CA1282893C - Process for the stabilisation of spherically polymerised polyolefins - Google Patents
Process for the stabilisation of spherically polymerised polyolefinsInfo
- Publication number
- CA1282893C CA1282893C CA000508015A CA508015A CA1282893C CA 1282893 C CA1282893 C CA 1282893C CA 000508015 A CA000508015 A CA 000508015A CA 508015 A CA508015 A CA 508015A CA 1282893 C CA1282893 C CA 1282893C
- Authority
- CA
- Canada
- Prior art keywords
- tert
- butyl
- amine
- process according
- stabilisers
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 18
- 230000006641 stabilisation Effects 0.000 title claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 239000003381 stabilizer Substances 0.000 claims abstract description 28
- 150000001412 amines Chemical class 0.000 claims abstract description 23
- 239000000839 emulsion Substances 0.000 claims abstract description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 4
- 125000003341 7 membered heterocyclic group Chemical group 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 3
- 239000006185 dispersion Substances 0.000 claims description 24
- 150000002148 esters Chemical class 0.000 claims description 10
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 7
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 4
- WPMYUUITDBHVQZ-UHFFFAOYSA-M 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=CC(CCC([O-])=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-M 0.000 claims description 2
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 claims 1
- -1 polypropylene Polymers 0.000 description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 238000003756 stirring Methods 0.000 description 14
- 239000004743 Polypropylene Substances 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 229920001155 polypropylene Polymers 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 8
- 239000003995 emulsifying agent Substances 0.000 description 7
- 239000007983 Tris buffer Substances 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000011324 bead Substances 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 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 4
- 229940043237 diethanolamine Drugs 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 4
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000001593 sorbitan monooleate Substances 0.000 description 4
- 235000011069 sorbitan monooleate Nutrition 0.000 description 4
- 229940035049 sorbitan monooleate Drugs 0.000 description 4
- 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 4
- 229960004418 trolamine Drugs 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000001273 butane Substances 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 150000002815 nickel Chemical class 0.000 description 3
- 229920000053 polysorbate 80 Polymers 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 2
- UTBIMNXEDGNJFE-UHFFFAOYSA-N 2,3,6-trimethylpyridine Chemical compound CC1=CC=C(C)C(C)=N1 UTBIMNXEDGNJFE-UHFFFAOYSA-N 0.000 description 2
- BWZVCCNYKMEVEX-UHFFFAOYSA-N 2,4,6-Trimethylpyridine Chemical compound CC1=CC(C)=NC(C)=C1 BWZVCCNYKMEVEX-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 2
- 241000905957 Channa melasoma Species 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 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 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 239000000155 melt Substances 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
- 229910052759 nickel Inorganic materials 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000006353 oxyethylene group Chemical group 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002530 phenolic antioxidant Substances 0.000 description 2
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229940116351 sebacate Drugs 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- KJYSXRBJOSZLEL-UHFFFAOYSA-N (2,4-ditert-butylphenyl) 3,5-ditert-butyl-4-hydroxybenzoate Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OC(=O)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 KJYSXRBJOSZLEL-UHFFFAOYSA-N 0.000 description 1
- HQEPZWYPQQKFLU-UHFFFAOYSA-N (2,6-dihydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC(O)=C1C(=O)C1=CC=CC=C1 HQEPZWYPQQKFLU-UHFFFAOYSA-N 0.000 description 1
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical class OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 1
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- ZEBMSMUPGIOANU-UHFFFAOYSA-N (3,5-ditert-butyl-4-hydroxyphenyl)methylphosphonic acid Chemical class CC(C)(C)C1=CC(CP(O)(O)=O)=CC(C(C)(C)C)=C1O ZEBMSMUPGIOANU-UHFFFAOYSA-N 0.000 description 1
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- MQQKTNDBASEZSD-UHFFFAOYSA-N 1-(octadecyldisulfanyl)octadecane Chemical compound CCCCCCCCCCCCCCCCCCSSCCCCCCCCCCCCCCCCCC MQQKTNDBASEZSD-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
- IOHCSOXUCWUZQJ-UHFFFAOYSA-J 2,2'-spirobi[1,3,2-benzodioxastannole] Chemical compound O1c2ccccc2O[Sn]11Oc2ccccc2O1 IOHCSOXUCWUZQJ-UHFFFAOYSA-J 0.000 description 1
- AFHLFBRAUWBAFJ-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol hexane-1,6-diol 2-(2-hydroxyethoxy)ethanol 2-[2-(2-hydroxyethoxy)ethoxy]ethanol methanol octadecan-1-ol Chemical compound OCC(CO)(CO)CO.C(CCCCCO)O.C(COCCOCCO)O.C(CCCCCCCCCCCCCCCCC)O.C(COCCO)O.CO AFHLFBRAUWBAFJ-UHFFFAOYSA-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
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- JWOWIZVDYKUULJ-UHFFFAOYSA-N 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OPOCC11COPOC1 JWOWIZVDYKUULJ-UHFFFAOYSA-N 0.000 description 1
- 125000003764 2,4-dimethylpentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- KUFFULVDNCHOFZ-UHFFFAOYSA-N 2,4-xylenol Chemical compound CC1=CC=C(O)C(C)=C1 KUFFULVDNCHOFZ-UHFFFAOYSA-N 0.000 description 1
- SKCLFSWRVSVQRL-UHFFFAOYSA-N 2,5-bis(2-methylbutan-2-yl)benzene-1,4-diol;2,5-ditert-butylbenzene-1,4-diol;2,6-ditert-butyl-4-methoxyphenol;4-octadecoxy-2,6-diphenylphenol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O.COC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1.CCC(C)(C)C1=CC(O)=C(C(C)(C)CC)C=C1O.C=1C(OCCCCCCCCCCCCCCCCCC)=CC(C=2C=CC=CC=2)=C(O)C=1C1=CC=CC=C1 SKCLFSWRVSVQRL-UHFFFAOYSA-N 0.000 description 1
- BVNPSIYFJSSEER-UHFFFAOYSA-H 2-[2-(1,3,2-benzodioxastibol-2-yloxy)phenoxy]-1,3,2-benzodioxastibole Chemical compound O([Sb]1Oc2ccccc2O1)c1ccccc1O[Sb]1Oc2ccccc2O1 BVNPSIYFJSSEER-UHFFFAOYSA-H 0.000 description 1
- HHPDFYDITNAMAM-UHFFFAOYSA-N 2-[cyclohexyl(2-hydroxyethyl)amino]ethanol Chemical compound OCCN(CCO)C1CCCCC1 HHPDFYDITNAMAM-UHFFFAOYSA-N 0.000 description 1
- OMCYEZUIYGPHDJ-UHFFFAOYSA-N 2-hydroxy-N-[(2-hydroxyphenyl)methylideneamino]benzamide Chemical compound OC1=CC=CC=C1C=NNC(=O)C1=CC=CC=C1O OMCYEZUIYGPHDJ-UHFFFAOYSA-N 0.000 description 1
- UORSDGBOJHYJLV-UHFFFAOYSA-N 2-hydroxy-n'-(2-hydroxybenzoyl)benzohydrazide Chemical compound OC1=CC=CC=C1C(=O)NNC(=O)C1=CC=CC=C1O UORSDGBOJHYJLV-UHFFFAOYSA-N 0.000 description 1
- MZZYGYNZAOVRTG-UHFFFAOYSA-N 2-hydroxy-n-(1h-1,2,4-triazol-5-yl)benzamide Chemical compound OC1=CC=CC=C1C(=O)NC1=NC=NN1 MZZYGYNZAOVRTG-UHFFFAOYSA-N 0.000 description 1
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 1
- MQWCQFCZUNBTCM-UHFFFAOYSA-N 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylphenyl)sulfanyl-4-methylphenol Chemical compound CC(C)(C)C1=CC(C)=CC(SC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O MQWCQFCZUNBTCM-UHFFFAOYSA-N 0.000 description 1
- GPNYZBKIGXGYNU-UHFFFAOYSA-N 2-tert-butyl-6-[(3-tert-butyl-5-ethyl-2-hydroxyphenyl)methyl]-4-ethylphenol Chemical compound CC(C)(C)C1=CC(CC)=CC(CC=2C(=C(C=C(CC)C=2)C(C)(C)C)O)=C1O GPNYZBKIGXGYNU-UHFFFAOYSA-N 0.000 description 1
- BKZXZGWHTRCFPX-UHFFFAOYSA-N 2-tert-butyl-6-methylphenol Chemical compound CC1=CC=CC(C(C)(C)C)=C1O BKZXZGWHTRCFPX-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
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-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
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- MDWVSAYEQPLWMX-UHFFFAOYSA-N 4,4'-Methylenebis(2,6-di-tert-butylphenol) Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 MDWVSAYEQPLWMX-UHFFFAOYSA-N 0.000 description 1
- VYTHNBNYXNKXEW-UHFFFAOYSA-N 4-butyl-2,6-ditert-butylphenol;2,6-ditert-butyl-4-ethylphenol Chemical compound CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1.CCCCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VYTHNBNYXNKXEW-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
- LZAIWKMQABZIDI-UHFFFAOYSA-N 4-methyl-2,6-dioctadecylphenol Chemical compound CCCCCCCCCCCCCCCCCCC1=CC(C)=CC(CCCCCCCCCCCCCCCCCC)=C1O LZAIWKMQABZIDI-UHFFFAOYSA-N 0.000 description 1
- 125000004195 4-methylpiperazin-1-yl group Chemical group [H]C([H])([H])N1C([H])([H])C([H])([H])N(*)C([H])([H])C1([H])[H] 0.000 description 1
- NTDQQZYCCIDJRK-UHFFFAOYSA-N 4-octylphenol Chemical compound CCCCCCCCC1=CC=C(O)C=C1 NTDQQZYCCIDJRK-UHFFFAOYSA-N 0.000 description 1
- DBOSBRHMHBENLP-UHFFFAOYSA-N 4-tert-Butylphenyl Salicylate Chemical compound C1=CC(C(C)(C)C)=CC=C1OC(=O)C1=CC=CC=C1O DBOSBRHMHBENLP-UHFFFAOYSA-N 0.000 description 1
- ISAVYTVYFVQUDY-UHFFFAOYSA-N 4-tert-Octylphenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C=C1 ISAVYTVYFVQUDY-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- DXUGJXDOICODOB-UHFFFAOYSA-N C(C)(C1=C(C(=CC(=C1)C(C)(C)C)C(C)(C)C)O)C1=C(C(=CC(=C1)C(C)(C)C)C(C)(C)C)O.C(C1=C(C(=CC(=C1)C(C)(C)C)C(C)(C)C)O)C1=C(C(=CC(=C1)C(C)(C)C)C(C)(C)C)O.C(C1=C(C(=CC(=C1)C)CCCCCCCCC)O)C1=C(C(=CC(=C1)C)CCCCCCCCC)O Chemical compound C(C)(C1=C(C(=CC(=C1)C(C)(C)C)C(C)(C)C)O)C1=C(C(=CC(=C1)C(C)(C)C)C(C)(C)C)O.C(C1=C(C(=CC(=C1)C(C)(C)C)C(C)(C)C)O)C1=C(C(=CC(=C1)C(C)(C)C)C(C)(C)C)O.C(C1=C(C(=CC(=C1)C)CCCCCCCCC)O)C1=C(C(=CC(=C1)C)CCCCCCCCC)O DXUGJXDOICODOB-UHFFFAOYSA-N 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
- VSRRGPPFTIJBJG-UHFFFAOYSA-N DL-4-hydroxy stearic acid Chemical compound CCCCCCCCCCCCCCC(O)CCC(O)=O VSRRGPPFTIJBJG-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- YIKSCQDJHCMVMK-UHFFFAOYSA-N Oxamide Chemical class NC(=O)C(N)=O YIKSCQDJHCMVMK-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 208000037062 Polyps Diseases 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- ZBZOOZMRHMCRBU-UHFFFAOYSA-N S1SC(=CC1)C1=CC(=CC=C1C(=O)OCC1=C(C(=C(C=C1C)C(C)(C)C)O)C)C(=O)OCC1=C(C(=C(C=C1C)C(C)(C)C)O)C.C(C)(C)(C)C=1C=C(CSCC(=O)OCCCCCC(C)C)C=C(C1O)C(C)(C)C Chemical compound S1SC(=CC1)C1=CC(=CC=C1C(=O)OCC1=C(C(=C(C=C1C)C(C)(C)C)O)C)C(=O)OCC1=C(C(=C(C=C1C)C(C)(C)C)O)C.C(C)(C)(C)C=1C=C(CSCC(=O)OCCCCCC(C)C)C=C(C1O)C(C)(C)C ZBZOOZMRHMCRBU-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000003490 Thiodipropionic acid Substances 0.000 description 1
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 1
- BEIOEBMXPVYLRY-UHFFFAOYSA-N [4-[4-bis(2,4-ditert-butylphenoxy)phosphanylphenyl]phenyl]-bis(2,4-ditert-butylphenoxy)phosphane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(C=1C=CC(=CC=1)C=1C=CC(=CC=1)P(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C BEIOEBMXPVYLRY-UHFFFAOYSA-N 0.000 description 1
- HHFMFWAFQGUGOB-UHFFFAOYSA-N [5-(4-tert-butylbenzoyl)-2,4-dihydroxyphenyl]-(4-tert-butylphenyl)methanone Chemical compound C1=CC(C(C)(C)C)=CC=C1C(=O)C1=CC(C(=O)C=2C=CC(=CC=2)C(C)(C)C)=C(O)C=C1O HHFMFWAFQGUGOB-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000003931 anilides Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000000649 benzylidene group Chemical group [H]C(=[*])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 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 1
- SZRLKIKBPASKQH-UHFFFAOYSA-M dibutyldithiocarbamate Chemical compound CCCCN(C([S-])=S)CCCC SZRLKIKBPASKQH-UHFFFAOYSA-M 0.000 description 1
- 125000006182 dimethyl benzyl group Chemical group 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- SWRGUMCEJHQWEE-UHFFFAOYSA-N ethanedihydrazide Chemical compound NNC(=O)C(=O)NN SWRGUMCEJHQWEE-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 210000004905 finger nail Anatomy 0.000 description 1
- 229960004594 fominoben Drugs 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 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
- YIMHRDBSVCPJOV-UHFFFAOYSA-N n'-(2-ethoxyphenyl)-n-(2-ethylphenyl)oxamide Chemical compound CCOC1=CC=CC=C1NC(=O)C(=O)NC1=CC=CC=C1CC YIMHRDBSVCPJOV-UHFFFAOYSA-N 0.000 description 1
- FPQJEXTVQZHURJ-UHFFFAOYSA-N n,n'-bis(2-hydroxyethyl)oxamide Chemical compound OCCNC(=O)C(=O)NCCO FPQJEXTVQZHURJ-UHFFFAOYSA-N 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
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- NTTIENRNNNJCHQ-UHFFFAOYSA-N octyl n-(3,5-ditert-butyl-4-hydroxyphenyl)carbamate Chemical compound CCCCCCCCOC(=O)NC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NTTIENRNNNJCHQ-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- AHLBNYSZXLDEJQ-FWEHEUNISA-N orlistat Chemical compound CCCCCCCCCCC[C@H](OC(=O)[C@H](CC(C)C)NC=O)C[C@@H]1OC(=O)[C@H]1CCCCCC AHLBNYSZXLDEJQ-FWEHEUNISA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 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
- 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
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229960000969 phenyl salicylate Drugs 0.000 description 1
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical class OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- MQOCIYICOGDBSG-UHFFFAOYSA-M potassium;hexadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCC([O-])=O MQOCIYICOGDBSG-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000002226 simultaneous effect Effects 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- IJRHDFLHUATAOS-DPMBMXLASA-M sodium ricinoleate Chemical compound [Na+].CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O IJRHDFLHUATAOS-DPMBMXLASA-M 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000004094 surface-active agent 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
- 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
- CNUJLMSKURPSHE-UHFFFAOYSA-N trioctadecyl phosphite Chemical compound CCCCCCCCCCCCCCCCCCOP(OCCCCCCCCCCCCCCCCCC)OCCCCCCCCCCCCCCCCCC CNUJLMSKURPSHE-UHFFFAOYSA-N 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- BOXSVZNGTQTENJ-UHFFFAOYSA-L zinc dibutyldithiocarbamate Chemical compound [Zn+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC BOXSVZNGTQTENJ-UHFFFAOYSA-L 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
- C08J3/2053—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the additives only being premixed with a liquid phase
-
- 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
- C08K5/17—Amines; Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
Abstract
Process for the stabilisation of spherically polymerised polyolefins Abstract of the Disclosure Spherically polymerised polyolefins can by advantageously stabilised by being treated with at least one emulsion or dispesion containing a stabiliser or a mixture of stabilisers and an amine of formula I
Description
3-15331/~
Process Eor the stabilisation of spherically polymerised poly-olefins The present invention relates to a proce~s for the stabilisation of ~pherically polymeris~d polyolefins by treating said polyslefins with an emulsion or dlspersion of a stabilisar or of a mlxture of stabilisers, a~ well as to th~ polyolefins stabilised in this mannsr .
No satisfactory method of stabilisation is known for the recently developed spherically polymerised polyolefins as described e.g. by P. &alli, P.C. Barbé and L. ~oristi in "~igh YiPld Catalyst~ in Olefin Polymerization", Die Angewandte Nakromolekulare Chemie ~Applied Macromolecular Chemistry) 120 (1984), pp, 73-90 tNo. 1935).
The cus~omary methods oE stahilising polyolefins in powdered form, e.g. by incorporat~on of the ætabiliser in powdered form and subsequent extrusion, can not be applied since they do not allow a sufficiently homogeneous distribution. A process for the stabili-sation of spherically pol~merised polypropylene is d~scribed in Japanose Rokai Sho S9-150719. In said process, the spherlcally polymerised polypropylene is treated in a high-speed mixer at temparat~res up to a ma~l~um of 162C with a stabillser or mlxtura of 3tabilisers, the meltlng point of which is lower than 162C. The spharic~l poly~er particles are thereby coated wlth the stabiliser melt. Also when applyin~ this ~ethod problems of distrib~ion aris~, for the result are not entirely satisf~ctory. The addition of, praferably, 3 to 15 % by weight of a binder~ based on the poly-propylene, can i~prove the resul-ts somewhat.
Surpris~ngly, it has now been found that the above-mentioned 3pherlcally polymerised polyolefin~ can be stabilised in very satisfactory manner even without the addition oE a binder~if they are treated wlth an emul~ion or dispersion of a stablliser or of a mixture oE stabilisers, which emlllsion or dispersion contains a small amount of an amine.
Stable aqueo~ls dispersions containing a phenolic antioxidant, a soap and a non-ionic or anionic surface-active compound are descri'oed in VS patent 3 962 123. Said dispersions are suitable for example for the stabilisation of acrylonitrile/butadiene/styrene or acrylo-nitrile/methyl acrylate.
Aqueous dispersions of phenolic antioxidants are also described in Japanese Kokai Sho 60-63274.
The present invention relates to a process for the stabilisation of spherically poly~erised polyolefins by treating said polyolefins with at least one emulsion or dispersion containing a stabiliser or a ~ixture of stabilisers and 0.05 to 1 % by weight, based on the polyolefin, of an amine of formula I
R1- ~ R3 (I) wherein R1 is C1-C20alkyl which may be substituted by -OH, or is C3-Csoalkyl which is interrupted by one o~ more oxygen atoms, or is C1-C8alkoxy, and each of R2 and R3 independently of the other is hydrogen or has one of the mPanings indicated for R1, or Rz and R3, together with the nitrogen atom to which they are attached, form a 5~ to 7-membered heterocyclic ring.
R1, R2 and R3 as C1-C20alkyl are for example methyl~ ethyl~ propyl, isopropyl, butyl, tert-butyl, n pentyl, ~-methylpentyl, hexyl, 2,4-dimethylpentyl~ n-octyl, 6-methylheptyl, 2-ethylhexyl, decyl, dodecyl, octadecyl, octadecylethyl or eico~yl. Linear alkyl is pre-ferred, with linear Cl2-C1galkyl being most preferred.
~,8~Z~
R1, R2 and R3 a~ al~yl which is substituted by -OH are preferably Cl-C3alkyl which 19 substituted terminally by ~OH, e.g. hydroxy-methyl, 2-hydroxyethyl, 3-hydroxypropyl, 1-hydroxyisopropyl, 6-hydroxyhexyl or ~-hydroxyoctyl, with 1-hydroxyisopropyl being preferred and 2-hydroxyethyl being most preferred.
Rl, R2 and R3 as alkyl which i~3 interrupted by oxygen are preferably alkyl whlch i8 interrupted by more than one oxygen atom, e.g. by 2 to 20 oxygen atom~. Particularly preferred are radical~ of the formula ~CHzCH2(~;H
wherein n is an integer from 2 to 20~
If Rz and R3, together ~ith the nitrogen atom to whlch they are attached, form a heterocyclic ring, then sa~d rlng i~ e.g. pyr-azolidin-1-yl, piperidi~o, morpholino, piperazin-l-yl, 4-methyl-piperazin-1-yl, hexahydroazepin-l-yl, ho~opiperazin-l-yl or 4-methylhomopiperazin-l-yl.
R1, R~ and R3 as alkoxy are e.g. methoxy~ etho~y, 3-propoxy, 4-n-butoxy or 1-n-ortyloxy.
Liquid a~ine~ of formula I are preferred. Liquid amines of formula I
wherein at least one of the radical~ Rz and R3 has one of the meanings indicated above for Rl are particularly preferred. Amine~
~herein R~ traight chain C1z-Clgalkyl and at laast one of the radicals Rz and R3 i~ a group ~cH2cH2o~n ~
wherein n is an integer fro~ 1 to 10~ ara li~ewise preferred.
1~2~93 The liquid aminas of formula I wherein R1, R2 and R3 are C2-CI,alkyl which is subs~ituted terminally by -OH, e.gO triethanolamine, are also particularly preferred.
Examples of suitable amines are butylamine, dibutylamine, tri-ethanolamine, triisopropanolamine, N,N-bis(diethanol)dodecylamine, N,N-bis(diethanol)octadecylamine, 2,4,6-trimethylpyridine, 2,3,6-trimethylpyridine and mixtures thereof and technical amine mixtures for example that which is commercially avail.able under the name of Atmer 163~ (manufact~red by ATLAS) or that which is commercially available under the name of Armostat A 400~ (manufactured by AKZO~.
The emulsion or dispersion which the polyolefin is treated with contains the stabiliser or mixture of stabilisers preferably in an amount of 0.03 to 5 % by weight, most p~eferably O.1 to 1.0 % by weight, based on the polyolefin.
Examples of suitable stabilisers are the following:
1 Antioxidants 1.1. Alkvlated monophenols 2,6-di-tert-butyl-4-methylphenol 2-tert-butyl~4,6-dimethylphenol 2,6-di-tert-butyl-4 ethylphenol 2,6-di-tert-butyl-4-n-butylphenol 2~6-di-tert-butyl-4-isobutylphenol 2,6-dicyolopentyl-4-methylphenol 2~ methylcyclohexyl)-4,6-dimethylphenol 2,6-dioctadecyl-4-methylphenol 2,4,6-tricyclohaxylphenol 2,6~di~tert-butyl-4-methoxymetbylphenol 1.2. Alkylated hydroquinone~
2,6-di-tert-butyl-4-methoxyphenol 2,5-di-tert-butylhydroquinone 2,5-di-tert-amylhydroquinone 2,6-diphenyl-4-octadecyloxyphenol 1.3. Hydro~ylated thiodiphenyl ethers 2,2'-thiobis(6-tert-butyl-4-methylphenol) 2,2'-thlobi~(4-octylphenol) 4,4'-thiobis(6-tert-butyl-3-m0thylphenol) 4,4'-thiobis(6-tert-butyl-2-methylphenol~
1.4. Alkxlid0nebisphenols 2,2' methylenebi~(6-tert-butyl-4-methylphenol) 2,2'-methylenebis(6-tert-butyl-4-ethylphenol) 2,2'-methylenebis[4-methyl-6-(~-methylcyclohexyl)phenol]
2,2'-methylenebis~4-methyl-6-cyclohexylphenol) 2,2'-methylenebis(6-nonyl-4-methylphenol) 2,2'-methylenebis(4,6-di-tert-butylphenol) 2,2'-ethylidenebis(4,6-di-tert-butylphenol) 2,2'-ethylidenebis(6-tert-butyl-4-i~obutylphenol) 2,2'-methylenebis[6-~-methylben~yl)-4-nonylphenol]
2,2'-methylenebis[6~ dimethylbenzyl~-4-nonylphenol]
4,4'-methylenebis(2,6-di-tert-butylphenol) 4,4'-methylenebis(6~tert-butyl-2-methylphenol) 1,1-b$s(5-tert-butyl-4-hydroxy-2-methylphenyl)butane 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybPnzyl)-4-mathylphenol 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl~butane l~l-bis(5-tert-b~tyl-4-hydroxy-2-methylphenyl~-3-n-dodecyl-mercaptobutane ethylene glycol bi~[3,3-bis~3'-tert-butyl-4'-hydroxyphanyl)butyr~te]
bis(3-tert-butyl-4-hydroxy 5-methylph0nyl)dicyclopentadiene bi~[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphenyl] terephthalate 1.5. Benzyl compounds 1,3,5-trig(3,5-cli-tert-butyl-4-hydroxybenzyl)-2,4,6 trimethylbenzqne bi3(3,5-di-tert-butyl-4-hyclroxyben2yl) sulfide isooctyl 3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithiolterephthalate 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl~ isocyanurata 1,3,5-tris(4-tert-butyl-3~hydroxy-2,6-dimethylbenzyl) isocyanurate dioctadecyl 3,5-di-tert-butyl-4-hydroxyhen~ylphosphonate c~lcium salt of monoethyl 3,5-di-ter~-butyl-4-hydroxybenzylphos-phonate _6 cylaminoph~nols anilide of 4-hydroxylauric acid anilide of 4-hydroxystearic acid 2,4-bls(octylmercapto)-6-(3,5-di-tert-butyl~4-hydroxyanilino) -3-tria~irle octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate 1.?. E~ters of ~-(3~ di- ert-butyl-4-h~drDxyE~y~ropionic acld with mono- or polyhydric alcohols, e.g. with methanol diethylene glycol octadecanol triethylene glycol 1,6-hexanediol pentaerythritol neopsntyl glycol tris(hydroxyethyl) isocyanur~te thiodiethylene glycol N,N'-bis(hydroxyethyl)oxalic acid diamide 1.8. Esterg of ~-(S-tcrt-butyl-4-hydroxy-3-methy~phenyl~propioni-c acid with mono- or polyhydric alcohol-~, e.g. with methanol diethylsne glycol octadecanol triethyl~ne glycol 1,6-hexanediol pantaerythritol neopentyl glycol tris(hydroxyethyl~ isocyanurate thiodiethylene glycol N,N'-bis(hydroxy~thyl)oxalic acid dlamide 1.~. Amldes of ~-~3,5-di tert-butyl-4-h~droxypheny--l-)propionic acid e.g.
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl~hexamethylene diamine N,N'-bis~3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylene-diamine N,N'-bis(3,5-di-tert-butyl--4-hydroxyphenylpropionyl)hydrazine.
2. W absorbers and light_stabilisers 2.1. 2-~2~ydroxyphenyl?ben~otriazoles~ for exampl~ the 5'-methyl, 3' 9 5'-di-tert-butyl, S'-tert-butyl, 5'-~1,1,3,3-tetramethylbutyl), 5-chloro-3'~5'-di-tert-butyl, 5-chloro-3'-tert-butyl-5'-methyl, 3'-sec-butyl-5'-tert-butyl, 4'-octoxy, 3',5'-di-tert-amyl and 3',5'-bis(~,~-dimethylbenzyl~ derivatiYes.
2.2. 2 HYdroxybenzophenones, for exa~ple the 4-hydroxy, 4-methoxy, 4-octoxy, 4-decyloxy, 4-dsdecyloxy, 4-b~nzyloxy, 4,21,4'-trlhydroxy and 2'-hydroxy-4,4'-dimethoxy derivati~e~.
2.3. Esters of ~ubstitotod and un~ubstituted ben~oic aclds~ for exa~plep 4-tert-butylphenyl salicylate, phenyl salicylate, octyl-phenyl sallcylate, dlbenzoylresorcinol, bis(4 tert-butylbenzoyl)-resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate and hexadecyl 3,5-di-tert-butyl-4-hydroxy-ben~o~te.
? . 4 Acrylate~, for example ethyl ~-cyano-~,B-diphenylac}ylate, isooctyl ~-cyano~ diphenylacrylate9 methyl ~-carbumethoxycinn-amate, methyl a-cyano-B-methyl-p-methoxy-cinnamate, butyl ~-cyano-B-~ethyl-p-mQthoxycinnamat2~ methyl ~-carbomethoxy-p methoxy-cinna~ate and N-~B-carbom~thoxy-B~cyanovinyl)-2-methyllndoline.
32~
2.5. Nickel com~ounds, for example nickel co~plexe~ oE 2,2'-thio-bls[4-(1,1,3,3-tetramethylbutyl)phenol~, 3uch a8 the 1:1 or 1:2 complex, with or without additlonal ligands ~uch as n-butyl~mine, triethanolamine or N-cyclohexyldiethanolamine, nlckel dibutyldi-thiocarbamate, nickel salts of 4-hydroxy-3,5-di-tert-butylbenzyl-phosphonic acid monoalkyl esters, e.g. of the methyl or ethyl ester, nickel complexes of ketoxime~, e.g. of 2-hydroxy-4-methyl-phenyl undecyl ketoneoxime, nickel complexes of l~phenyl-4-lauroyl-S-hydroxypyrazole, with or without additional ligands.
2.6. St rically hlndered amines~ for example bis(2,2,S,6-tetra-methylpiperidyl) sebacate, bis(l,2,~,6,6-pentamethylpiperidyl) sebacate, bi3(1,2,2,6,6 pentamethylplperidyl) n-butyl-3,5-di-tsrt-butyl-4-hyd~oxybenzylmalonate, the condensation product of l-hydroxycthyl-2,2,6~6-tetramethyl-4-hydroxypiperidine and succinic acid, tha condensation product of N,N'-bis(2,2,6l6-tetramethyl-4-piperidyl)hsxamethylenediamine and 4-tert-octylamino-2,6-dichloro-1~3,~-s-triazine, tris(2,2,6,6-tetramethyl-4-pipelidyl) nitrllotri-acetats, tetrakis(2,2,696-tetramethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate, 1,1'-(1,2-ethanediyl)bis(3,3,5,~-tetramethyl-piperazinone).
2.~. Oxalic acid diamides, for example 4,4'-dloctyloxyoxanilide, 2,2'-dioctyloxy-5,5'-di-ter~-butyloxanlllde, 2,2'-didodecyloxy-5,5'-di-tert-butyloxanilide, 2-ethoxy-2'-ethyloxanilide, ~,N'-bis(3-di~ethylaminopropyl)oxalamida, 2-ethoxy-5-t~rt-butyl-2'-ethylox-anilids and its mix~ure ~lth 2-ethoxy-2'-ethyl-5,4'-di-tert-butylox-anilide and mixtures of ortho- and para-methoxy-disubstituted oxanilides and mixturcs of o- and p-ethoxy-disubstituted oxanilides.
3. Metal deactivators, for example N,~'-diphenyloxalic acid diamide, . . .
N-salicylal-N'-salicyloylhydrazine, N,N'-bis(salicyloyl)hydrazine, N,N'-bis~3,5-dl-tcrt-butyl-4-hydroxyphenylpropionyl)hyd~azine, 3-salicyloylamino-1,2,4-triazole, bi~(benzylidene)oxalic acid dihydrazide.
~IL~ 3 g 4. Phosphites and phosphonites, Eor example trip}lenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tris(nonyl-phenyl) phosphite, trilsuryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis~2,4-di-tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol tri-phosph~te, tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenylene diphosphonite, 3,9-bis(2,4-di-tert-butyl pheno~y~2,4,8,10-tetra-oxa-3,9-diphosphaspiro[5.5]undecane.
Process Eor the stabilisation of spherically polymerised poly-olefins The present invention relates to a proce~s for the stabilisation of ~pherically polymeris~d polyolefins by treating said polyslefins with an emulsion or dlspersion of a stabilisar or of a mlxture of stabilisers, a~ well as to th~ polyolefins stabilised in this mannsr .
No satisfactory method of stabilisation is known for the recently developed spherically polymerised polyolefins as described e.g. by P. &alli, P.C. Barbé and L. ~oristi in "~igh YiPld Catalyst~ in Olefin Polymerization", Die Angewandte Nakromolekulare Chemie ~Applied Macromolecular Chemistry) 120 (1984), pp, 73-90 tNo. 1935).
The cus~omary methods oE stahilising polyolefins in powdered form, e.g. by incorporat~on of the ætabiliser in powdered form and subsequent extrusion, can not be applied since they do not allow a sufficiently homogeneous distribution. A process for the stabili-sation of spherically pol~merised polypropylene is d~scribed in Japanose Rokai Sho S9-150719. In said process, the spherlcally polymerised polypropylene is treated in a high-speed mixer at temparat~res up to a ma~l~um of 162C with a stabillser or mlxtura of 3tabilisers, the meltlng point of which is lower than 162C. The spharic~l poly~er particles are thereby coated wlth the stabiliser melt. Also when applyin~ this ~ethod problems of distrib~ion aris~, for the result are not entirely satisf~ctory. The addition of, praferably, 3 to 15 % by weight of a binder~ based on the poly-propylene, can i~prove the resul-ts somewhat.
Surpris~ngly, it has now been found that the above-mentioned 3pherlcally polymerised polyolefin~ can be stabilised in very satisfactory manner even without the addition oE a binder~if they are treated wlth an emul~ion or dispersion of a stablliser or of a mixture oE stabilisers, which emlllsion or dispersion contains a small amount of an amine.
Stable aqueo~ls dispersions containing a phenolic antioxidant, a soap and a non-ionic or anionic surface-active compound are descri'oed in VS patent 3 962 123. Said dispersions are suitable for example for the stabilisation of acrylonitrile/butadiene/styrene or acrylo-nitrile/methyl acrylate.
Aqueous dispersions of phenolic antioxidants are also described in Japanese Kokai Sho 60-63274.
The present invention relates to a process for the stabilisation of spherically poly~erised polyolefins by treating said polyolefins with at least one emulsion or dispersion containing a stabiliser or a ~ixture of stabilisers and 0.05 to 1 % by weight, based on the polyolefin, of an amine of formula I
R1- ~ R3 (I) wherein R1 is C1-C20alkyl which may be substituted by -OH, or is C3-Csoalkyl which is interrupted by one o~ more oxygen atoms, or is C1-C8alkoxy, and each of R2 and R3 independently of the other is hydrogen or has one of the mPanings indicated for R1, or Rz and R3, together with the nitrogen atom to which they are attached, form a 5~ to 7-membered heterocyclic ring.
R1, R2 and R3 as C1-C20alkyl are for example methyl~ ethyl~ propyl, isopropyl, butyl, tert-butyl, n pentyl, ~-methylpentyl, hexyl, 2,4-dimethylpentyl~ n-octyl, 6-methylheptyl, 2-ethylhexyl, decyl, dodecyl, octadecyl, octadecylethyl or eico~yl. Linear alkyl is pre-ferred, with linear Cl2-C1galkyl being most preferred.
~,8~Z~
R1, R2 and R3 a~ al~yl which is substituted by -OH are preferably Cl-C3alkyl which 19 substituted terminally by ~OH, e.g. hydroxy-methyl, 2-hydroxyethyl, 3-hydroxypropyl, 1-hydroxyisopropyl, 6-hydroxyhexyl or ~-hydroxyoctyl, with 1-hydroxyisopropyl being preferred and 2-hydroxyethyl being most preferred.
Rl, R2 and R3 as alkyl which i~3 interrupted by oxygen are preferably alkyl whlch i8 interrupted by more than one oxygen atom, e.g. by 2 to 20 oxygen atom~. Particularly preferred are radical~ of the formula ~CHzCH2(~;H
wherein n is an integer from 2 to 20~
If Rz and R3, together ~ith the nitrogen atom to whlch they are attached, form a heterocyclic ring, then sa~d rlng i~ e.g. pyr-azolidin-1-yl, piperidi~o, morpholino, piperazin-l-yl, 4-methyl-piperazin-1-yl, hexahydroazepin-l-yl, ho~opiperazin-l-yl or 4-methylhomopiperazin-l-yl.
R1, R~ and R3 as alkoxy are e.g. methoxy~ etho~y, 3-propoxy, 4-n-butoxy or 1-n-ortyloxy.
Liquid a~ine~ of formula I are preferred. Liquid amines of formula I
wherein at least one of the radical~ Rz and R3 has one of the meanings indicated above for Rl are particularly preferred. Amine~
~herein R~ traight chain C1z-Clgalkyl and at laast one of the radicals Rz and R3 i~ a group ~cH2cH2o~n ~
wherein n is an integer fro~ 1 to 10~ ara li~ewise preferred.
1~2~93 The liquid aminas of formula I wherein R1, R2 and R3 are C2-CI,alkyl which is subs~ituted terminally by -OH, e.gO triethanolamine, are also particularly preferred.
Examples of suitable amines are butylamine, dibutylamine, tri-ethanolamine, triisopropanolamine, N,N-bis(diethanol)dodecylamine, N,N-bis(diethanol)octadecylamine, 2,4,6-trimethylpyridine, 2,3,6-trimethylpyridine and mixtures thereof and technical amine mixtures for example that which is commercially avail.able under the name of Atmer 163~ (manufact~red by ATLAS) or that which is commercially available under the name of Armostat A 400~ (manufactured by AKZO~.
The emulsion or dispersion which the polyolefin is treated with contains the stabiliser or mixture of stabilisers preferably in an amount of 0.03 to 5 % by weight, most p~eferably O.1 to 1.0 % by weight, based on the polyolefin.
Examples of suitable stabilisers are the following:
1 Antioxidants 1.1. Alkvlated monophenols 2,6-di-tert-butyl-4-methylphenol 2-tert-butyl~4,6-dimethylphenol 2,6-di-tert-butyl-4 ethylphenol 2,6-di-tert-butyl-4-n-butylphenol 2~6-di-tert-butyl-4-isobutylphenol 2,6-dicyolopentyl-4-methylphenol 2~ methylcyclohexyl)-4,6-dimethylphenol 2,6-dioctadecyl-4-methylphenol 2,4,6-tricyclohaxylphenol 2,6~di~tert-butyl-4-methoxymetbylphenol 1.2. Alkylated hydroquinone~
2,6-di-tert-butyl-4-methoxyphenol 2,5-di-tert-butylhydroquinone 2,5-di-tert-amylhydroquinone 2,6-diphenyl-4-octadecyloxyphenol 1.3. Hydro~ylated thiodiphenyl ethers 2,2'-thiobis(6-tert-butyl-4-methylphenol) 2,2'-thlobi~(4-octylphenol) 4,4'-thiobis(6-tert-butyl-3-m0thylphenol) 4,4'-thiobis(6-tert-butyl-2-methylphenol~
1.4. Alkxlid0nebisphenols 2,2' methylenebi~(6-tert-butyl-4-methylphenol) 2,2'-methylenebis(6-tert-butyl-4-ethylphenol) 2,2'-methylenebis[4-methyl-6-(~-methylcyclohexyl)phenol]
2,2'-methylenebis~4-methyl-6-cyclohexylphenol) 2,2'-methylenebis(6-nonyl-4-methylphenol) 2,2'-methylenebis(4,6-di-tert-butylphenol) 2,2'-ethylidenebis(4,6-di-tert-butylphenol) 2,2'-ethylidenebis(6-tert-butyl-4-i~obutylphenol) 2,2'-methylenebis[6-~-methylben~yl)-4-nonylphenol]
2,2'-methylenebis[6~ dimethylbenzyl~-4-nonylphenol]
4,4'-methylenebis(2,6-di-tert-butylphenol) 4,4'-methylenebis(6~tert-butyl-2-methylphenol) 1,1-b$s(5-tert-butyl-4-hydroxy-2-methylphenyl)butane 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybPnzyl)-4-mathylphenol 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl~butane l~l-bis(5-tert-b~tyl-4-hydroxy-2-methylphenyl~-3-n-dodecyl-mercaptobutane ethylene glycol bi~[3,3-bis~3'-tert-butyl-4'-hydroxyphanyl)butyr~te]
bis(3-tert-butyl-4-hydroxy 5-methylph0nyl)dicyclopentadiene bi~[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphenyl] terephthalate 1.5. Benzyl compounds 1,3,5-trig(3,5-cli-tert-butyl-4-hydroxybenzyl)-2,4,6 trimethylbenzqne bi3(3,5-di-tert-butyl-4-hyclroxyben2yl) sulfide isooctyl 3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithiolterephthalate 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl~ isocyanurata 1,3,5-tris(4-tert-butyl-3~hydroxy-2,6-dimethylbenzyl) isocyanurate dioctadecyl 3,5-di-tert-butyl-4-hydroxyhen~ylphosphonate c~lcium salt of monoethyl 3,5-di-ter~-butyl-4-hydroxybenzylphos-phonate _6 cylaminoph~nols anilide of 4-hydroxylauric acid anilide of 4-hydroxystearic acid 2,4-bls(octylmercapto)-6-(3,5-di-tert-butyl~4-hydroxyanilino) -3-tria~irle octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate 1.?. E~ters of ~-(3~ di- ert-butyl-4-h~drDxyE~y~ropionic acld with mono- or polyhydric alcohols, e.g. with methanol diethylene glycol octadecanol triethylene glycol 1,6-hexanediol pentaerythritol neopsntyl glycol tris(hydroxyethyl) isocyanur~te thiodiethylene glycol N,N'-bis(hydroxyethyl)oxalic acid diamide 1.8. Esterg of ~-(S-tcrt-butyl-4-hydroxy-3-methy~phenyl~propioni-c acid with mono- or polyhydric alcohol-~, e.g. with methanol diethylsne glycol octadecanol triethyl~ne glycol 1,6-hexanediol pantaerythritol neopentyl glycol tris(hydroxyethyl~ isocyanurate thiodiethylene glycol N,N'-bis(hydroxy~thyl)oxalic acid dlamide 1.~. Amldes of ~-~3,5-di tert-butyl-4-h~droxypheny--l-)propionic acid e.g.
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl~hexamethylene diamine N,N'-bis~3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylene-diamine N,N'-bis(3,5-di-tert-butyl--4-hydroxyphenylpropionyl)hydrazine.
2. W absorbers and light_stabilisers 2.1. 2-~2~ydroxyphenyl?ben~otriazoles~ for exampl~ the 5'-methyl, 3' 9 5'-di-tert-butyl, S'-tert-butyl, 5'-~1,1,3,3-tetramethylbutyl), 5-chloro-3'~5'-di-tert-butyl, 5-chloro-3'-tert-butyl-5'-methyl, 3'-sec-butyl-5'-tert-butyl, 4'-octoxy, 3',5'-di-tert-amyl and 3',5'-bis(~,~-dimethylbenzyl~ derivatiYes.
2.2. 2 HYdroxybenzophenones, for exa~ple the 4-hydroxy, 4-methoxy, 4-octoxy, 4-decyloxy, 4-dsdecyloxy, 4-b~nzyloxy, 4,21,4'-trlhydroxy and 2'-hydroxy-4,4'-dimethoxy derivati~e~.
2.3. Esters of ~ubstitotod and un~ubstituted ben~oic aclds~ for exa~plep 4-tert-butylphenyl salicylate, phenyl salicylate, octyl-phenyl sallcylate, dlbenzoylresorcinol, bis(4 tert-butylbenzoyl)-resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate and hexadecyl 3,5-di-tert-butyl-4-hydroxy-ben~o~te.
? . 4 Acrylate~, for example ethyl ~-cyano-~,B-diphenylac}ylate, isooctyl ~-cyano~ diphenylacrylate9 methyl ~-carbumethoxycinn-amate, methyl a-cyano-B-methyl-p-methoxy-cinnamate, butyl ~-cyano-B-~ethyl-p-mQthoxycinnamat2~ methyl ~-carbomethoxy-p methoxy-cinna~ate and N-~B-carbom~thoxy-B~cyanovinyl)-2-methyllndoline.
32~
2.5. Nickel com~ounds, for example nickel co~plexe~ oE 2,2'-thio-bls[4-(1,1,3,3-tetramethylbutyl)phenol~, 3uch a8 the 1:1 or 1:2 complex, with or without additlonal ligands ~uch as n-butyl~mine, triethanolamine or N-cyclohexyldiethanolamine, nlckel dibutyldi-thiocarbamate, nickel salts of 4-hydroxy-3,5-di-tert-butylbenzyl-phosphonic acid monoalkyl esters, e.g. of the methyl or ethyl ester, nickel complexes of ketoxime~, e.g. of 2-hydroxy-4-methyl-phenyl undecyl ketoneoxime, nickel complexes of l~phenyl-4-lauroyl-S-hydroxypyrazole, with or without additional ligands.
2.6. St rically hlndered amines~ for example bis(2,2,S,6-tetra-methylpiperidyl) sebacate, bis(l,2,~,6,6-pentamethylpiperidyl) sebacate, bi3(1,2,2,6,6 pentamethylplperidyl) n-butyl-3,5-di-tsrt-butyl-4-hyd~oxybenzylmalonate, the condensation product of l-hydroxycthyl-2,2,6~6-tetramethyl-4-hydroxypiperidine and succinic acid, tha condensation product of N,N'-bis(2,2,6l6-tetramethyl-4-piperidyl)hsxamethylenediamine and 4-tert-octylamino-2,6-dichloro-1~3,~-s-triazine, tris(2,2,6,6-tetramethyl-4-pipelidyl) nitrllotri-acetats, tetrakis(2,2,696-tetramethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate, 1,1'-(1,2-ethanediyl)bis(3,3,5,~-tetramethyl-piperazinone).
2.~. Oxalic acid diamides, for example 4,4'-dloctyloxyoxanilide, 2,2'-dioctyloxy-5,5'-di-ter~-butyloxanlllde, 2,2'-didodecyloxy-5,5'-di-tert-butyloxanilide, 2-ethoxy-2'-ethyloxanilide, ~,N'-bis(3-di~ethylaminopropyl)oxalamida, 2-ethoxy-5-t~rt-butyl-2'-ethylox-anilids and its mix~ure ~lth 2-ethoxy-2'-ethyl-5,4'-di-tert-butylox-anilide and mixtures of ortho- and para-methoxy-disubstituted oxanilides and mixturcs of o- and p-ethoxy-disubstituted oxanilides.
3. Metal deactivators, for example N,~'-diphenyloxalic acid diamide, . . .
N-salicylal-N'-salicyloylhydrazine, N,N'-bis(salicyloyl)hydrazine, N,N'-bis~3,5-dl-tcrt-butyl-4-hydroxyphenylpropionyl)hyd~azine, 3-salicyloylamino-1,2,4-triazole, bi~(benzylidene)oxalic acid dihydrazide.
~IL~ 3 g 4. Phosphites and phosphonites, Eor example trip}lenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tris(nonyl-phenyl) phosphite, trilsuryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis~2,4-di-tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol tri-phosph~te, tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenylene diphosphonite, 3,9-bis(2,4-di-tert-butyl pheno~y~2,4,8,10-tetra-oxa-3,9-diphosphaspiro[5.5]undecane.
5. Peroxida scaven~ers, for example esters of ~-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis(~-dodecylmercapto)propionate.
6. Basic co-stabilisers, for example melamine, polyvinylpyrroli-dons, dicyandiam~de, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkallne earth metal salts of higher ~atty acids for example calcium stearate, zinc stearate, magnesium stearate, sodium ricin-oleate and potassium palmitate, antimony pyrocatecholate or tin pyrocatecholate.
Particularly suitable stabilisers are antioxidants. Preferrred antioxidan~s are those from the group of hindered phenols, in particular esters of ~-(3,5-di~tert-butyl-4-hydroxyphenyl~propionic acid, some of which esters are listed under section 1.7.
Mixtures of those esters listed under section 1.7 are of particular interest. Mixtures comprising one such ester which has a melting point below the boiling range oE water and another ester from the same groupS which ester has, however, a melting point above the boiling range of water, are preferred.
-- ~o --The above-mentioned mixtures addLtionally containlng a pho~phite stabiliser are particularly preferred. Examples of such stabiliser~
are listed under sectlon 4.
It is most parti~ularly preferred to Pmploy a combination of the followlng three compounds:
-pentaerythrityl tetrakis[3 (3,5-di-tert-butyl-4-hydroxyphenyl)-propionate3 -octadecyl 3-~3,5~d~-tert-butyl-4-hydroxyphenyl)propionate -tris(2,4-di-tert-butylphenyl) phosphite.
These compounds may be present either in the same emulsion or dispersion or~ preferably, in dlfferent emulsions (dispersions) which are applied simultaneou~ly or, preferably, in succession.
Stsbilisers or mixtures of stabilisers which have a melting point below the boiling range of water are conveniently amulsified together with ths amine of formula I and the polyolefins to be stabillsed are treated wlth the emulsion thus obtained. Stabilisers or mixtures of stablllsers which have a melting point above the hoiling range of water are, on the other hand, dispersed and the polyolefins are treated with the resultant dispersion.
Different stabiliser~ may also be incorporated into different emulsions or dispersions ~hich are then applied 6imultaneously or ln succession to the polyolefin. The use of separate dispersions (or emulsion~ is reco~mended in partioular when employing phosphites.
The emulsions or dispersions of the present invention are preferably aqueous systems which may also contain water-miscible organic solvents, e.g. ketones, in particular acetone.
The stabili~er emulsion or tispersion is prepared for example as follows:
~328~3 The stabilisers to be e~ulsifiecl or dispersed are processed together with the amine of formula I and with a customary, preferably non-ionlc, emulsifier or mixture of emulsifler~ to gi~e a homo-geneous melt. (If stabili~er~ with a melting point above the boiling range of water are employed, th~n the mixture is subsequently cooled to a temperature below the boiling range of water.) Then at a temperature which must be held below the boiling range of water and with vigorous stirring by means of a high-3pesd agltator, first a portion, preferably e.g. 113 to 112, of the total amount of water i8 added. Subsequen~ly, wlth slower stirring, the remainder of the water i~ added. If desired, a minor amount of an organic solvent such as acetone i3 also added.
The stabilisers to be dispersed can for exampls also be rharged to the reaction vessel in the for~ of a fine powder together with the amine and the emulsifierO A portion, e.g. l/3 to 1/2, of the total amount of water is subsequently added, wlth ~lgorou3 stirring. (If de~ired, this mixture can be ground in order to reduce the particle si~e of the solid even further). With normal stirriDg, the remainder of the water 1~ then addPd.
The content of substance ti.e. stabiliser + amine) to be emulsified (ar dispersed) i~ for example 3 to 50 % by weight 9 preferably 5 to 25 % by ~ight, based on th~ e~tire emulsion or dlspersion.
The emulsifier or the mixture of emulsifier~ is employed for example in an amount of 5 to 50 % by welght, preferably lO to 35 % by wei~ht, basad on the 3ub3tance (i.e. stabiliser ~ amine) to be em~lsified (or dispersed).
Sultable emulsifiers (or dispersants~ are all customary emul3ifiers such ~3 thoae described in Ullmann~ Encyclopadie der technischen Chemie ~Ullmann's Encyclopaedia of Industrial Chemis~ry), 3rd ~ditinn (l955~, Volume 6, pp. 504-505. Non-ionic emulsiflers, e.g. nonylphenoxypoly(oxyethylene~ethanol9 polyo~yethylene (20) sorbitan monooleate or sorbitan monooleate, are pre~erred.
2~3 All spherlcally polymerised polyolefins, e.g. polyethylens, poly-propylene, ethylenelpropylene oopolymers, whlch are obtained by polymsrization with thlrd generation cataly~ts (such a~ those described in the above~cited publication by P. Galli, P.C. Barbé and L. Noristi) can be stabilised advantageously by the process of the present invention. Preferred polyolefins ars polypropylene and copolymers of propylene.
The invention i8 illustrated by the following non-limitative Examples.
Exam~les 1 to ~
a) ~E~ra~ion of the emulsion (dis~rslons) 1) 2 g of pentaerythrityl tetrakis~3-(3,5-di-tert-butyl-4-hydroxy-phenyl)propionate] and 2 g of th~ technical fatty alkyl diethanol-amine available under the name of Atmer 163~ (~anufactured by ATLAS) are malted at 160G together with 1.35 g of a mixture of e~ulsif~ers, whicb mixture comprises 20 % o$ sorbitan ~onooleate and ~0 % of polyoxyethylene (20) sorbitan monooleate. After the ~elt has cooled to 97~C, 20 ml of water are added, with vigorous stirrlng. A
solutiDn of 5 ml of acetone is then added, and stirring is continued at normal spe~d (dlsper~ion 1~.
-~ 2 g of pentaerythrityl tetrakis~3-~3,5-di-tert-butyl-4-hydroxy-phenyl)propionate~ and 2 g of the technical fatty al~yl dlethanol-amine available under the name of Ar~ostat A 400~ (~anufactured by AKZ0) are heated to 130C together with 1.10 g of a mixture of emulsifiers, which mixture comprises 20 % of so~bitan monooleate and 80 % of polyoxyethylene (20) sorbitan monooleate. During heating, the solid substance goes lnto solution. After said solution ha~
cooled to 95DC, 10 ml o$ water are added, with vigorous stirring. A
solution of 2 ~1 of acetone in lO ~1 of water is then sdded, and stirring is continued at normal ~pead ~dispersion 2~.
~ 13 -3) 4 g of pentaerythrityl tetrakisl3-(3,S-di-t~rt-butyl 4-hydroxy-phenyl)propionate] and 4 g of triethanolamine are heated to 85C ln a beaker together with 2 g of a mixtu~e oE emulsifier~, which mixture comprises 20 % of sorbitan monooleate and 80 % of polyoxy-ethylene (20) sorbitan monooleate, and the batch is then cooled to 50C. With vigorous ~tirring, 20 ml of water and 9 ml of acetone are then added. Subsequently, with ~low~r stlrring, a further 20 ml of water are added (dispersion 3).
4) 5 g of octadecyl 3-(3,5 di-tert-butyl 4-hydroxyphenyl)propionate and 5 g of the technical fatty alkyl diethanolamine available under the name of Armostat A 400~ ~manu~actursd by AKZ0) are heated to 70C together wlth l.7 g of a mixture of emulsifiers, whlch mixture comprise~ 20 % of ~orbitan monooleate and 80 % of polyoxysthyl-ene (20) ~orbitan monool~ate. With vlgorous stirring by means of a high-~peed agitator, 40 ml of ~ater are added, durlng whtch additlon the temperature is held at 50C. Subsequently, with slower stirring, a further 40 ml of watsr a~ well a~ 9 ml of acetone are added (~m~ls1on 4).
b) Oven agein~ test A 5 litre vessel with pressur~-equalising means is charged with l 000 g of ~pherical polypropyl~ne (Spheripol~, manufactur~d by HIMONT~ MFI 9-10), and the respective dispersion or emulsion listsd in Table l below ls then added. The mixture is treated by being shaken fvr 45 minutes by means of an ecc~ntric tumbling mixer. Th~
spherical polypropylene i9 then aged in the oven at 120, 135 and l49C. The criterion of ~tabillsation is the oven ageing time in hours until decompositlon of the beads under a mechanical load.
~X~32893 The results are shown in Table 1 Table 1 ExampleDispersion/ Oven ageing time in hours at Emulsion 120C 135C 149C
~ _~
. _ - .. .____ .. __ 2 2 2952 1440 4~0 . _ _ ~_ .... _ . _ .. .. _ 4 4 > 900 864 120 .. ~ __ .. __ . __ . __ untreated spherical 12 5 2 polypropylene _ _ _ _ _ Example S
a) Prep DisDersion A
50 g of tris(2,4-di-tert-butylphenyl) phosphite and 100 g of the technical fatty alkyl diethanolamine available under the name of Armostat A 4009 (manu'`actured by AKZO) are heated together with 33 g of a mixture of emul~sifiers, which mixture comprises 20 % of sorbitan monooleate and 80 % of polyoxyethylene (20) sorbitan monooleate. At 160C, a clear pale yellow solution iB obtained which i8 then cooled to 98C. With vigorous stirring, 700 ml of water are added. Stirring is then continued for about 15 minutes. Subsequent-ly, 120 ml of water are added, and stirring is continued for a further 15 minutes. The disper~ion may separate after prolonged storage but i~ completely homogenised again by stirring.
~32~3~3 Emulsion B
40 g of pentaerythrityl tetraklsl3~(3,5-di-tert-butyl-4-hydroxy-phenyl)propionate], 40 g of octadecyl 3~(3,5-di-tert-butyl-4-hydroxyphenyl)proplonate and 10 g of nonylphenoxypoly(oxyethylene)-ethanol are melted at 110C. The melt ia allowed to cool to 90C, and then 60 ml of ~ater are added, with vigorous stirring. During the additlon, the temperature drops to 70C. The white emulsion i3 poured at once into 250 ml of cold water, and stlrring is contlnued slowly for about 15 minutes.
b) Ov agein~ test In a 5 litre ve~sel with pressure-equalislng means, 1 OU0 g of 6phsrical polyp~opylene are first treated with 10 ml of disper~ion A
by being shaken for 20 minutes by means of an eccentric tumbling mixer. 10 ~1 of emulsion B are then added, and the batch is shaken for a further 20 minutes. Subsequently, the oven ageing test a3 de~cribed in Example~ 1 to 4 is carrisd out. The re~ults are ~hown in Table 2 below.
Table 2 Ex,mp1e Dispersion ~
120~C 135C149C
~ ~ _ _, _ _ A + B ~ 1800 172~ 576 untreated spherical 12 5 2 polypropylene __~__~ _ xample 6 a) Prepar_ lon of the dispersions Dispersion C
lO g of pentaerythrityl tetrakis[3-(3,5-di~tert-butyl-4-hydroxy-phenyl~propionate~ and 10 g of octadecyl 3-(3,5-di tert-butyl-4-hydroxyphenyl~propionate are melted at 120C together with 1.25 g of nonylphenoxypoly(oxyethylene)ethanol. After the melt has cooled to 75C, first 30 ~l of water are added, followed by the addition of a further 49.3 ml of water9 with vigorous stirring.
Dispersion D
5 g of trisS2,4-di-tert-butylphenyl) phosphite in powdered form and 2.5 g of the technical fatty alkyl diethanolamine commercially available under the name of Armastat A 400~ ~manufactured by ARzo?
are stirred at room temperature together with 1 g of nonylphenoxy-poly(oxyethylene)ethanol. Subsequently, 91.5 g of water are added in 3 stages.
b) Oven a~ein~ test l 000 g of spherical polypropylene are placed in a 5 litre glass flask. 20 ml of dispersion D are then poured over the polypropylene beads. The glass ~lask is fixed on a mi~er which is run for 5 min-utes. 5 ml oE dispersion C are then diluted with 10 ml of water and poured over the polypropylene beads. The mixar is run for a further 20 minutes. The polypropylene beads are then placed in a glass dish and aged at 149C in an oven with reoirculating air. The cri-terion of stabilisation is the oven ageing time in hours until decompo-sition of the beads under the pressure of a finger nail.
Z~3~3 - lJ -The results are shown in Table 3.
Table 3 -_ . . . _ . . _ , _ _ . . _ ~ ,, _ E~ample ¦ Dispersi~n g lg49C
6 C + D 744 untreated spherlcal 2 polypropylene . _ _ . ~
Particularly suitable stabilisers are antioxidants. Preferrred antioxidan~s are those from the group of hindered phenols, in particular esters of ~-(3,5-di~tert-butyl-4-hydroxyphenyl~propionic acid, some of which esters are listed under section 1.7.
Mixtures of those esters listed under section 1.7 are of particular interest. Mixtures comprising one such ester which has a melting point below the boiling range oE water and another ester from the same groupS which ester has, however, a melting point above the boiling range of water, are preferred.
-- ~o --The above-mentioned mixtures addLtionally containlng a pho~phite stabiliser are particularly preferred. Examples of such stabiliser~
are listed under sectlon 4.
It is most parti~ularly preferred to Pmploy a combination of the followlng three compounds:
-pentaerythrityl tetrakis[3 (3,5-di-tert-butyl-4-hydroxyphenyl)-propionate3 -octadecyl 3-~3,5~d~-tert-butyl-4-hydroxyphenyl)propionate -tris(2,4-di-tert-butylphenyl) phosphite.
These compounds may be present either in the same emulsion or dispersion or~ preferably, in dlfferent emulsions (dispersions) which are applied simultaneou~ly or, preferably, in succession.
Stsbilisers or mixtures of stabilisers which have a melting point below the boiling range of water are conveniently amulsified together with ths amine of formula I and the polyolefins to be stabillsed are treated wlth the emulsion thus obtained. Stabilisers or mixtures of stablllsers which have a melting point above the hoiling range of water are, on the other hand, dispersed and the polyolefins are treated with the resultant dispersion.
Different stabiliser~ may also be incorporated into different emulsions or dispersions ~hich are then applied 6imultaneously or ln succession to the polyolefin. The use of separate dispersions (or emulsion~ is reco~mended in partioular when employing phosphites.
The emulsions or dispersions of the present invention are preferably aqueous systems which may also contain water-miscible organic solvents, e.g. ketones, in particular acetone.
The stabili~er emulsion or tispersion is prepared for example as follows:
~328~3 The stabilisers to be e~ulsifiecl or dispersed are processed together with the amine of formula I and with a customary, preferably non-ionlc, emulsifier or mixture of emulsifler~ to gi~e a homo-geneous melt. (If stabili~er~ with a melting point above the boiling range of water are employed, th~n the mixture is subsequently cooled to a temperature below the boiling range of water.) Then at a temperature which must be held below the boiling range of water and with vigorous stirring by means of a high-3pesd agltator, first a portion, preferably e.g. 113 to 112, of the total amount of water i8 added. Subsequen~ly, wlth slower stirring, the remainder of the water i~ added. If desired, a minor amount of an organic solvent such as acetone i3 also added.
The stabilisers to be dispersed can for exampls also be rharged to the reaction vessel in the for~ of a fine powder together with the amine and the emulsifierO A portion, e.g. l/3 to 1/2, of the total amount of water is subsequently added, wlth ~lgorou3 stirring. (If de~ired, this mixture can be ground in order to reduce the particle si~e of the solid even further). With normal stirriDg, the remainder of the water 1~ then addPd.
The content of substance ti.e. stabiliser + amine) to be emulsified (ar dispersed) i~ for example 3 to 50 % by weight 9 preferably 5 to 25 % by ~ight, based on th~ e~tire emulsion or dlspersion.
The emulsifier or the mixture of emulsifier~ is employed for example in an amount of 5 to 50 % by welght, preferably lO to 35 % by wei~ht, basad on the 3ub3tance (i.e. stabiliser ~ amine) to be em~lsified (or dispersed).
Sultable emulsifiers (or dispersants~ are all customary emul3ifiers such ~3 thoae described in Ullmann~ Encyclopadie der technischen Chemie ~Ullmann's Encyclopaedia of Industrial Chemis~ry), 3rd ~ditinn (l955~, Volume 6, pp. 504-505. Non-ionic emulsiflers, e.g. nonylphenoxypoly(oxyethylene~ethanol9 polyo~yethylene (20) sorbitan monooleate or sorbitan monooleate, are pre~erred.
2~3 All spherlcally polymerised polyolefins, e.g. polyethylens, poly-propylene, ethylenelpropylene oopolymers, whlch are obtained by polymsrization with thlrd generation cataly~ts (such a~ those described in the above~cited publication by P. Galli, P.C. Barbé and L. Noristi) can be stabilised advantageously by the process of the present invention. Preferred polyolefins ars polypropylene and copolymers of propylene.
The invention i8 illustrated by the following non-limitative Examples.
Exam~les 1 to ~
a) ~E~ra~ion of the emulsion (dis~rslons) 1) 2 g of pentaerythrityl tetrakis~3-(3,5-di-tert-butyl-4-hydroxy-phenyl)propionate] and 2 g of th~ technical fatty alkyl diethanol-amine available under the name of Atmer 163~ (~anufactured by ATLAS) are malted at 160G together with 1.35 g of a mixture of e~ulsif~ers, whicb mixture comprises 20 % o$ sorbitan ~onooleate and ~0 % of polyoxyethylene (20) sorbitan monooleate. After the ~elt has cooled to 97~C, 20 ml of water are added, with vigorous stirrlng. A
solutiDn of 5 ml of acetone is then added, and stirring is continued at normal spe~d (dlsper~ion 1~.
-~ 2 g of pentaerythrityl tetrakis~3-~3,5-di-tert-butyl-4-hydroxy-phenyl)propionate~ and 2 g of the technical fatty al~yl dlethanol-amine available under the name of Ar~ostat A 400~ (~anufactured by AKZ0) are heated to 130C together with 1.10 g of a mixture of emulsifiers, which mixture comprises 20 % of so~bitan monooleate and 80 % of polyoxyethylene (20) sorbitan monooleate. During heating, the solid substance goes lnto solution. After said solution ha~
cooled to 95DC, 10 ml o$ water are added, with vigorous stirring. A
solution of 2 ~1 of acetone in lO ~1 of water is then sdded, and stirring is continued at normal ~pead ~dispersion 2~.
~ 13 -3) 4 g of pentaerythrityl tetrakisl3-(3,S-di-t~rt-butyl 4-hydroxy-phenyl)propionate] and 4 g of triethanolamine are heated to 85C ln a beaker together with 2 g of a mixtu~e oE emulsifier~, which mixture comprises 20 % of sorbitan monooleate and 80 % of polyoxy-ethylene (20) sorbitan monooleate, and the batch is then cooled to 50C. With vigorous ~tirring, 20 ml of water and 9 ml of acetone are then added. Subsequently, with ~low~r stlrring, a further 20 ml of water are added (dispersion 3).
4) 5 g of octadecyl 3-(3,5 di-tert-butyl 4-hydroxyphenyl)propionate and 5 g of the technical fatty alkyl diethanolamine available under the name of Armostat A 400~ ~manu~actursd by AKZ0) are heated to 70C together wlth l.7 g of a mixture of emulsifiers, whlch mixture comprise~ 20 % of ~orbitan monooleate and 80 % of polyoxysthyl-ene (20) ~orbitan monool~ate. With vlgorous stirring by means of a high-~peed agitator, 40 ml of ~ater are added, durlng whtch additlon the temperature is held at 50C. Subsequently, with slower stirring, a further 40 ml of watsr a~ well a~ 9 ml of acetone are added (~m~ls1on 4).
b) Oven agein~ test A 5 litre vessel with pressur~-equalising means is charged with l 000 g of ~pherical polypropyl~ne (Spheripol~, manufactur~d by HIMONT~ MFI 9-10), and the respective dispersion or emulsion listsd in Table l below ls then added. The mixture is treated by being shaken fvr 45 minutes by means of an ecc~ntric tumbling mixer. Th~
spherical polypropylene i9 then aged in the oven at 120, 135 and l49C. The criterion of ~tabillsation is the oven ageing time in hours until decompositlon of the beads under a mechanical load.
~X~32893 The results are shown in Table 1 Table 1 ExampleDispersion/ Oven ageing time in hours at Emulsion 120C 135C 149C
~ _~
. _ - .. .____ .. __ 2 2 2952 1440 4~0 . _ _ ~_ .... _ . _ .. .. _ 4 4 > 900 864 120 .. ~ __ .. __ . __ . __ untreated spherical 12 5 2 polypropylene _ _ _ _ _ Example S
a) Prep DisDersion A
50 g of tris(2,4-di-tert-butylphenyl) phosphite and 100 g of the technical fatty alkyl diethanolamine available under the name of Armostat A 4009 (manu'`actured by AKZO) are heated together with 33 g of a mixture of emul~sifiers, which mixture comprises 20 % of sorbitan monooleate and 80 % of polyoxyethylene (20) sorbitan monooleate. At 160C, a clear pale yellow solution iB obtained which i8 then cooled to 98C. With vigorous stirring, 700 ml of water are added. Stirring is then continued for about 15 minutes. Subsequent-ly, 120 ml of water are added, and stirring is continued for a further 15 minutes. The disper~ion may separate after prolonged storage but i~ completely homogenised again by stirring.
~32~3~3 Emulsion B
40 g of pentaerythrityl tetraklsl3~(3,5-di-tert-butyl-4-hydroxy-phenyl)propionate], 40 g of octadecyl 3~(3,5-di-tert-butyl-4-hydroxyphenyl)proplonate and 10 g of nonylphenoxypoly(oxyethylene)-ethanol are melted at 110C. The melt ia allowed to cool to 90C, and then 60 ml of ~ater are added, with vigorous stirring. During the additlon, the temperature drops to 70C. The white emulsion i3 poured at once into 250 ml of cold water, and stlrring is contlnued slowly for about 15 minutes.
b) Ov agein~ test In a 5 litre ve~sel with pressure-equalislng means, 1 OU0 g of 6phsrical polyp~opylene are first treated with 10 ml of disper~ion A
by being shaken for 20 minutes by means of an eccentric tumbling mixer. 10 ~1 of emulsion B are then added, and the batch is shaken for a further 20 minutes. Subsequently, the oven ageing test a3 de~cribed in Example~ 1 to 4 is carrisd out. The re~ults are ~hown in Table 2 below.
Table 2 Ex,mp1e Dispersion ~
120~C 135C149C
~ ~ _ _, _ _ A + B ~ 1800 172~ 576 untreated spherical 12 5 2 polypropylene __~__~ _ xample 6 a) Prepar_ lon of the dispersions Dispersion C
lO g of pentaerythrityl tetrakis[3-(3,5-di~tert-butyl-4-hydroxy-phenyl~propionate~ and 10 g of octadecyl 3-(3,5-di tert-butyl-4-hydroxyphenyl~propionate are melted at 120C together with 1.25 g of nonylphenoxypoly(oxyethylene)ethanol. After the melt has cooled to 75C, first 30 ~l of water are added, followed by the addition of a further 49.3 ml of water9 with vigorous stirring.
Dispersion D
5 g of trisS2,4-di-tert-butylphenyl) phosphite in powdered form and 2.5 g of the technical fatty alkyl diethanolamine commercially available under the name of Armastat A 400~ ~manufactured by ARzo?
are stirred at room temperature together with 1 g of nonylphenoxy-poly(oxyethylene)ethanol. Subsequently, 91.5 g of water are added in 3 stages.
b) Oven a~ein~ test l 000 g of spherical polypropylene are placed in a 5 litre glass flask. 20 ml of dispersion D are then poured over the polypropylene beads. The glass ~lask is fixed on a mi~er which is run for 5 min-utes. 5 ml oE dispersion C are then diluted with 10 ml of water and poured over the polypropylene beads. The mixar is run for a further 20 minutes. The polypropylene beads are then placed in a glass dish and aged at 149C in an oven with reoirculating air. The cri-terion of stabilisation is the oven ageing time in hours until decompo-sition of the beads under the pressure of a finger nail.
Z~3~3 - lJ -The results are shown in Table 3.
Table 3 -_ . . . _ . . _ , _ _ . . _ ~ ,, _ E~ample ¦ Dispersi~n g lg49C
6 C + D 744 untreated spherlcal 2 polypropylene . _ _ . ~
Claims (10)
1. A process for the stabilisation of a spherically polymerised polyolefin by treating said polyolefin with at least one emulsion or dispersion containing a stabiliser or a mixture of stabilisers and 0.05 to 1.0 % by weight, based on the polyolefin, of an amine of formula I
(I) wherein R1 is C1-C20alkyl or C1-C20alkyl which is substituted by -OH, or is C3 C50alkyl which is interrupted by one or more oxygen atoms, or is C1-C8alkoxy, and each of R2 and R3 independently of the other is hydrogen or has one of the meanings indicated for R1, or R2 and R3, together with the nitrogen atom to which they are attached, form a 5- to 7-membered heterocyclic ring.
(I) wherein R1 is C1-C20alkyl or C1-C20alkyl which is substituted by -OH, or is C3 C50alkyl which is interrupted by one or more oxygen atoms, or is C1-C8alkoxy, and each of R2 and R3 independently of the other is hydrogen or has one of the meanings indicated for R1, or R2 and R3, together with the nitrogen atom to which they are attached, form a 5- to 7-membered heterocyclic ring.
2. A process according to claim 1, wherein the amine of formula I is a liquid amine.
3. A process according to claim 1, wherein the amine 18 a liquid amine of formula I wherein at least one of the radicals R2 and R3 has one of the meanings indicated for R1 in claim 1.
4. A process according to claim 1, wherein the amine is a liquid amine of formula I wherein R1 is straight chain C12-C18alkyl and at least one of R2 and R3 is a group ?CH2CH2C?
wherein n is an integer from 1 to 10.
wherein n is an integer from 1 to 10.
5. A process according to claim 1, wherein the amine is a liquid amine of formula I wherein R1, R2 and R3 are C2-C4alkyl which is substituted terminally by -OH.
6. A process according to claim 1, wherein the emulsion or disper-sion contains the stabiliser or the mixture of stabilisers in an amount of 0.03 to 5.0 % by weight, based on the polyolefin.
7. A process according to claim 1, wherein esters of .beta.-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid are employed as stabilisers.
8. A process according to claim 7, wherein a phosphite is addition-ally employed as stabiliser.
9. A process according to claim 1, wherein - pentaerythrityl tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate]
- octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphanyl)propionate - tris(2,4 di-tert-butylphenyl) phosphite are employed together as stabilisers.
- octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphanyl)propionate - tris(2,4 di-tert-butylphenyl) phosphite are employed together as stabilisers.
10. A polyolefin which has been stabilised according to claim 1.
FO 7.3 SR/hc*
FO 7.3 SR/hc*
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US5274016A (en) * | 1985-12-06 | 1993-12-28 | Ciba-Geigy Corporation | Light-stabilized polymer microparticles |
US4818799A (en) * | 1987-11-13 | 1989-04-04 | Shell Oil Company | Process for the in-reactor stabilization of polyolefins |
US4960617A (en) * | 1988-02-29 | 1990-10-02 | Shell Oil Company | Post-reactor stabilization of polyolefins |
US5204022A (en) * | 1989-08-11 | 1993-04-20 | Eastman Kodak Company | Solid-form additive systems dispersible in aqueous media |
US5153029A (en) * | 1989-08-11 | 1992-10-06 | Eastman Kodak Company | Solid-form additive systems dispersible in aqueous media, methods for the preparation and application thereof to polymeric particles |
US5041310A (en) * | 1990-06-21 | 1991-08-20 | Becton, Dickinson And Company | Process for uniform coating of polymer particles with an additive |
JPH0641348A (en) * | 1992-03-31 | 1994-02-15 | Union Carbide Chem & Plast Technol Corp | Dispersion of polymer additive in fatty acid ester |
US5385961A (en) * | 1993-01-27 | 1995-01-31 | General Electric Company | Amino silicone/phosphite compositions |
US5559167A (en) * | 1993-07-22 | 1996-09-24 | General Electric Company | Gamma irradiated thermoplastics and articles |
US5543102A (en) * | 1993-07-22 | 1996-08-06 | General Electric Company | Melt extrusion process |
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JPS6063274A (en) * | 1983-09-16 | 1985-04-11 | Mitsui Toatsu Chem Inc | Antioxidant dispersion |
-
1986
- 1986-04-25 EP EP86810189A patent/EP0200684B1/en not_active Expired - Lifetime
- 1986-04-25 DE DE8686810189T patent/DE3673055D1/en not_active Expired - Lifetime
- 1986-04-25 US US06/856,083 patent/US4708979A/en not_active Expired - Lifetime
- 1986-04-30 CA CA000508015A patent/CA1282893C/en not_active Expired - Lifetime
- 1986-05-02 JP JP61102968A patent/JPH0764959B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
EP0200684A2 (en) | 1986-11-05 |
JPH0764959B2 (en) | 1995-07-12 |
JPS61261333A (en) | 1986-11-19 |
EP0200684B1 (en) | 1990-08-01 |
US4708979A (en) | 1987-11-24 |
DE3673055D1 (en) | 1990-09-06 |
EP0200684A3 (en) | 1988-08-10 |
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