R 6
)(R
7 R4 has one of the meanings given for
R
3 when n 1, is a group -X-R 8 or -NI >C1 2 Cli2-N(R' when n 2, is a group -N(R 6
)-(CH
2 M_ _(CH 2 M_ w~hen n and is a group -N(,R 6 )-HC2 -HCZ--HC or
S-N(R
6
)-CH
2
CH
2
CH
2 -4-(CH2) p- -C1 2
C
2 CHz-N(R 6 when n =4, 5 is Cl-Cizalkyl, cyclohexyl, benzyl, phenyl or tolyl, R 6 is hydrogen, ,4 Ci-Cazalkyl, cyclohexyl, benzyl or a group of the formula II, TV is *44CI-Gazalkyl, cyclohexyl or a group of the formula II or R6 and R 7 are 4 together tetramethylene, pentamethylene or 3-oxapentamethylene, R8 is C2-Clzalkylene, cyclohexylene or 'henylene, X and Y are or -N(R 6 m is 2 or 3 and p is 2-6.
4 Preferably, R1 is methyl and R 2 is CI-Cealkyl or a group of the formula II. Preferably R 3 is a group -N(RB)(RI) When n I in *formula I, R4 is preferably a group -N(R (R 7 When n 2, X and Y are preferably a group and RI is preferably CZ-Csalkylene.
When n =3 or 4, RB is preferably hydrogen or Cl-Ci~alkyl, particularly methyl.
The compounds of the formula I are known compounds or can be prepare4d by analogy thereto. Compounds of this type are described for example in 'Us-A 3,925,376, US-A 4,108,829, EP-A 107 615, DE-A 3 727 977, DE-A 3 809 628, Er-A 292 437, EP-A 299 925.
Examples of piperidine compounds which may be used according to the invention are the compounds of the following formulae: -6- 19 01131K kli 9 X 2I CHN3C-N \0 9 4-11N 4, CH3 >-C13 t 1 i C 8 11 4 44 4 *1 NJ1 ,.N>-Cfl3 7- 8. R- R13 (022 A H
I
I qln(Ci 3 2
,N\
N R2 8 7/ V 2 11 >t 1 N
N
R2-.
8- AH3 R3= A4Rz
A
y2H R /2~-R A3 y 16. R i 4 1 19 4 1 16 Ri -(fl)-y-CC
H
I2- -(CHiz, 3
_R
\R ILI\N 'R
A
1 R el "OR~ I Y8/ v/) R"3 3 R/3 "N R 3A 3 -9- 19- CH3- 9/
C~
3 ~V\.i4 H9 /NN CH/ -N>-CH 3 1kHC 8 Hl7.
21. CU3-NI Ei N-CH1 3 21, H~N(1.RIgk \s N-CH 3 \/i *44. 22 W A4 A I 4 1 24, -Rla
A
t 0 1.4I** t H- 4ll I Q 4'1
A
1 BLN i> R .4 4 WiNtx R l'R 4e
N
/1 I\
R
5 -I-cU 2 CN\ X- 4444
NH
'4 4r *d In: the fomulae 1-:26, is a 1 ,2,2,6,6-pentamethylpptdine raidical.
4.44 4 4o The polymerization ctal~ysts used ar~e solid catalysts. They comprise an anhydrous mognesium dihalicle in aqtivo form and a titanium compound, A magnesium dihalido in actiVq form is to be umur~stood As meaning a magnesium dihalide Jin whose X~-ray spectrum the I tli the stronsest reflection is broadened in compai*son with the 0oz'esponding l~ine in the spectrom of the inactive wagnesiur halide.
The maneSoi'm halide used is prefEerably magnosiom diohlordo or magnesium bromide, Preforablys spherical maonosiom chloride is used The titanium.
compound preferably contains At least o titaniur-halogen bond, And titanium tetrachlorid is particularly preferably used, 11 The titanium compound can be used in combination with an electron donor, for example a carboxylic acid ester, as described in EP-A 45.977.
After the reaction of the magnesium halide component with the titanium compound and, if desired, with the electron donor, the excess of titanium compound and the excess of electron donor are expediently washed out with an inert solvent for example with hexane or heptane.
The catalyst prepared in this way is activated by reaction with an aluminiumalkyl, which is preferably used as a solution in an alkane.
Examples of suitable aluminium alkyls are Al(CzH 5 3 or Al(C4H9) 3 Here, an electron donor can be added as coactivator, for example an organosilicon compound which contains at least one Si-O-C bond, as described for example in EP-A 45 977. Example.. of silicon compounds of this type are phenyltriethoxysilane, phenyltri ethoxysilano, diphenyldimethoxysilane methyltriethoxysilane, dimethyldiethoxysilane or ethyltrimethoxysilane.
1 o o.
99 9 4,j The polymerization with these catalysts can be carried out in the liquid 0 *0 Sor gaseous phase, It is preferable to operate in the liquid phase, for SD" example in alkanes or in the liquid monomer.
The stabilizer (piperidine compound) can be added at the beginning of the polymerization, during the polymerization.r ate-- th- end- -thc p- .er- Saation. It is preferably added during the polymerization.
Vigorous stirring is expediently used to ensure as homogeneous a distribution as possible of the catalyst and of the stabilizer in the polymerization medium, 9 9 The quantity of piperidine stabilizer added is governed by the desired degree of stabilization. Generally 0.01 to 5 by weight, particularly 0.05 to 1 by weight, relative to the polymer are added.
-12 Ap~irt from the piperidine stabilizer, other stabilizers may also be added during polymerization. Phospho~rus'III) esters aire particularly suitable as other .ztabiJl,zers. These may be phosphites, phosphonites or phosphinites. They may contain one or more phosphorus ester groups. Preferably A trio rg anopho sphi te is added. Examples of phosphorus(III) esters of this type are: tripheny. phosphite, decyl diphenyl phosphite, phenyl didecyl phosphite, tris.(nonylphenyl) phosphite, trilauryl phosphite, trioctaf*'-cyl phosphite distearyl pentaerythritol diphosphite, tris(2, 4 di-tert-'butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, te traki s(2, 4-di- ter t-bu tylphenyl N-4, 4'-biphenylene diphosphonite, bis(2,6-di-tert-butyl-4.-methylphenyl) pentaerythritol diphosphite.
Alternatively or in addition to the phosphQrus-(III) esters, other stabilizers or additives which do not impair the polymerization. process may also be added, for example antioxidants of the sterically hindered phenol type.
*The following compounds are examples of antioxidants of this type: Alkyl'-substituted monophenols,, for example 2, 6-di-tqrt-butyl-4-methylphenol, 2-tert-butyl-4,6-diiethylphenol, 2 ,6-di-tert-butyl-4-ethylphenol, t2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, t ?,6-dicyclopentyl-4-niethylphenol, 2 -(ct-me thylcycl ohexyl) -4 6 -dime tbyl- I phenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 1. 2,6,,di-tert-butyl-4-methoxymethylphenoI and 2,6-dinonyJ,-4-methylphenol.
Alkyl-substituted hydrociuinones, for example 2,6-di-tert-butyl--4-methoxy- Sphenol, 2,5-di-tert-butyihydroquinone, a,5-di-tert-amylhydroquinone and 2,6-diphenyl-4-octadeoyloxyphdnol.
Iydroxyl-substituted thiodiphenyl ethers, for examplte 2,2'-thio-bis(6ter t-bu tyli-4-me thylphenol) 202'-thio-bis(4-octylphanol), 4,4'-thio-bis- (6-tert-butyl-3-.methylphenol) and 4,4'-thiio-bis(S-ter~'-butyl1-2-methylphenol).
11 Alkylidene-bisphenols, for example 2,2'-methylene-bia(E.-tort-buty'--4methylphenol), 2,2 '-methylene-bis(6-tert-buty!l-4-ethj-,lhenol), 2,2methylene-bis (4--methyl-6-(ci-methylcyclohexyl) phenol I, 2,2 '-methylenebis( 4-me thyl-6-cyclohexylpheno 2,2'-me thylene-bis( 6-nonyi.4-methylphenol), 2,2 '-inethylene-bis(,4,6-di-tert-butylphenol), 2,2'-ethylidene-, bis(4,6-di-tert-butylpbenol), 2,2'-ethylidene--bis(6-tert-butyl-4-isobutylyphenolt), 22 mtyeebs6(Lr~hlezl--oypeo] 2,2 '-methylene-bis[6-(c,a-dimethylbenzyl)-4-nonylphenolI, 4,4'-methyloinebis(2,6-di-tert-butylphenol), 4, 4'-me thylene-bis tert-butyl-2-ie thy 1phenol), 1, I -bi ter t-bu tyl-4-hydroxy-2.-me thyphenyl) butane, 2,6-his- (3-tert-butyl-5-methyl--hydroxybeniyl)-4-methylphenoll,1, -ri( tert-butyl-4-hydroxy-2-me, hylphenyl)butane, 1 ,1-bis(5-tert-butyl-4hydroxy-2-ne thylph enyl) 3n-do de cylne r cap tobu tane ethylene glycol bis f3,3-bis(3'-'tert-butyl-4'-hydroxyphenyl) butyra.tel, bis(3-tert-buillyl-4- 4 00I hydroxy- 5-me thy lpbenyl) dicyclopen tadiene and bisl2-(3'-tert-butyl-2'- *NO# hydroxy-5-methylbenzyl)--6-tert-butyl-4-metliylphenylI terephthalate.,
I,
4 44 4 .4 9, 9 9, 44 9 .94' 9, 99 44 4 o A -9 4~ 44 9, 9 9 44 4 9 4 49 44 49 0 4444 4 4 4 9A 4 9 44 4 44 Benzyl compounds, for example 1,3,5-tris-(,5-di- tert-butyl-4-hydIroxybenzyl)-2,4, 6-trimethylbenzene, bis(3,5-di-tert-butyl-4-hydro, :,zl) sulfide, isooctyl. 3, 5-di-tert-butyl-4-hydroxybenzylmerqaptoa f bis(4-tert-buty-3-hydroxy-2 ,6-dimethylbenzyl)dithiql, tereplhali 1 i-tris(3,5-dU,-tert-butyl-4-hydroxybenzy1) isocyanurate, 1, tert- butylt-3-hydroxy-2 ,6-dimethylbenzyl isoayanurate, dio, 3,5-di-tert-butyl-4-yroxybenzylphosphona.Ze, 'he Ca salt of monoethyl 31,5-'di-tert-buty,-4-hydoxybenzylphosphoriate atid 1 ,3,S-tris(3,j5-dcycJloboxyl-4-hydroxybenzyl) isocyanurate.
Acylaminophenol s, for example 4-hydroxylauranilide, 4-hydroxcystearanilide, 2,4-bis(octylmercapto)-6-(3,5-di-tet-bity'- 4 hydroxyanilino)-s-riaine and octyl N-(3,5-di-tet-butyl-4-hydroxyphenyl)carbarnate.
I
14 Esters of R-(3,5-di-tert-butyl-4-ydroyphenyl)-propionic acid with monohydric or polyhydric alcohols, for example with methanol, octadecanol, 1, 6-hexanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tri(hydroxyethyl) isocyanurate or N4li'-bis(hydroxyethyl)oxalamide.
Esters of 5-tert-butyl-4-hydroxy-3-methylplen y])-propionic acid with monohydric or polyhydric alcohols, for example with ilethanol, octadecanol, 1 ,6-hexanedio,, neopentyl gl~ycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pen1taerythritol, tris(hydroxy) eLtyl isocyanurate or N,N'-bis(hydroxyethyl)oxgiamide.
Esters of B-(3,5-dicyclohexyl-4-hydroxyphonyl)-propionic acid with monohydric or polyhydric alcohols, for example wi,,h methanol, octadecanol, 1,6-hexanediol, neopenty. glycol, thLodiethylene glcyol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxy) ethyl isocyanurate or N,N'-bis(hydroxvyethyl)oxalamide.
Amides of_1-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid, for example N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropi'onyl)hexamethylenediamine, N ,N -bis( 3,5-di-tert-buty1--4-hydroxyphenylpropionil)t rime thylenediamine and N,N'-bis(3,5-di-tert-butYl-4-hydroxyphenylpropionyl)hydrazine.
The amount of phosphor'Us(III) estev or other stabilizers is governed by the amount of piperidine compound added. Generall~y 0.01 to 1 by weight, *Qparticularly 0.05 to 0.5 by weight, is used relative to the polymer.
The process according to the invention relates tt, the addition of stabilizers to the polymerization or copolymerizaton of olefins. The olefins may be ethylene or ca-olefins. Examples of an a-oJlef in are propylene, 1-butenej I-pentene, 3-me thyl-1 tone, 4-methyl-I-pentr'ne or For copolymer~ization, mixtures of olefins witb one another can be used, or mixtures of olefins wit~h other ethylenically 15 unsaturated compounds, for example with vinyl acetate, vinyl chloride or alkyl acrylates. The process is of particular interest for the polymerization of propylene.
The invention also relates to the polymers or copolymers of olefins which have been stabilized according to the invention, particularly a polypropylene stabilized in this way.
The following examples illustrate the process in more detail without limiting it to the scope of the examples. Parts and percentages therein are by weight, unless stated otherwise.
Example 1: Polymer'zation of propylene The polymerization is carried out in a thermostatically controlled 4-litre stainless steel autoclave, equipped with a stirrer, which is dried before the beginning of the polymerization by purging for one hour with propylene gas at 70°C. The preparation of the solid catalyst component made from spherical MgClz and TiCl1 is carried out as described in Example 1 of US-A 4,111,835. It contains 2.9 of Ti and 19 of Mg.
mg of this catalyst are suspended in 25 ml of n-hexane and a mixture of 685 mg of triethylaluminium, 80 mg of phenyltriethoxysilane and 200 ml of hexane is added. This catalyst suspension is transferred under propylene gas to the autoclave. After closing the autoclave 1.25 1 of highly pure hydrogen are injected and finally 1.2 kg of liquid propylene are added under pressure. The contents are heated to 700C with stirring (500 rpm) and kept at this temperature for 2 hours. Then the excess of c propylene is released and the polymer obtained is treated with steam at 100 0 C for 10 minutes and subsequently dried at 50°C for 8 hours. The polymer consists of spherical particles. The following investigations of the polymer are carried out.
The catalyst activity (g of polymer/g of catalyst) is calculated from the Mg; content determined by atomic absorption and from the polymer yield.
I
16 The isotacticity is determined as the percentage proportion of the polymer which is insoluble in hot xylene. For this purpose the polymer is dissolved in hot xylene and after cooling the insoluble portion is filtered off and dried to constant weight.
The polymer morphology is qualitatively assessed visually, in order to determine wihether agglomerations have occurred.
The colour of the polymer is characterized by the Yellowness Index in accordance with ASTM D 1925-70.
As an indirect measure of the molecular weight, the intrinsic viscosity in tetrachloroethylene at 135°C is determined as well as the melt flow index in accordance with ASTM D 1238 at 230°C/2160 g.
.41
I
polo 4 04 4 W 0 4 4) ea *4 a 4.
«<4 4* 44 4 4* 4 4 The stability to oxidative degradation is determined from the time which elapses until there is a discernible emb_-c.lement of the polymer during oven ageing at elevated temperature. This cest is carried out on sheets, which are produced by press moulding at 220°C.
The following values resulted for the unstabilized polypropylene described above: Catalyst activity Isotacticity Intrinsic viscosity Morphology Melt flow index Yellowness Index Oven ageing of sheets 45.5 kg 97.0% 1.8 dl/g spherical 15 g/10 min at 135C. 0.75 h at 150°C: 0.50 h l -uL r^rrrrr.
17 Example 2: Stabilization The procedure described in Example 1 is repeated. About 10 minutes after the beginning of the polymerization a solution of 0.45 g of the stabilizer (piperidine compound) given in Table 1 in 50 ml of hexane is added to the autoclave. Polymerization, working-up and characterization of the polymer are carried out as in Example 1. The characteristic values obtained are listed in Table 1.
Table 1 49 w 91 4 9*
,J
4Q Stabiliser (Comp. no.) 1 2 4 8 9 10 11 Catalyst activity (kg/g) 45,5 43 41,8 40 43 45,5 45,5 Isotacticity 97.1 97.1 96.8 96.9 97.0 97.1 97.2 Intrinsic viscosity (dl/g) 1.9 1.8 2.0 1.8 1.84 1.56 1.55 Morphology Melt flow index (g/10 min) 6.6 9.0 6.0 6.3 13.3 15.3 14.2 Yellowness Index 2.2 1.9 2.4 2.5 2.2 2.4 2.3 Oven ageing at 135°C >700 >700 700 >700 860 900 860 at 150°C 180 325 370 320 250 55 240 as in Example 1 Table 1 (continued) Stabiliser (Comp. no.) 13 14 15 17 18 Catalyst activity (kg/g) 45.5 45.5 40.9 45.5 45.5 Isotacticity 97.0 96.9 97.0 97.0 97.0 Intrinsic viscosity (dl/g) 1.55 1.73 1.54 1.90 1.75 Morphology Melt flow index (g/10 min) 16.7 13.8 14.2 8.1 12.6 Yellowness Index 2.8 2.6 4.4 2.8 2.4 Oven ageing at 1350C 410 458 220 700 860 at 150 0 C 25 250 70 370 119 as in Example 1 :I ;ai I t 18 Table 1 (continued) Stabiliser (Comp. no.) 19 20 21 22 23 124 Catalyst activity (kg/g) 43. 2 45. 5 45. 5 43 43.2 45.5 44.1 Isotacticity ()97 97 97 97 97 92.2 97 Morphology MHelt flow index (g/10 min) 5.8 5.4 7.3 8.4 6.2 14.2 2.8 Yellowness index 3.2 3.4 3.3 3.4 3.2 4.0 3.7 Oven ageing at 150'C 288 216 408 400 410 240 400 Example 3: The procedure described in Example 1 is repeated. One h-our after the beginning of the polymerization a solution of 0.21 g of compound No. 3 in 50 ml of hexane is added to the polymerization mixture.
Working-up and -characterization are carried out as in Example 1.
The following values were obtained: a ~a a o ~a
O~
o a~ o a a a, a, a p a a a aa a, 9* a. a a, qa a a a.
A,
p Catalyst activity Isotacticity Intrinsic viscosity Morphology Melt flow index Yellowness Index Oven ageing of sheets 45. 5 kg 97,0% 1.9 dlfg as in '.xample 1 7.4 (g/10 min) at 13500: >100 h at 150'C: 144 h a a a. a.
a a.
Claims (12)
1. A process for the stabilization of poJlyolefins and olefin copolymers, which are prepared by low pressure polymerization on a solid catalyst, which is prepared by the reaction of an aluminium al~kyl with a solid pioduct of a magnesium dihalide in active form and a titanium compound, the stabilization being carried out by the addition of a sterically hindered piperidine derivative to the reaction mixture before or during polymerization, wherein a piperidine derivative of the formula I is used, C 3 CH 3 Cfi\CH 3 L in in which n is 1-4, RI is CI-C~alkyl, allyl, benzyl or acetyl, and Is S also hydrogen in the case of n R 2 is Cl-Claalkyl, Cs-Cl2cyclo- alkyl, C7-Cl2phenylalkyl, C3-CI2alkyl interrupted by or -N(R1 or is a group of the formula II, C 3 /CH3 R1 (n) o" cw3 R 3 is a group -0R5 -SR$ or '\R7 R 4 has one of the meanings given for R 3 when n 1, is one of the groups -X-R 8 Y-, 0- K or -I -CH 2) in which 9 is 2-6, when n 2f is one of the groups IA4/ I -C2 wcH 2 B) 3 -N or -OCH 2 CH 2 R 8 CH 2 CH2o- when n and is a group -N(R 5 )-CH 2 CHi 2 -A-CH2CH2--1C1H 2 CH 2 or 2 3 -A-(CH 2 p-k(H)3NR) when n 4, R 5 is Cl-CBalkyl, C 3 -G 1 2 alkenyl, Cs-C 1 2 tycloakyl, Cr-Clapheny2,alkyl, phenyl or phenyl substituted by Cl-Ci~alkyl, CI-C~.alkoxy or halogen, RI and R 7 are independently of one another hydrogen; Ci-C,8alkyl, CS-C12- cycjloalkyl, C 7 "Clzphenylalkyl. or a group of the formula II, or R 6 and R 7 are together 04-Cioalkylene ot CS-C7oxa- or azaal1kylene, RI is C 2 -C12- al1kylene, Ci-Cazalkylene interrupted by or -N(R 6 C 5 -C1 2 CYClo- .alkylene or phenylene, R 9 is hydrogen or methyl, X and Y are indepen- 4 dently of one another or -N(R 6 m is 2 or 3 and p is 2-10.
2. The process according to claim 1 wherein a piperidine derivative of the formula I is used, in which n is 1-4, R! isC-C4alkyl, and is also *#JtlA.SJ 5 *S 14 tO0C 'JA U )2 4* .0 Jj U. 5, tJ 4I4~O *0*4 9 9, 4a 4 aa 4 9 4* @4 9 S 4aa4 U 4 4* 4 44 4
4. a a 4 49 group of the .ioruiula II', R 3 is a grouip -ORS or has one of the meanings, given for R 3 whem n is a group or -<>-CH2CH2-N(R6)- when n is a group -NR -C1)m -CZmNR) when n =3 and is a group -N(R~6 )-Cfl 2 C1Iz-g-C zH--t2Cl-() or -N(R6)-CHl2CH 2 CHZ-A(C"iz) p-kC1C2C2Re) when n -4, R5 is CI-Ca2alkylo cyclohexyl, benZyl, pbenyl. or tolyl, R' 6 is hydrogen, Cl-Cl2alkyl, rqyclobexcyl, bemzyl or a group of the formula II, R 7 is CI-C12alkyJ, cqyclohexyl or a group of the formula 11 ov 10 and R1 are together tetramethyleme, pentamethylene or 3-oxapen tame thylene R' is C2-Clzalkylene, cyclohexylene or phenylone, X and Y are or m is 2 or 3 and p is 2-6. <4 21 3. The process according to claim 1 wherein in formula I, R I is methyl. 4. The process according Ci-Csalkyl or a group of The p-oce,is according -N(R 6 (R 7
6. The process according is a group -N(R 6 )(R 7 to claim 1 wherein in the formula II. formula I, R 2 is to claim 1 wherein in formula I, R 3 is a group to claim 1 wherein in formula I, n 1 and R 4
7. The process according to claim 1 wherein in formula I, n 2, X and Y are a group -N(R 6 and R 8 is Cz-Csalkylene.
8. The process according to clainm I wherein in formula I, n 2 and RI *4 94 a 04 4 4 4 9 4 0 44* as 4' *44 4 4 a. is a group -NH-CH2C 2
9. The process according to claim 1 wherein in R 6 is hydrogen or Ci-Cialkyl. formula I, n= 3 or 4 and The process according to claim I wherein the catalyst from spherical magnesium chloride. is prepared
11. The process according to claim 1 wherein titanium tetrachloride is used as titanium compound in the preparation of the catalyst.
12. The process the addition of
13. The process having at least according to claim 1 wherein the catalyst is activated by an electron donor. according to claim 12 wherein an or nosilkco compound one Si-O-C bond is used as electro .,nor. 22 14, The process according to claim 1 wherein, apart from the sterically hindered piperidin compound, a phosphorus(III) ester is added to the polymerization. The process according to claim 14 wherein a triorganophosphite is added, 16, The process according to either of claims 1 or 14, wherein an anti- oxidant of the sterically hindered phenol type is additionally added to the polymerization, 17, The process according to qlai 1 wherein the process is used for the polymerization of propylene
18. A polymer stabilized by the process of claim 1. a ts<' g4th I
19. A polypropylene stabilized by the process of claim 1. ,4 S 20, A process a4cording to Claim L, or a polymer According to Is 1 Claim 18, substantially as herein desaribed, with reference to Pc 6 a ny one of the foQregoing examples thereof, *4 I Dated the 20Wt .M or ue 1989 CIBA-GEIGY A 4 G. a Oy Its Patent Attorneys ARTHUR S. CAVE CO.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH250288 | 1988-06-30 | ||
| CH2502/88 | 1988-06-30 |
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|---|---|
| AU3669089A AU3669089A (en) | 1990-06-14 |
| AU621630B2 true AU621630B2 (en) | 1992-03-19 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU36690/89A Ceased AU621630B2 (en) | 1988-06-30 | 1989-06-21 | Process for the stabilization of polyolefins |
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|---|---|
| EP (1) | EP0350444A1 (en) |
| JP (1) | JPH0253807A (en) |
| KR (1) | KR910000880A (en) |
| CN (1) | CN1039605A (en) |
| AU (1) | AU621630B2 (en) |
| BR (1) | BR8903236A (en) |
| CA (1) | CA1340912C (en) |
| DD (1) | DD297832A5 (en) |
| MX (1) | MX169511B (en) |
| ZA (1) | ZA894936B (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE58909021D1 (en) * | 1988-06-30 | 1995-03-30 | Ciba Geigy Ag | Process for the production of thermally stable olefin polymers. |
| IT1237129B (en) * | 1989-11-10 | 1993-05-18 | Valerio Borzatta | PIPERIDIN TRIAZINIC COMPOUNDS SUITABLE FOR USE AS STABILIZERS FOR ORGANIC MATERIALS. |
| IT1237541B (en) * | 1989-12-28 | 1993-06-08 | Ciba Geigy | PIPERIDIN TRIAZIN COMPOUNDS SUITABLE FOR USE AS STABILIZERS FOR ORGANIC MATERIALS |
| IT1252205B (en) * | 1991-12-13 | 1995-06-05 | Himont Inc | PROCESS FOR THE PREPARATION OF STABILIZED POLYOLEFINS AND PRODUCTS SO OBTAINED. |
| IT1255233B (en) * | 1992-07-17 | 1995-10-20 | Himont Inc | PROCEDURE FOR THE STABILIZATION OF OLEFINIC POLYMERS |
| IT1263993B (en) * | 1993-04-05 | 1996-09-06 | Ciba Geigy Spa | PIPERIDIN-TRIAZIN COMPOUNDS SUITABLE FOR USE AS STABILIZERS FOR ORGANIC MATERIALS |
| EP0921181A1 (en) * | 1997-12-05 | 1999-06-09 | Fina Research S.A. | Production of propylene |
| TR201901553T4 (en) | 2013-10-17 | 2019-02-21 | Basf Se | Blocked amine light stabilizers based on triazine, piperidine and pyrrolidine and prolidine. |
| EP3478731B1 (en) * | 2016-06-30 | 2020-08-05 | Dow Global Technologies LLC | Procatalyst compositions useful for low comonomer incorporation and process for preparing the same |
| CN109810398A (en) * | 2017-11-21 | 2019-05-28 | 中国石油天然气股份有限公司 | A kind of ultra-high molecular weight isotactic polypropylene resin composition and preparation method thereof |
| CN109134928B (en) * | 2018-10-31 | 2020-05-19 | 天集化工助剂（沧州）有限公司 | N-substituted triazine hindered amine light stabilizer, and preparation method and application thereof |
| EP4077313B1 (en) * | 2019-12-16 | 2026-04-08 | Basf Se | Process for the preparation of piperidine compounds |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU576021B2 (en) * | 1984-11-09 | 1988-08-11 | Ian James O'brien | Position control mechanism |
| AU3668889A (en) * | 1988-06-30 | 1990-01-04 | Ciba Specialty Chemicals Holding Inc. | Process for the preparation of heat-stable olefin polymers |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1207491B (en) * | 1985-01-30 | 1989-05-25 | Himont Inc | PROCESS FOR PREPARING OLEFINIC, THERMALLY STABLE POLYMERS. |
| IT1196980B (en) * | 1986-07-23 | 1988-11-25 | Enichem Sintesi | (CO) POLYMERIZATION PROCESS OF ALPHA-OLEFINS IN THE PRESENCE OF ANTIOXIDANTS |
-
1989
- 1989-06-21 AU AU36690/89A patent/AU621630B2/en not_active Ceased
- 1989-06-21 EP EP89810480A patent/EP0350444A1/en not_active Withdrawn
- 1989-06-28 CA CA000604127A patent/CA1340912C/en not_active Expired - Fee Related
- 1989-06-28 DD DD89330071A patent/DD297832A5/en not_active IP Right Cessation
- 1989-06-28 KR KR1019890008914A patent/KR910000880A/en not_active Ceased
- 1989-06-29 MX MX016650A patent/MX169511B/en unknown
- 1989-06-29 ZA ZA894936A patent/ZA894936B/en unknown
- 1989-06-30 BR BR898903236A patent/BR8903236A/en not_active IP Right Cessation
- 1989-06-30 CN CN89104462A patent/CN1039605A/en not_active Withdrawn
- 1989-06-30 JP JP1169746A patent/JPH0253807A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU576021B2 (en) * | 1984-11-09 | 1988-08-11 | Ian James O'brien | Position control mechanism |
| AU3668889A (en) * | 1988-06-30 | 1990-01-04 | Ciba Specialty Chemicals Holding Inc. | Process for the preparation of heat-stable olefin polymers |
Also Published As
| Publication number | Publication date |
|---|---|
| KR910000880A (en) | 1991-01-30 |
| CN1039605A (en) | 1990-02-14 |
| AU3669089A (en) | 1990-06-14 |
| MX169511B (en) | 1993-07-08 |
| BR8903236A (en) | 1990-02-13 |
| EP0350444A1 (en) | 1990-01-10 |
| DD297832A5 (en) | 1992-01-23 |
| CA1340912C (en) | 2000-02-29 |
| JPH0253807A (en) | 1990-02-22 |
| ZA894936B (en) | 1990-03-28 |
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