CN102428139A - 耐划痕聚丙烯 - Google Patents
耐划痕聚丙烯 Download PDFInfo
- Publication number
- CN102428139A CN102428139A CN2010800211680A CN201080021168A CN102428139A CN 102428139 A CN102428139 A CN 102428139A CN 2010800211680 A CN2010800211680 A CN 2010800211680A CN 201080021168 A CN201080021168 A CN 201080021168A CN 102428139 A CN102428139 A CN 102428139A
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- CN
- China
- Prior art keywords
- phenyl
- polypropylene
- weight
- tertiary butyl
- butyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- -1 polypropylene Polymers 0.000 title claims abstract description 144
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 47
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 25
- 230000003678 scratch resistant effect Effects 0.000 title claims abstract description 14
- 229920000098 polyolefin Polymers 0.000 claims abstract description 22
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 20
- 239000000194 fatty acid Substances 0.000 claims abstract description 20
- 229930195729 fatty acid Natural products 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000000945 filler Substances 0.000 claims abstract description 12
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 12
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 claims abstract description 11
- 239000004299 sodium benzoate Substances 0.000 claims abstract description 11
- 235000010234 sodium benzoate Nutrition 0.000 claims abstract description 11
- 159000000007 calcium salts Chemical class 0.000 claims abstract description 10
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 10
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract description 9
- UMRZSTCPUPJPOJ-KNVOCYPGSA-N norbornane Chemical compound C1C[C@H]2CC[C@@H]1C2 UMRZSTCPUPJPOJ-KNVOCYPGSA-N 0.000 claims abstract description 9
- LRGQZEKJTHEMOJ-UHFFFAOYSA-N propane-1,2,3-triol;zinc Chemical compound [Zn].OCC(O)CO LRGQZEKJTHEMOJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 8
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 27
- 239000012445 acidic reagent Substances 0.000 claims description 24
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 19
- 239000000047 product Substances 0.000 claims description 19
- 150000001336 alkenes Chemical group 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical group OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- HSEMFIZWXHQJAE-UHFFFAOYSA-N hexadecanamide Chemical compound CCCCCCCCCCCCCCCC(N)=O HSEMFIZWXHQJAE-UHFFFAOYSA-N 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- 229920001519 homopolymer Polymers 0.000 claims description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- 229920001169 thermoplastic Polymers 0.000 claims 1
- 239000004416 thermosoftening plastic Substances 0.000 claims 1
- 239000000654 additive Substances 0.000 abstract description 33
- 229920002397 thermoplastic olefin Polymers 0.000 abstract description 21
- 125000005313 fatty acid group Chemical group 0.000 abstract description 12
- 239000000454 talc Substances 0.000 abstract description 6
- 229910052623 talc Inorganic materials 0.000 abstract description 6
- 229920000089 Cyclic olefin copolymer Polymers 0.000 abstract description 5
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric Acid Chemical compound [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 abstract description 5
- 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 abstract description 5
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 5
- 239000004711 α-olefin Substances 0.000 abstract description 3
- 239000012462 polypropylene substrate Substances 0.000 abstract 2
- FUSNPOOETKRESL-ZPHPHTNESA-N (z)-n-octadecyldocos-13-enamide Chemical compound CCCCCCCCCCCCCCCCCCNC(=O)CCCCCCCCCCC\C=C/CCCCCCCC FUSNPOOETKRESL-ZPHPHTNESA-N 0.000 abstract 1
- 229910019142 PO4 Inorganic materials 0.000 abstract 1
- VMRGZRVLZQSNHC-ZCXUNETKSA-N n-[(z)-octadec-9-enyl]hexadecanamide Chemical compound CCCCCCCCCCCCCCCC(=O)NCCCCCCCC\C=C/CCCCCCCC VMRGZRVLZQSNHC-ZCXUNETKSA-N 0.000 abstract 1
- 239000002667 nucleating agent Substances 0.000 abstract 1
- 239000010452 phosphate Substances 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract 1
- 229920005629 polypropylene homopolymer Polymers 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 37
- 229910052757 nitrogen Inorganic materials 0.000 description 34
- 239000002585 base Substances 0.000 description 29
- 230000000996 additive effect Effects 0.000 description 28
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 19
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 19
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 18
- 239000000126 substance Substances 0.000 description 18
- 150000002148 esters Chemical class 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 229910052760 oxygen Inorganic materials 0.000 description 14
- 239000001301 oxygen Substances 0.000 description 14
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 13
- 150000001412 amines Chemical class 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 238000005804 alkylation reaction Methods 0.000 description 9
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 8
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 8
- REIUXOLGHVXAEO-UHFFFAOYSA-N pentadecan-1-ol Chemical compound CCCCCCCCCCCCCCCO REIUXOLGHVXAEO-UHFFFAOYSA-N 0.000 description 8
- KJIOQYGWTQBHNH-UHFFFAOYSA-N undecanol Chemical compound CCCCCCCCCCCO KJIOQYGWTQBHNH-UHFFFAOYSA-N 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 7
- 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 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- DKHJONPHCWFBAX-UHFFFAOYSA-N 3-butyl-3h-1-benzofuran-2-one Chemical group C1=CC=C2C(CCCC)C(=O)OC2=C1 DKHJONPHCWFBAX-UHFFFAOYSA-N 0.000 description 5
- 150000001408 amides Chemical class 0.000 description 5
- 150000001993 dienes Chemical class 0.000 description 5
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 5
- 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 5
- 239000003921 oil Substances 0.000 description 5
- 229940059574 pentaerithrityl Drugs 0.000 description 5
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 235000012222 talc Nutrition 0.000 description 5
- OJOWICOBYCXEKR-APPZFPTMSA-N (1S,4R)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical group CC=C1C[C@@H]2C[C@@H]1C=C2 OJOWICOBYCXEKR-APPZFPTMSA-N 0.000 description 4
- SVTBMSDMJJWYQN-RXMQYKEDSA-N (4r)-2-methylpentane-2,4-diol Chemical compound C[C@@H](O)CC(C)(C)O SVTBMSDMJJWYQN-RXMQYKEDSA-N 0.000 description 4
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 4
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 4
- GXURZKWLMYOCDX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;dihydroxyphosphanyl dihydrogen phosphite Chemical class OP(O)OP(O)O.OCC(CO)(CO)CO GXURZKWLMYOCDX-UHFFFAOYSA-N 0.000 description 4
- GLDQAMYCGOIJDV-UHFFFAOYSA-N 2,3-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC(O)=C1O GLDQAMYCGOIJDV-UHFFFAOYSA-N 0.000 description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- IYXGSMUGOJNHAZ-UHFFFAOYSA-N Ethyl malonate Chemical compound CCOC(=O)CC(=O)OCC IYXGSMUGOJNHAZ-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Natural products OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 4
- COVMBDWAODLWIB-UHFFFAOYSA-N n'-(2-hydroxyethyl)oxamide Chemical compound NC(=O)C(=O)NCCO COVMBDWAODLWIB-UHFFFAOYSA-N 0.000 description 4
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 4
- 229950006389 thiodiglycol Drugs 0.000 description 4
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- 229940057402 undecyl alcohol Drugs 0.000 description 4
- HTSVYUUXJSMGQC-UHFFFAOYSA-N 2-chloro-1,3,5-triazine Chemical class ClC1=NC=NC=N1 HTSVYUUXJSMGQC-UHFFFAOYSA-N 0.000 description 3
- ACZGCWSMSTYWDQ-UHFFFAOYSA-N 3h-1-benzofuran-2-one Chemical compound C1=CC=C2OC(=O)CC2=C1 ACZGCWSMSTYWDQ-UHFFFAOYSA-N 0.000 description 3
- 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 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- YIKSCQDJHCMVMK-UHFFFAOYSA-N Oxamide Chemical compound NC(=O)C(N)=O YIKSCQDJHCMVMK-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 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 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- ODGYWRBCQWKSSH-UHFFFAOYSA-N n'-ethylpropane-1,3-diamine Chemical compound CCNCCCN ODGYWRBCQWKSSH-UHFFFAOYSA-N 0.000 description 3
- FTWUXYZHDFCGSV-UHFFFAOYSA-N n,n'-diphenyloxamide Chemical compound C=1C=CC=CC=1NC(=O)C(=O)NC1=CC=CC=C1 FTWUXYZHDFCGSV-UHFFFAOYSA-N 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 125000003518 norbornenyl group Chemical class C12(C=CC(CC1)C2)* 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000000600 sorbitol Substances 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 3
- 229920001897 terpolymer Polymers 0.000 description 3
- GPOGLVDBOFRHDV-UHFFFAOYSA-N (2-nonylphenyl) dihydrogen phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(O)O GPOGLVDBOFRHDV-UHFFFAOYSA-N 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 2
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 2
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 description 2
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 2
- 150000005208 1,4-dihydroxybenzenes Chemical group 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 2
- JLZIIHMTTRXXIN-UHFFFAOYSA-N 2-(2-hydroxy-4-methoxybenzoyl)benzoic acid Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1C(O)=O JLZIIHMTTRXXIN-UHFFFAOYSA-N 0.000 description 2
- LCQXXVFFJHBYME-UHFFFAOYSA-N 2-butyl-4-hydroxybenzoic acid Chemical group CCCCC1=CC(O)=CC=C1C(O)=O LCQXXVFFJHBYME-UHFFFAOYSA-N 0.000 description 2
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 2
- 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 2
- BKZXZGWHTRCFPX-UHFFFAOYSA-N 2-tert-butyl-6-methylphenol Chemical compound CC1=CC=CC(C(C)(C)C)=C1O BKZXZGWHTRCFPX-UHFFFAOYSA-N 0.000 description 2
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 2
- MSGFMKMFGGXSTO-UHFFFAOYSA-N C(C)(C)(C)C=1C=C(C(=CC1O)CN)CCCC Chemical compound C(C)(C)(C)C=1C=C(C(=CC1O)CN)CCCC MSGFMKMFGGXSTO-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
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- GCDJFNYVSDFWDB-UHFFFAOYSA-N n-hexadecylhexadecan-1-imine oxide Chemical compound CCCCCCCCCCCCCCCC[N+]([O-])=CCCCCCCCCCCCCCCC GCDJFNYVSDFWDB-UHFFFAOYSA-N 0.000 description 1
- FHAFFFSIDLDWQA-UHFFFAOYSA-N n-hexadecyloctadecan-1-imine oxide Chemical compound CCCCCCCCCCCCCCCCCC=[N+]([O-])CCCCCCCCCCCCCCCC FHAFFFSIDLDWQA-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- VNPWYJMHLZEKFZ-UHFFFAOYSA-N n-methyl-n-octadecylhydroxylamine Chemical compound CCCCCCCCCCCCCCCCCCN(C)O VNPWYJMHLZEKFZ-UHFFFAOYSA-N 0.000 description 1
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- LVZUNTGFCXNQAF-UHFFFAOYSA-N n-nonyl-n-phenylaniline Chemical compound C=1C=CC=CC=1N(CCCCCCCCC)C1=CC=CC=C1 LVZUNTGFCXNQAF-UHFFFAOYSA-N 0.000 description 1
- ZXGDIORKSOYRMQ-UHFFFAOYSA-N n-octadecylheptadecan-1-imine oxide Chemical compound CCCCCCCCCCCCCCCCCC[N+]([O-])=CCCCCCCCCCCCCCCCC ZXGDIORKSOYRMQ-UHFFFAOYSA-N 0.000 description 1
- MCMMSXFAWOGWQE-UHFFFAOYSA-N n-octadecylhexadecan-1-imine oxide Chemical compound CCCCCCCCCCCCCCCCCC[N+]([O-])=CCCCCCCCCCCCCCCC MCMMSXFAWOGWQE-UHFFFAOYSA-N 0.000 description 1
- HORBOHJHQGXXOR-UHFFFAOYSA-N n-octadecyloctadecan-1-imine oxide Chemical compound CCCCCCCCCCCCCCCCCC[N+]([O-])=CCCCCCCCCCCCCCCCCC HORBOHJHQGXXOR-UHFFFAOYSA-N 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
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- SLYJXPKHTZCZOG-UHFFFAOYSA-N n-tetradecyltetradecan-1-imine oxide Chemical compound CCCCCCCCCCCCCC[N+]([O-])=CCCCCCCCCCCCCC SLYJXPKHTZCZOG-UHFFFAOYSA-N 0.000 description 1
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
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- IJRHDFLHUATAOS-DPMBMXLASA-N sodium;(z,12r)-12-hydroxyoctadec-9-enoic acid Chemical compound [Na+].CCCCCC[C@@H](O)C\C=C/CCCCCCCC(O)=O IJRHDFLHUATAOS-DPMBMXLASA-N 0.000 description 1
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- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- AOBORMOPSGHCAX-DGHZZKTQSA-N tocofersolan Chemical compound OCCOC(=O)CCC(=O)OC1=C(C)C(C)=C2O[C@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C AOBORMOPSGHCAX-DGHZZKTQSA-N 0.000 description 1
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- 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
- IVIIAEVMQHEPAY-UHFFFAOYSA-N tridodecyl phosphite Chemical compound CCCCCCCCCCCCOP(OCCCCCCCCCCCC)OCCCCCCCCCCCC IVIIAEVMQHEPAY-UHFFFAOYSA-N 0.000 description 1
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
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- 235000019354 vermiculite Nutrition 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 235000019154 vitamin C Nutrition 0.000 description 1
- 239000011718 vitamin C Substances 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
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- 239000002023 wood Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000002076 α-tocopherol Substances 0.000 description 1
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- QUEDXNHFTDJVIY-DQCZWYHMSA-N γ-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1 QUEDXNHFTDJVIY-DQCZWYHMSA-N 0.000 description 1
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- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
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Abstract
公开了耐划痕聚丙烯模制品,其包含a)聚丙烯基质和掺入其中的如下组分的组合:b)α,β-不饱和羧酸试剂官能化烯烃聚合物或共聚物、c)伯或仲脂肪酸酰胺和d)选自如下的成核剂:苯甲酸钠、2,2’-亚甲基-双(4,6-二-叔丁基苯基)磷酸酯、甘油锌、1,2-二羧酸环己烷的钙盐和1,2-二羧酸降冰片烷的钠盐。还公开了一种通过掺入所述添加剂给聚丙烯模制品提供耐划痕性的方法。聚丙烯基质例如为聚丙烯均聚物或热塑性聚烯烃(TPO)。组分b)例如为马来酸化聚丙烯或α-烯烃和马来酸酐的反应产物。脂肪酸酰胺例如为硬脂基芥酸酰胺或油基棕榈酰胺。模制品适于汽车部件。模制品还有利地含有填料如滑石。
Description
本申请要求2009年10月1日提交的美国临时申请Nos.61/247,682、2009年7月7日提交的61/223,500和2009年5月26日提交的61/217,059的优先权,通过引用将所述申请的内容结合到本文中。
本发明旨在耐划痕聚丙烯组合物。本发明还旨在一种赋予聚丙烯组合物耐划痕性的方法。聚丙烯组合物例如为热塑性烯烃(TPO)模制品。模制品例如用于汽车应用中。
美国专利No.7,026,391教导了聚烯烃和聚烯烃与α,β不饱和羧酸酯、酸或酐的反应产物如丙烯酸化或马来酸化聚丙烯的混合物。
U.S.2006/0276571教导了含有羧酸试剂官能化烯烃聚合物和伯或仲脂肪酸酰胺的聚烯烃基质。
通过引用将此处所列美国专利和出版的申请结合到本文中。
发明概述
公开聚丙烯模制品,其包含:
a)聚丙烯基质,和
掺入其中的如下组分的组合:
b)α,β-不饱和羧酸试剂官能化烯烃聚合物或共聚物,
c)伯或仲脂肪酸酰胺,和
d)选自如下的成核剂:苯甲酸钠、2,2’-亚甲基-双(4,6-二-叔丁基苯基)磷酸酯、甘油锌、1,2-二羧酸环己烷的钙盐和1,2-二羧酸降冰片烷的钠盐。
还公开聚丙烯模制品,其包含:
a)聚丙烯基质,和
掺入其中的如下组分的组合:
b)α,β-不饱和羧酸试剂官能化烯烃聚合物或共聚物,
c)伯或仲脂肪酸酰胺,
d)选自如下的成核剂:苯甲酸钠、2,2’-亚甲基-双(4,6-二-叔丁基苯基)磷酸酯、甘油锌、1,2-二羧酸环己烷的钙盐和1,2-二羧酸降冰片烷的钠盐,和
e)填料。
还公开了一种给聚丙烯模制品提供耐划痕性的方法,所述方法包括向所述聚丙烯制品中掺入:
b)α,β-不饱和羧酸试剂官能化烯烃聚合物或共聚物,
c)伯或仲脂肪酸酰胺,和
d)选自如下的成核剂:苯甲酸钠、2,2’-亚甲基-双(4,6-二-叔丁基苯基)磷酸酯、甘油锌、1,2-二羧酸环己烷的钙盐和1,2-二羧酸降冰片烷的钠盐。
还公开一种给聚丙烯模制品提供耐划痕性的方法,所述方法包括向所述聚丙烯制品中掺入:
b)α,β-不饱和羧酸试剂官能化烯烃聚合物或共聚物,
c)伯或仲脂肪酸酰胺,
d)选自如下的成核剂:苯甲酸钠、2,2’-亚甲基-双(4,6-二-叔丁基苯基)磷酸酯、甘油锌、1,2-二羧酸环己烷的钙盐和1,2-二羧酸降冰片烷的钠盐,和
e)填料。
详述
本发明组分a)例如为聚丙烯均聚物。
聚丙烯均聚物还包括长链支化聚丙烯。
聚丙烯可通过不同的方法制备。实例为;
使用通常含一种或多于一种周期表族IVb、Vb、VIb或VIII金属的催化剂催化聚合。这些金属通常具有一个或大于一个配体,通常为氧化物、卤化物、醇化物、酯、醚、胺、烷基、链烯基和/或芳基,其可以为π-或σ-配位的。这些金属配合物可以为游离形式或固定在基质上,通常在活性氯化镁、氯化钛(III)、氧化铝或氧化硅上。这些催化剂可以为在聚合介质中可溶或不可溶的。催化剂可直接用于聚合中或可使用其它活化剂,通常为烷基金属、金属氢化物、金属烷基卤化物、金属烷基氧化物或金属烷基烷,其中所述金属为周期表族Ia、IIa和/或IIIa的元素。活化剂可以便利地被其它酯、醚、胺或甲硅烷基醚基团改性。这些催化剂体系通常称为Phillips,Standard Oil Indiana,Ziegler(-Natta),TNZ(DuPont),金属茂或单中心催化剂(SSC)。
根据本发明另一实施方案,组分a)为聚丙烯无规共聚物,含一种或多种选自乙烯、C4-C20α-烯烃、乙烯基环己烷、乙烯基环己烯、C4-C20链烷二烯、C9-C12环烷二烯和降冰片烯衍生物的共聚单体的交替或多嵌段共聚物或嵌段共聚物;丙烯和共聚单体的总摩尔量为100%。
聚丙烯共聚物还包括长链支化聚丙烯共聚物。
合适C4-C20α-烯烃的实例为1-丁烯、1-戊烯、1-己烯、1-庚烯、1-辛烯、1-壬烯、1-癸烯、1-十一碳烯、1-十二碳烯、1-十四碳烯、1-十六碳烯、1-十八碳烯、1-二十碳烯和4-甲基-1-戊烯。
合适C4-C20链烷二烯的实例为己二烯和辛二烯。
合适C5-C12环烷二烯的实例为环戊二烯、环己二烯和环辛二烯。
合适降冰片烯衍生物的实例为5-亚乙基-2-降冰片烯(ENB)、二环戊二烯(DCP)和亚甲基-二亚甲基(domethylene)-六氢化萘(MEN)。
丙烯/乙烯共聚物含有例如50-99.9重量%,优选80-99.9重量%,特别是90-99.9重量%的丙烯。
其中共聚单体为C9-C20α-烯烃如1-壬烯、1-癸烯、1-十一碳烯、1-十二碳烯、1-十四碳烯、1-十六碳烯、1-十八碳烯或1-二十碳烯;C9-C20链烷二烯、C9-C12环烷二烯或降冰片烯衍生物如5-亚乙基-2-降冰片烯(ENB)或亚甲基-二亚甲基-六氢化萘(MEN)的丙烯共聚物含有优选大于90摩尔%,特别是90-99.9摩尔%或90-99摩尔%的丙烯。
其中共聚单体为C4-C8α-烯烃如1-丁烯、1-戊烯、1-己烯、1-庚烯、1-辛烯或4-甲基-1-戊烯;乙烯基环己烷、乙烯基环己烯、C4-C8链烷二烯或C5-C8环烷二烯的丙烯共聚物含有优选大于80摩尔%,特别是80-99.9摩尔%或80-99摩尔%的丙烯。
组分a)的其它实例为丙烯/异丁烯共聚物、丙烯/丁二烯共聚物、丙烯/环烯烃共聚物、丙烯与乙烯和二烯如己二烯、二环戊二烯或亚乙基-降冰片烯的三元共聚物;其中1-烯烃原位产生的丙烯/1-烯烃共聚物;和丙烯/一氧化碳共聚物。
本发明聚丙烯特别是聚丙烯均聚物、聚丙烯抗冲(多相)共聚物、其和TPO的共混物如聚丙烯均聚物和抗冲改性剂如EPDM或乙烯/α-烯烃共聚物的共混物。
TPO(热塑性烯烃)例如为约10至约90份丙烯均聚物、共聚物或三元共聚物,和约90至约10份(重量计)乙烯和C3-C8α-烯烃的弹性体共聚物。弹性体共聚物例如为乙烯/丙烯共聚物(EPM)或乙烯/丙烯/非共轭二烯(EPDM)。TPO例如公开于美国专利No.6,048,942中,通过引用结合到本文中。
组分b)为α,β-不饱和羧酸试剂官能化烯烃聚合物或共聚物。
羧酸试剂官能化烯烃聚合物或共聚物例如公开于美国专利No.7,026,391中,通过引用结合到本文中。
官能化烯烃聚合物或共聚物的烯烃聚合物或共聚物例如为组分a)的聚丙烯。
官能化烯烃聚合物或共聚物例如为至少一种聚丙烯和至少一种α,β-不饱和羧酸试剂如羧酸、酯或酐的反应产物。
在一个实施方案中,该组分中所用聚丙烯的数均分子量可以为约2,000至约10,000。这些聚合物通常具有约8至约40,或约10至约35,或约15至约30g/10min的熔体流动。与聚丙烯反应的羧酸试剂的量可以为约0.5重量%至约30重量%,或约1重量%至约20重量%,或约2重量%至约15重量%,或约4重量%至约10重量%。
α,β-不饱和羧酸试剂可以为单-或二羧酸试剂。羧酸试剂包括羧酸、酯和盐。一元α,β-不饱和羧酸试剂包括丙烯酸、甲基丙烯酸、肉桂酸(annamic)、巴豆酸和酯如具有1至约12个碳原子的酯,和盐如钠、钙或镁盐。二羧酸试剂的实例包括马来酸、马来酸酐、富马酸、甲基富马酸、降冰片烯二酸酐、衣康酸、柠康酸、衣康酸酐、柠康酸酐、马来酸单甲酯、马来酸单钠等。特别优选的α,β-不饱和羧酸试剂试剂为丙烯酸、甲基丙烯酸、丙烯酸酯、甲基丙烯酸酯和马来酸酐。
羧酸试剂与聚丙烯聚合物或共聚物之间的反应可通过本领域技术人员已知的方式进行。例如,反应可在自由基引发剂的存在下通过熔体方法在溶液中进行。自由基引发剂通常为过氧化物或各种有机偶氮化合物。所用引发剂的量通常基于聚烯烃和羧酸试剂的组合重量为约0.01重量%至约5重量%。
羧酸试剂与丙烯酸聚合物或共聚物之间的反应称为“接枝”。例如本发明官能化聚丙烯聚合物或共聚物为与丙烯酸、甲基丙烯酸、丙烯酸甲酯、甲基丙烯酸甲酯、甲基丙烯酸2-羟基丙酯、丙烯酸丁酯或马来酸酐接枝的聚丙烯聚合物或共聚物。在例如与马来酸酐接枝的情况下,这称为“马来酸化”。
丙烯酸化聚烯烃的实例为可由Uniroyal Chemical Company得到的POLYBOND聚合物。特别有用的聚合物为POLYBOND 1002,其具有15-25g/10min的熔体流动和5.5-7.0重量%的丙烯酸含量。市售马来酸接枝聚丙烯的实例为来自Eastman Chemical Products,Inc.的Epolene E-43蜡。EPOLENE E-43具有47的酸值和4500的近似数均分子量。EPOLENEC-16和C-18蜡为分别具有8000和4000的近似分子量的马来酸接枝聚乙烯。马来酸化乙烯-丙烯弹性体也是有用的,这种弹性体可在标识号99-10、99-14和99-26下由Exxon Chemical Company得到。这些共聚物分别含有77%、64%和43%的乙烯,马来酸化产品分别含有0.76%、0.56%和0.35%的马来酸或酐。
市售马来酸酐接枝聚烯烃的其它实例包括来自Shell的KRATONFG1901X,其通常称为马来酸化选择性氢化SEBS共聚物;可在名称LOTADER 3200(由88重量%乙烯、9重量%丙烯酸丁酯和3%马来酸酐的混合物制备)、LOTADER 6600(70%乙烯、27%丙烯酸酯和3%马来酸酐)等下由CdF Chimie得到的三元共聚物;与马来酸酐接枝的乙烯乙酸乙烯酯共聚物(EVA-MAH)可由Quantum Chemical Corp.得到。
作为选择,组分b)的官能化烯烃聚合物或共聚物为α-烯烃与如上所述α,β-不饱和羧酸试剂的反应产物。反应通过本领域已知方式进行。例如反应可在自由基引发剂的存在下通过熔体方法进行。自由基引发剂例如为过氧化物或有机偶氮化合物。不饱和羧酸试剂也例如为丙烯酸、甲基丙烯酸、丙烯酸酯、甲基丙烯酸酯或马来酸酐。
例如,α-烯烃为C3至约C33,例如α-烯烃为C18-C26α-烯烃,例如C22-26或C18α-烯烃。
例如,官能化烯烃为马来酸化α-烯烃,即α-烯烃和马来酸酐的反应产物。例如马来酸化α-烯烃具有下式:
其中:
R为C16-C24烷基,且
n为整数,使得平均分子量为约20,000至约50,000。
伯或仲脂肪酸酰胺例如为其中脂肪酸的脂肪基团为C11-C21烷基或链烯基。
伯或仲脂肪酸酰胺例如为至少一种选自如下的化合物:油酰胺、芥酸酰胺、硬脂酰胺、山萮酰胺、油基棕榈酰胺、硬脂基芥酸酰胺、亚乙基-双-硬脂酰胺和亚乙基-双-油酰胺。
特别地,本发明脂肪酸酰胺为仲脂肪酸酰胺如硬脂基芥酸酰胺或油基棕榈酰胺。
合适脂肪酸酰胺例如公开于美国专利No.6,228,915中,通过引用将其相关公开内容结合到本文中。
烷基为直链或支链,且例如为甲基、乙基、丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基、2-乙基丁基、正戊基、异戊基、1-甲基戊基、1,3-二甲基丁基、正己基、1-甲基己基、正庚基、异庚基、1,1,3,3-四甲基丁基、1-甲基庚基、3-甲基庚基、正辛基、2-乙基己基、1,1,3-三甲基己基、1,1,3,3-四甲基戊基、壬基、癸基、十一烷基、1-甲基十一烷基、十二烷基、1,1,3,3,5,5-六甲基己基、十三烷基、十四烷基、十五烷基、十六烷基、十七烷基、十八烷基、二十烷基或二十二烷基。
链烯基为烯属不饱和烷基,例如烯丙基。
官能化烯烃聚合物或共聚物添加剂与伯或仲脂肪酸酰胺添加剂的重量比例如为约20∶1至约1∶20,约10∶1至约1∶10,约1∶1至约20∶1,例如约1∶1至约15∶1,约1∶1至约10∶1,约1∶1至约7∶1,或约1∶1至约5∶1。例如,官能化烯烃与伯或仲脂肪酸酰胺的重量比为约1.5∶1,约2∶1,约3∶1或约4∶1。
待掺入聚丙烯基质中的官能化烯烃聚合物或共聚物b)和伯或仲脂肪酸酰胺添加剂c)组合的总量基于聚丙烯基质的总重量例如为约1重量%至约15重量%。例如,添加剂组合以基于聚丙烯基质的重量约1重量%至约10重量%,约3重量%至约7重量%,或约3重量%至约5重量%存在。例如,本发明b)和c)的组合以基于聚丙烯基质的重量约1重量%至约3重量%,约1重量%至约5重量%,或约1重量%至约7重量%存在。
组分d),本发明成核剂选自苯甲酸钠、2,2-亚甲基-双(4,6-二-叔丁基苯基)磷酸酯和甘油锌。
预期其它已知成核剂在本发明配制剂中也会良好地起作用。这类其它成核剂例如公开于美国专利Nos.6,465,551和6,878,443中,通过引用结合到本文中。其它可能的成核剂例如为二亚苄基山梨醇化合物,例如单甲基二亚苄基山梨醇如1,3:2,4-双(对-甲基亚苄基)山梨醇或二甲基亚苄基山梨醇如1,3:2,4-双(3,4-二甲基亚苄基)山梨醇。其它已知的成核剂为[2.2.1]庚烷-二环二羧酸(1,2-二羧酸降冰片烷)和1,2-二羧酸环己烷。除苯甲酸钠外,其它有机酸的金属盐也可以为合适的,例如1,2-二羧酸环己烷和1,2-二羧酸降冰片烷的金属盐,例如钠或钙盐。其它环状双酚磷酸酯也可以是合适的。
本发明成核剂例如以基于聚丙烯的重量约1至约50,000重量ppm的水平使用。例如,本发明成核剂以基于聚丙烯的重量约10至约20,000重量ppm,约100至约10,000重量ppm或约1000至约5000重量ppm的水平使用。
可将本发明添加剂单独或相互混合地加入聚丙烯基质中。如果需要的话,可将各个组分在掺入聚丙烯中以前例如通过干混合、压实或以熔体相互混合。
本发明添加剂的掺入通过已知方法如以粉末的形式干混合,或以例如在惰性溶剂、水或油中的溶液、分散体或悬浮液的形式湿混合而进行。本发明添加剂可例如在模塑以前或以后,或还通过将溶解或分散的添加剂或添加剂混合物应用于聚丙烯材料上,随后蒸发或不蒸发溶剂或悬浮/分散剂而掺入。它们可例如作为干混合物或粉末或作为溶液或分散体或悬浮液或熔体直接加入加工设备(如挤出机、密炼机等)中。
掺入可以在任何装配有搅拌器的可加热容器中,例如在密闭设备如捏合机、混合机或搅拌容器中进行。掺入优选在挤出机或捏合机中进行。加工在惰性气氛中还是在氧存在下进行不是关键的。
将添加剂加入聚丙烯基质中可在其中将聚丙烯熔融并与添加剂混合的所有常规混合机器中进行。合适的机器为本领域技术人员已知的。它们主要为混合机、捏合机和挤出机。
加工包括挤出、共捏合、拉挤、压缩模塑、板挤出、热成型、注塑或旋转模塑。方法优选在挤出机中通过在熔体加工期间引入添加剂而进行。
特别优选的加工机器为单螺杆挤出机、反向旋转和同向旋转双螺杆挤出机、旋转模塑装置、行星齿轮挤出机、环形挤出机或共捏合机。也可使用具有至少一个可施加真空的除气室的加工机器。
合适的挤出机和捏合机例如描述于Handbuch der Kunststoffex-trusion,第1卷Grundlagen,编者F.Hensen,W.Knappe,H.Potente,1989,第3-7页,ISBN:3-446-14339-4(第2卷Extrusionsanlagen 1986,ISBN3-446-14329-7)中。
例如,螺杆长度为1-60螺杆直径,优选35-48螺杆直径。螺杆转速优选为10-600转/分(rpm),非常优选25-300rpm。
最大处理量取决于螺杆直径、转速和驱动力。本发明方法还可通过改变所述参数或使用赋予剂量的称重机在低于最大处理量的水平下进行。
如果加入多个组分,则可将这些组分预混合或单独地加入。
也可将本发明添加剂喷雾在聚丙烯基质上。它们能稀释其它添加剂(如上述常规添加剂)或它们的熔体,使得它们也可与这些添加剂一起喷雾在基质上。在聚合催化剂减活期间通过喷雾加入是特别有利的;在这种情况下,放出的蒸汽可用于催化剂的减活。在球形聚合聚丙烯的情况下,可例如有利地通过喷雾任选与其它添加剂一起应用本发明添加剂。
也可将本发明添加剂和任选其它添加剂以母料(“浓缩物”)的形式加入聚丙烯中,其含有掺入聚合物中的浓度为例如约1重量%至约40重量%,优选约2重量%至约20重量%的组分。聚合物未必与最终加入添加剂的聚丙烯相同。在这种操作中,聚合物可以以粉末、颗粒、溶液、悬浮液或胶乳的形式使用。
掺入可在成型操作以前或期间,或通过将溶解或分散的化合物应用于聚丙烯上,随后蒸发或不蒸发溶剂而进行。将本发明添加剂掺入聚丙烯基质中的另一可能是在相应单体的聚合以前、期间或恰在以后或在交联以前加入它们。在本文中,本发明添加剂可直接或以胶囊化形式(如在蜡、油或聚合物中)加入。
本文所述含本发明添加剂的聚丙烯可用于生产模制品、旋转模塑制品、注塑制品、吹塑制品、型材等。
本发明聚丙烯还可任选含有约0.01至约5%,优选约0.025至约2%,尤其是约0.1至约1重量%的各种常规添加剂,例如下列材料或其混合物。
1.抗氧化剂
1.1烷基化单酚,例如2,6-二-叔丁基-4-甲基苯酚、2-叔丁基-4,6-二甲基苯酚、2,6-二-叔丁基-4-乙基苯酚、2,6-二-叔丁基-4-正丁基苯酚、2,6-二-叔丁基-4-异丁基苯酚、2,6-二环戊基-4-甲基苯酚、2-(α-甲基环己基)-4,6-二甲基苯酚、2,6-二-十八烷基-4-甲基苯酚、2,4,6-三环己基苯酚、2,6-二-叔丁基-4-甲氧基甲基苯酚,在侧链中为线性或支化的壬酚,例如2,6-二-壬基-4-甲酚、2,4-二甲基-6-(1-甲基十一烷-1-基)苯酚、2,4-二甲基-6-(1-甲基十七烷-1-基)苯酚、2,4-二甲基-6-(1-甲基十三烷-1-基)苯酚及其混合物。
1.2.烷硫基甲酚,例如2,4-二辛硫基甲基-6-叔丁基苯酚、2,4-二辛硫基甲基-6-甲基苯酚、2,4-二辛硫基甲基-6-乙基苯酚、2,6-二-十二烷硫基甲基-4-壬基苯酚。
1.3.氢醌和烷基化氢醌,例如2,6-二-叔丁基-4-甲氧基苯酚、2,5-二-叔丁基氢醌、2,5-二-叔戊基氢醌、2,6-二苯基-4-十八烷氧基苯酚、2,6-二-叔丁基氢醌、2,5-二-叔丁基-4-羟基茴香醚、3,5-二-叔丁基-4-羟基茴香醚、硬脂酸3,5-二-叔丁基-4-羟基苯酯、己二酸双-(3,5-二-叔丁基-4-羟基苯基)酯。
1.4.生育酚,例如α-生育酚、β-生育酚、γ-生育酚、δ-生育酚及其混合物(维生素E)。
1.5.羟化硫代二苯醚,例如2,2′-硫代双(6-叔丁基-4-甲基苯酚)、2,2′-硫代双(4-辛基苯酚)、4,4′-硫代双(6-叔丁基-3-甲基苯酚)、4,4′-硫代双(6-叔丁基-2-甲基苯酚)、4,4′-硫代双-(3,6-二-仲戊基苯酚)、4,4′-双(2,6-二甲基-4-羟基苯基)二硫化物。
1.6.亚烷基双酚,例如2,2′-亚甲基双(6-叔丁基-4-甲基苯酚)、2,2′-亚甲基双(6-叔丁基-4-乙基苯酚)、2,2′-亚甲基双[4-甲基-6-(α-甲基环己基)苯酚]、2,2′-亚甲基双(4-甲基-6-环己基苯酚)、2,2′-亚甲基双(6-壬基-4-甲基苯酚)、2,2′-亚甲基双(4,6-二-叔丁基苯酚)、2,2′-亚乙基双(4,6-二-叔丁基苯酚)、2,2′-亚乙基双(6-叔丁基-4-异丁基苯酚)、2,2′-亚甲基双[6-(α-甲基苄基)-4-壬基苯酚]、2,2′-亚甲基双[6-(α,α-二甲基苄基)-4-壬基苯酚]、4,4′-亚甲基双(2,6-二-叔丁基苯酚)、4,4′-亚甲基双(6-叔丁基-2-甲基苯酚)、1,1-双(5-叔丁基-4-羟基-2-甲基苯基)丁烷、2,6-双(3-叔丁基-5-甲基-2-羟基苄基)-4-甲基苯酚、1,1,3-三(5-叔丁基-4-羟基-2-甲基苯基)丁烷、1,1-双(5-叔丁基-4-羟基-2-甲基-苯基)-3-正十二烷基巯基丁烷、乙二醇双[3,3-双(3-叔丁基-4-羟基苯基)丁酸酯]、双(3-叔丁基-4-羟基-5-甲基-苯基)二环戊二烯、双[2-(3′叔丁基-2-羟基-5-甲基苄基)-6-叔丁基-4-甲基苯基]对苯二甲酸酯、1,1-双-(3,5-二甲基-2-羟基苯基)丁烷、2,2-双-(3,5-二-叔丁基-4-羟基苯基)丙烷、2,2-双-(5-叔丁基-4-羟基-2-甲基苯基)-4-正十二烷基巯基丁烷、1,1,5,5-四-(5-叔丁基-4-羟基-2-甲基苯基)戊烷。
1.7.苄基化合物,例如3,5,3′,5′-四-叔丁基-4,4′-二羟基二苄醚、十八烷基-4-羟基-3,5-二甲基苄基巯基乙酸酯、十三烷基-4-羟基-3,5-二-叔丁基苄基巯基乙酸酯、三(3,5-二-叔丁基-4-羟基苄基)胺、1,3,5-三-(3,5-二-叔丁基-4-羟基苄基)-2,4,6-三甲基苯、二-(3,5-二-叔丁基-4-羟基苄基)硫化物、3,5-二-叔丁基-4-羟基苄基-巯基-乙酸异辛基酯、双-(4-叔丁基-3-羟基-2,6-二甲基苄基)二硫醇对苯二甲酸酯、1,3,5-三-(3,5-二-叔丁基-4-羟基苄基)异氰脲酸酯、1,3,5-三-(4-叔丁基-3-羟基-2,6-二甲基苄基)异氰脲酸酯、3,5-二-叔丁基-4-羟基苄基-磷酸二-十八烷基酯和3,5-二-叔丁基-4-羟基苄基-磷酸单乙基酯、钙盐。
1.8.羟基苄基化丙二酸酯,例如二-十八烷基-2,2-双-(3,5-二-叔丁基-2-羟基苄基)-丙二酸酯、二-十八烷基-2-(3-叔丁基-4-羟基-5-甲基苄基)-丙二酸酯、二-十二烷基巯基乙基-2,2-双-(3,5-二-叔丁基-4-羟基苄基)丙二酸酯、双[4-(1,1,3,3-四甲基丁基)苯基]-2,2-双(3,5-二-叔丁基-4-羟基苄基)丙二酸酯。
1.9.芳族羟基苄基化合物,例如1,3,5-三-(3,5-二-叔丁基-4-羟基苄基)-2,4,6-三甲基苯、1,4-双(3,5-二-叔丁基-4-羟基苄基)-2,3,5,6-四甲基苯、2,4,6-三(3,5-二-叔丁基-4-羟基苄基)苯酚。
1.10.三嗪化合物,例如2,4-双(辛基巯基)-6-(3,5-二-叔丁基-4-羟基苯胺基)-1,3,5-三嗪、2-辛基巯基-4,6-双(3,5-二-叔丁基-4-羟基苯胺基)-1,3,5-三嗪、2-辛基巯基-4,6-双(3,5-二-叔丁基-4-羟基苯氧基)-1,3,5-三嗪、2,4,6-三(3,5-二-叔丁基-4-羟基苯氧基)-1,2,3-三嗪、1,3,5-三-(3,5-二-叔丁基-4-羟基苄基)异氰脲酸酯、1,3,5-三(4-叔丁基-3-羟基-2,6-二甲基苄基)异氰脲酸酯、2,4,6-三(3,5-二-叔丁基-4-羟基苯基乙基)-1,3,5-三嗪、1,3,5-三(3,5-二-叔丁基-4-羟基苯基丙酰基)-六氢-1,3,5-三嗪、1,3,5-三(3,5-二环己基-4-羟基苄基)异氰脲酸酯。
1.11.苄基膦酸酯,例如二甲基-2,5-二-叔丁基-4-羟基苄基膦酸酯、二乙基-3,5-二-叔丁基-4-羟基苄基膦酸酯、二-十八烷基3,5-二-叔丁基-4-羟基苄基膦酸酯、二-十八烷基-5-叔丁基-4-羟基-3-甲基苄基膦酸酯、3,5-二-叔丁基-4-羟基苄基膦酸的单乙酯的钙盐。
1.12.酰氨基苯酚,例如4-羟基-月桂酰苯胺、4-羟基-硬脂酰苯胺、2,4-双-辛基巯基-6-(3,5-叔丁基-4-羟基苯胺基)-s-三嗪和辛基-N-(3,5-二-叔丁基-4-羟基苯基)-氨基甲酸酯。
1.13.β-(3,5-二-叔丁基-4-羟基苯基)丙酸与如下一元醇或多元醇的酯:例如与甲醇、乙醇、正辛醇、异辛醇、十八醇、1,6-己二醇、1,9-壬二醇、乙二醇、1,2-丙二醇、新戊二醇、硫二甘醇、二甘醇、三甘醇、季戊四醇、三(羟乙基)异氰脲酸酯、N,N′-双(羟乙基)草酰胺、3-噻十一醇、3-噻十五醇、三甲基己二醇、三羟甲基丙烷、4-羟基甲基-1-磷杂-2,6,7-三氧杂双环[2.2.2]辛烷。
1.14.β-(5-叔丁基-4-羟基-3-甲基苯基)丙酸与如下一元醇或多元醇的酯:例如与甲醇、乙醇、正辛醇、异辛醇、十八醇、1,6-己二醇、1,9-壬二醇、乙二醇、1,2-丙二醇、新戊二醇、硫二甘醇、二甘醇、三甘醇、季戊四醇、三(羟乙基)异氰脲酸酯、N,N′-双(羟乙基)草酰胺、3-噻十一醇、3-噻十五醇、三甲基己二醇、三羟甲基丙烷、4-羟基甲基-1-磷杂-2,6,7-三氧杂双环[2.2.2]辛烷。
1.15.β-(3,5-二环己基-4-羟基苯基)丙酸与如下一元醇或多元醇的酯:例如与甲醇、乙醇、辛醇、十八醇、1,6-己二醇、1,9-壬二醇、乙二醇、1,2-丙二醇、新戊二醇、硫二甘醇、二甘醇、三甘醇、季戊四醇、三(羟乙基)异氰脲酸酯、N,N′-双(羟乙基)草酰胺、3-噻十一醇、3-噻十五醇、三甲基己二醇、三羟甲基丙烷、4-羟基甲基-1-磷杂-2,6,7-三氧杂双环[2.2.2]辛烷。
1.16.3,5-二-叔丁基-4-羟基苯基乙酸与如下一元醇或多元醇的酯:例如与甲醇、乙醇、辛醇、十八醇、1,6-己二醇、1,9-壬二醇、乙二醇、1,2-丙二醇、新戊二醇、硫二甘醇、二甘醇、三甘醇、季戊四醇、三(羟乙基)异氰脲酸酯、N,N′-双(羟乙基)草酰胺、3-噻十一醇、3-噻十五醇、三甲基己二醇、三羟甲基丙烷、4-羟基甲基-1-磷杂-2,6,7-三氧杂双环[2.2.2]辛烷。
1.17.β-(3,5-二-叔丁基-4-羟基苯基)丙酸的酰胺,例如N,N′-双(3,5-二-叔丁基-4-羟苯基丙酰基)六亚甲基二酰胺、N,N′-双(3,5-二-叔丁基-4-羟苯基丙酰基)三亚甲基二酰胺、N,N′-双(3,5-二-叔丁基-4-羟苯基丙酰基)酰肼、N,N′-双[2-(3-[3,5-二-叔丁基-4-羟苯基]丙酰氧基)乙基]草酰胺(NaugardXL-1,由Uniroyal提供)。
1.18.抗坏血酸(维生素C)。
1.19.胺类抗氧化剂,例如N,N′-二-异丙基-对-苯二胺、N,N′-二-仲丁基-对-苯二胺、N,N′-双(1,4-二甲基戊基)-对-苯二胺、N,N′-双(1-乙基-3-甲基戊基)-对-苯二胺、N,N′-双(1-甲基庚基)-对-苯二胺、N,N′-二环己基-对-苯二胺、N,N′-二苯基-对-苯二胺、N,N′-双(2-萘基)-对-苯二胺、N-异丙基-N′-苯基-对-苯二胺、N-(1,3-二甲基丁基)-N′-苯基-对-苯二胺、N-(1-甲基庚基)-N′-苯基-对-苯二胺、N-环己基-N′-苯基-对-苯二胺、4-(对-甲苯胺磺酰基)二苯胺、N,N′-二甲基-N,N′-二-仲丁基-对-苯二胺、二苯胺、N-烯丙基二苯胺、4-异丙氧基二苯胺、N-苯基-1-萘基胺、N-(4-叔辛基苯基)-1-萘基胺、N-苯基-2-萘基胺、辛基化二苯胺如p,p′-二-叔辛基二苯胺、4-正丁基氨基苯酚、4-丁酰基氨基苯酚、4-壬酰基氨基苯酚、4-十二烷酰基氨基苯酚、4-十八烷酰基氨基苯酚、双(4-甲氧基苯基)胺、2,6-二-叔丁基-4-二甲基氨基甲基苯酚、2,4′-二氨基二苯基甲烷、4,4′-二氨基二苯基甲烷、N,N,N′,N′-四甲基-4,4′-二氨基二苯基甲烷、1,2-双[(2-甲基苯基)氨基]乙烷、1,2-双(苯基氨基)丙烷、(邻-甲苯基)双胍、双[4-(1′,3′-二甲基丁基)苯基]胺、叔辛基化N-苯基-1-萘基胺、单-和二-烷基化叔丁基/叔辛基二苯胺的混合物、单-和二-烷基化壬基二苯胺的混合物、单-和二-烷基化十二烷基二苯胺的混合物、单-和二-烷基化异丙基/异己基二苯胺的混合物、单-和二-烷基化叔丁基二苯胺的混合物、2,3-二氢-3,3-二甲基-4H-1,4-苯并噻嗪、吩噻嗪、单-和二-烷基化叔丁基/叔辛基吩噻嗪的混合物、单-和二-烷基化叔辛基-吩噻嗪的混合物、N-烷基吩噻嗪、N,N,N′,N′-四苯基-1,4-二氨基丁-2-烯、N,N-双(2,2,6,6-四甲基-哌啶-4-基-六亚甲基二胺、双(2,2,6,6-四甲基哌啶-4-基)癸二酸酯、2,2,6,6-四甲基哌啶-4-酮、2,2,6,6-四甲基哌啶-4-醇。
2.UV吸收剂和光稳定剂
2.1.2-(2-羟基苯基)-2H-苯并三唑,例如已知商业羟苯基-2H-苯并三唑和如美国专利Nos.3,004,896;3,055,896;3,072,585;3,074,910;3,189,615;3,218,332;3,230,194;4,127,586;4,226,763;4,275,004;4,278,589;4,315,848;4,347,180;4,383,863;4,675,352;4,681,905、4,853,471;5,268,450;5,278,314;5,280,124;5,319,091;5,410,071;5,436,349;5,516,914;5,554,760;5,563,242;5,574,166;5,607,987、5,977,219和6,166,218所公开的苯并三唑,例如2-(2-羟基-5-甲基苯基)-2H-苯并三唑、2-(3,5-二-叔丁基-2-羟基苯基)-2H-苯并三唑、2-(2-羟基-5-叔丁基苯基)-2H-苯并三唑、2-(2-羟基-5-叔辛基苯基)-2H-苯并三唑、5-氯-2-(3,5-二-叔丁基-2-羟基苯基)-2H-苯并三唑、5-氯-2-(3-叔丁基-2-羟基-5-甲基苯基)-2H-苯并三唑、2-(3-仲丁基-5-叔丁基-2-羟基苯基)-2H-苯并三唑、2-(2-羟基-4-辛氧基苯基)-2H-苯并三唑、2-(3,5-二-叔戊基-2-羟基苯基)-2H-苯并三唑、2-(3,5-双-α-异丙苯基-2-羟基苯基)-2H-苯并三唑、2-(3-叔丁基-2-羟基-5-(2-(ω-羟基-八-(亚乙基氧基)羰基-乙基)-苯基)-2H-苯并三唑、2-(3-十二烷基-2-羟基-5-甲基苯基)-2H-苯并三唑、2-(3-叔丁基-2-羟基-5-(2-辛氧基羰基)乙基苯基)-2H-苯并三唑、十二烷基化2-(2-羟基-5-甲基苯基)-2H-苯并三唑、2-(3-叔丁基-2-羟基-5-(2-辛氧基羰基乙基)苯基)-5-氯-2H-苯并三唑、2-(3-叔丁基-5-(2-(2-乙基己氧基)-羰基乙基)-2-羟基苯基)-5-氯-2H-苯并三唑、2-(3-叔丁基-2-羟基-5-(2-甲氧基羰基乙基)苯基)-5-氯-2H-苯并三唑、2-(3-叔丁基-2-羟基-5-(2-甲氧基羰基乙基)苯基)-2H-苯并三唑、2-(3-叔丁基-5-(2-(2-乙基己氧基)羰基乙基)-2-羟基苯基)-2H-苯并三唑、2-(3-叔丁基-2-羟基-5-(2-异辛氧基羰基乙基)苯基-2H-苯并三唑、2,2’-亚甲基-双(4-叔辛基-(6-2H-苯并三唑-2-基)苯酚)、2-(2-羟基-3-α-异丙苯基-5-叔辛基苯基)-2H-苯并三唑、2-(2-羟基-3-叔辛基-5-α-异丙苯基苯基)-2H-苯并三唑、5-氟-2-(2-羟基-3,5-二-α-异丙苯基苯基)-2H-苯并三唑、5-氯-2-(2-羟基-3,5-二-α-异丙苯基苯基)-2H-苯并三唑、5-氯-2-(2-羟基-3-α-异丙苯基-5-叔辛基苯基)-2H-苯并三唑、2-(3-叔丁基-2-羟基-5-(2-异辛氧基羰基乙基)苯基)-5-氯-2H-苯并三唑、5-三氟甲基-2-(2-羟基-3-α-异丙苯基-5-叔辛基苯基)-2H-苯并三唑、5-三氟甲基-2-(2-羟基-5-叔辛基苯基)-2H-苯并三唑、5-三氟甲基-2-(2-羟基-3,5-二-叔辛基苯基)-2H-苯并三唑、甲基3-(5-三氟甲基-2H-苯并三唑-2-基)-5-叔丁基-4-羟基氢化肉桂酸酯、5-丁基磺酰基-2-(2-羟基-3-α-异丙苯基-5-叔辛基苯基)-2H-苯并三唑、5-三氟甲基-2-(2-羟基-3-α-异丙苯基-5-叔丁基苯基)-2H-苯并三唑、5-三氟甲基-2-(2-羟基-3,5-二-叔丁基苯基)-2H-苯并三唑、5-三氟甲基-2-(2-羟基-3,5-二-α-异丙苯基苯基)-2H-苯并三唑、5-丁基磺酰基-2-(2-羟基-3,5-二-叔丁基苯基)-2H-苯并三唑和5-苯基磺酰基-2-(2-羟基-3,5-二-叔丁基苯基)-2H-苯并三唑
2.2.2-羟基二苯甲酮,例如4-羟基、4-甲氧基、4-辛氧基、4-癸氧基、4-十二烷氧基、4-苄氧基、4,2′,4′-三羟基和2′-羟基-4,4′-二甲氧基衍生物。
2.3.取代和未被取代的苯甲酸的酯,例如水杨酸4-叔丁基苯酯、水杨酸苯酯、水杨酸辛基苯酯、二苯甲酰间苯二酚、双(4-叔丁基苯甲酰)间苯二酚、苯甲酰间苯二酚、3,5-二-叔丁基-4-羟基苯甲酸2,4-二-叔丁基苯酯、3,5-二-叔丁基-4-羟基苯甲酸十六烷基酯、3,5-二-叔丁基-4-羟基苯甲酸十八烷基酯、3,5-二-叔丁基-4-羟基苯甲酸2-甲基-4,6-二-叔丁基苯酯。
2.4.丙烯酸酯和丙二酸酯,例如α-氰基-β,β-二苯基丙烯酸乙酯或异辛酯、α-碳甲氧基肉桂酸甲酯、α-氰基-β-甲基-对-甲氧基肉桂酸甲酯或丁酯、α-碳甲氧基-对-甲氧基肉桂酸甲酯、N-(β-碳甲氧基-β-氰基乙烯基)-2-甲基二氢吲哚、SanduvorPR25、对-甲氧基亚苄基丙二酸二甲酯(CAS#7443-25-6),和SanduvorPR31、二-(1,2,2,6,6-五甲基哌啶-4-基)对-甲氧基亚苄基丙二酸酯(CAS#147783-69-5)。
2.5.镍化合物,例如2,2′-硫代双[4-(1,1,3,3-四甲基丁基)苯酚]的镍配合物,例如1∶1或1∶2配合物,其具有或不具有其它配体如正丁胺、三乙醇胺或N-环己基二乙醇胺,二丁基二硫代氨基甲酸镍,4-羟基-3,5-二-叔丁基苄基膦酸的单烷基酯如甲基或乙基酯的镍盐,酮肟如2-羟基-4-甲基苯基十一烷基酮肟的镍配合物,1-苯基-4-月桂酰-5-羟基吡唑的镍配合物,其具有或不具有其它配体。
2.6.位阻胺稳定剂,例如4-羟基-2,2,6,6-四甲基哌啶、1-烯丙基-4-羟基-2,2,6,6-四甲基哌啶、1-苄基-4-羟基-2,2,6,6-四甲基哌啶、双(2,2,6,6-四甲基-4-哌啶基)癸二酸酯、双(2,2,6,6-四甲基-4-哌啶基)琥珀酸酯、双(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯、双(1-辛氧基-2,2,6,6-四甲基-4-哌啶基)癸二酸酯、双(1,2,2,6,6-五甲基-4-哌啶基)正丁基-3,5-二-叔丁基-4-羟基苄基丙二酸酯、1-(2-羟乙基)-2,2,6,6-四甲基-4-羟基哌啶和琥珀酸的缩合物、N,N′-双(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺和4-叔辛基氨基-2,6-二氯-1,3,5-三嗪的线性或环状缩合物、三(2,2,6,6-四甲基-4-哌啶基)次氮基三乙酸酯、四(2,2,6,6-四甲基-4-哌啶基)-1,2,3,4-丁烷-四羧酸酯、1,1′-(1,2-亚乙基)-双-(3,3,5,5-四甲基哌嗪酮)、4-苯甲酰基-2,2,6,6-四甲基哌啶、4-硬脂酰氧基-2,2,6,6-四甲基哌啶、双(1,2,2,6,6-五甲基哌啶基)-2-正丁基-2-(2-羟基-3,5-二-叔丁基苄基)丙二酸酯、3-正辛基-7,7,9,9-四甲基-1,3,8-三氮杂螺[4.5]癸-2,4-二酮、双(1-辛氧基-2,2,6,6-四甲基哌啶基)癸二酸酯、双(1-辛氧基-2,2,6,6-四甲基哌啶基)琥珀酸酯、N,N′-双-(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺和4-吗啉基-2,6-二氯-1,3,5-三嗪的线性或环状缩合物、2-氯-4,6-双(4-正丁基氨基-2,2,6,6-四甲基哌啶基)-1,3,5-三嗪和1,2-双(3-氨基丙基氨基)乙烷的缩合物、2-氯-4,6-二-(4-正丁基氨基-1,2,2,6,6-五甲基哌啶基)-1,3,5-三嗪和1,2-双-(3-氨基丙基氨基)乙烷的缩合物、8-乙酰基-3-十二烷基-7,7,9,9-四甲基-1,3,8-三氮杂螺[4.5]癸烷-2,4-二酮、3-十二烷基-1-(2,2,6,6-四甲基-4-哌啶基)吡咯烷-2,5-二酮、3-十二烷基-1-(1,2,2,6,6-五甲基-4-哌啶基)吡咯烷-2,5-二酮、4-十六烷氧基-和4-硬脂酰氧基-2,2,6,6-四甲基哌啶的混合物、N,N′-双(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺和4-环己基氨基-2,6-二氯-1,3,5-三嗪的缩合产物、1,2-双(3-氨基丙基氨基)乙烷和2,4,6-三氯-1,3,5-三嗪以及4-丁基氨基-2,2,6,6-四甲基哌啶(CAS Reg.No.[136504-96-6])的缩合产物;N-(2,2,6,6-四甲基-4-哌啶基)-正十二烷基琥珀酰亚胺、N-(1,2,2,6,6-五甲基-4-哌啶基)-正十二烷基琥珀酰亚胺、2-十一烷基-7,7,9,9-四甲基-1-氧杂-3,8-二氮杂-4-氧代-螺[4,5]癸烷、7,7,9,9-四甲基-2-环十一烷基-1-氧杂-3,8-二氮杂-4-氧代螺[4,5]癸烷和表氯醇的反应产物、1,1-双(1,2,2,6,6-五甲基-4-哌啶基氧基羰基)-2-(4-甲氧基苯基)乙烯、N,N′-双-甲酰基-N,N′-双(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺、4-甲氧基-亚甲基-丙二酸与1,2,2,6,6-五甲基-4-羟基哌啶的二酯、聚[甲基丙基-3-氧基-4-(2,2,6,6-四甲基-4-哌啶基)]硅氧烷、马来酸酐-α-烯烃共聚物与2,2,6,6-四甲基-4-氨基哌啶或1,2,2,6,6-五甲基-4-氨基哌啶的反应产物。
位阻胺也可以为美国专利No.5,980,783所述化合物中一种,通过引用将其相关部分结合到本文中,即组分I-a)、I-b)、I-c)、I-d)、I-e)、I-f)、I-g)、I-h)、I-i)、I-j)、I-k)或I-l)的化合物,特别是所述美国专利No.5,980,783第64-72栏所列光稳定剂1-a-1、1-a-2、1-b-1、1-c-1、1-c-2、1-d-1、1-d-2、1-d-3、1-e-1、1-f-1、1-g-1、1-g-2或1-k-1。
位阻胺也可以为美国专利Nos.6,046,304和6,297,299所述化合物中一种,通过引用将其公开内容结合到本文中,例如如权利要求10或38或实施例1-12或其中D-1至D-5所述化合物。
2.7.在N原子上被羟基取代烷氧基取代的位阻胺,例如化合物如1-(2-羟基-2-甲基丙氧基)-4-十八酰氧基-2,2,6,6-四甲基哌啶、1-(2-羟基-2-甲基丙氧基)-4-十六酰氧基-2,2,6,6-四甲基哌啶、1-氧基-4-羟基-2,2,6,6-四甲基哌啶与来自叔戊醇的碳基团的反应产物、1-(2-羟基-2-甲基丙氧基)-4-羟基-2,2,6,6-四甲基哌啶、1-(2-羟基-2-甲基丙氧基)-4-氧代-2,2,6,6-四甲基哌啶、双(1-(2-羟基-2-甲基丙氧基)-2,2,6,6-四甲基哌啶-4-基)癸二酸酯、双(1-(2-羟基-2-甲基丙氧基)-2,2,6,6-四甲基哌啶-4-基)己二酸酯、双(1-(2-羟基-2-甲基丙氧基)-2,2,6,6-四甲基哌啶-4-基)琥珀酸酯、双(1-(2-羟基-2-甲基丙氧基)-2,2,6,6-四甲基哌啶-4-基)戊二酸酯、2,4-双{N-[1-(2-羟基-2-甲基丙氧基)-2,2,6,6-四甲基哌啶-4-基]-N-丁基氨基}-6-(2-羟乙基氨基)-s-三嗪。
2.8.草酰胺,例如4,4′-二辛氧基草酰替苯胺、2,2′-二乙氧基草酰替苯胺、2,2′-二辛氧基-5,5′-二-叔-丁酰替苯胺、2,2′-二-十二烷氧基-5,5′-二-叔丁酰替苯胺、2-乙氧基-2′-乙基草酰替苯胺、N,N′-双(3-二甲基氨基丙基)草酰胺、2-乙氧基-5-叔丁基-2′-乙酰替苯胺和它与2-乙氧基-2′-乙基-5,4′-二-叔丁酰替苯胺的混合物、邻-和对-甲氧基-二取代草酰替苯胺的混合物和邻-和对-乙氧基-二取代草酰替苯胺的混合物。
2.9.三-芳基-邻-羟苯基-s-三嗪,例如已知商业三-芳基-邻-羟苯基-s-三嗪和如美国专利Nos.3,843,371;4,619,956;4,740,542;5,096,489;5,106,891;5,298,067;5,300,414;5,354,794;5,461,151;5,476,937;5,489,503;5,543,518;5,556,973;5,597,854;5,681,955;5,726,309;5,736,597;5,942,626;5,959,008;5,998,116;6,013,704;6,060,543;6,242,598和6,255,483所公开的三嗪,例如4,6-双-(2,4-二甲基苯基)-2-(2-羟基-4-辛氧基苯基)-s-三嗪,Cyasorb1164,Cytec Corp,4,6-双-(2,4-二甲基苯基)-2-(2,4-二羟基苯基)-s-三嗪、2,4-双(2,4-二羟基苯基)-6-(4-氯苯基)-s-三嗪、2,4-双[2-羟基-4-(2-羟基乙氧基)苯基]-6-(4-氯苯基)-s-三嗪、2,4-双[2-羟基-4-(2-羟基-4-(2-羟基乙氧基)苯基]-6-(2,4-二甲基苯基)-s-三嗪、2,4-双[2-羟基-4-(2-羟基乙氧基)苯基]-6-(4-溴苯基)-s-三嗪、2,4-双[2-羟基-4-(2-乙酰氧基乙氧基)苯基]-6-(4-氯苯基)-s-三嗪、2,4-双(2,4-二羟基苯基)-6-(2,4-二甲基苯基)-s-三嗪、2,4-双(4-联苯基)-6-(2-羟基-4-辛氧基羰基亚乙基氧基苯基)-s-三嗪、2-苯基-4-[2-羟基-4-(3-仲丁氧基-2-羟基丙氧基)苯基]-6-[2-羟基-4-(3-仲戊氧基-2-羟基丙氧基)苯基]-s-三嗪、2,4-双(2,4-二甲基苯基)-6-[2-羟基-4-(3-苄氧基-2-羟基丙氧基)苯基]-s-三嗪、2,4-双(2-羟基-4-正丁氧基苯基)-6-(2,4-二-正丁氧基苯基)-s-三嗪、2,4-双(2,4-二甲基苯基)-6-[2-羟基-4-(3-壬氧基*-2-羟基丙氧基)-5-α-异丙苯基苯基]-s-三嗪(*表示辛氧基、壬氧基和癸氧基的混合物)、亚甲基双-{2,4-双(2,4-二甲基苯基)-6-[2-羟基-4-(3-丁氧基-2-羟基丙氧基)苯基]-s-三嗪}、在3:5′、5:5′和3:3′位上以5:4:1比桥联的亚甲基桥联二聚物混合物、2,4,6-三(2-羟基-4-异辛氧基羰基异亚丙基氧基苯基)-s-三嗪、2,4-双(2,4-二甲基苯基)-6-(2-羟基-4-己氧基-5-α-异丙苯基苯基)-s-三嗪、2-(2,4,6-三甲基苯基)-4,6-双[2-羟基-4-(3-丁氧基-2-羟基丙氧基)苯基]-s-三嗪、2,4,6-三[2-羟基-4-(3-仲丁氧基-2-羟基丙氧基)苯基]-s-三嗪、4,6-双-(2,4-二甲基苯基)-2-(2-羟基-4-(3-十二烷氧基-2-羟基丙氧基)-苯基)-s-三嗪和4,6-双-(2,4-二甲基苯基)-2-(2-羟基-4-(3-十三烷氧基-2-羟基丙氧基)-苯基)-s-三嗪的混合物,Tinuvin400,Ciba Specialty Chemicals Corp.,4,6-双-(2,4-二甲基苯基)-2-(2-羟基-4-(3-(2-乙基己氧基)-2-羟基丙氧基)-苯基)-s-三嗪和4,6-二苯基-2-(4-己氧基-2-羟基苯基)-s-三嗪。
3.金属减活剂,例如N,N′-二苯基草酰胺、N-水杨醛-N′-水杨酰肼、N,N′-双(水杨酰)肼、N,N′-双(3,5-二-叔丁基-4-羟苯基丙酰)肼、3-水杨酰氨基-1,2,4-三唑、双(亚苄基)草酰二酰肼、草酰替苯胺、间苯二酰二酰肼、癸二酰双苯基酰肼、N,N′-二乙酰己二酰二酰肼、N,N′-双(水杨酰)草酰二酰肼、N,N′-双(水杨酰)硫代丙酰二酰肼。
4.亚磷酸酯和亚膦酸酯,例如亚磷酸三苯酯、亚磷酸二苯基烷基酯、亚磷酸苯基二烷基酯、亚磷酸三(壬基苯基)酯、亚磷酸三月桂酯、亚磷酸三-十八烷基酯、二硬脂基季戊四醇二亚磷酸酯、亚磷酸三(2,4-二-叔丁基苯基)酯、二异癸基季戊四醇二亚磷酸酯、双(2,4-二-叔丁基苯基)季戊四醇二亚磷酸酯、双(2,6-二-叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯、二异癸氧基季戊四醇二亚磷酸酯、双(2,4-二-叔丁基-6-甲基苯基)季戊四醇二亚磷酸酯、双(2,4,6-三(叔丁基苯基)季戊四醇二亚磷酸酯、三硬脂基山梨醇三亚磷酸酯、四(2,4-二-叔丁基苯基)4,4′-亚联苯基二亚膦酸酯、6-异辛氧基-2,4,8,10-四-叔丁基-二苯并[d,f]-[1,3,2]-二磷杂庚英(dioxaphosphepin)、6-氟-2,4,8,10-四-叔丁基-12-甲基-二苯并[d,g][1,3,2]二氧杂磷杂八环、甲基亚磷酸双(2,4-二-叔丁基-6-甲基苯基)酯、乙基亚磷酸双(2,4-二-叔丁基-6-甲基苯基)酯、2,2′,2″-次氮基[三乙基三(3,3′5,5′-四-叔丁基-1,1’-联苯-2,2′-二基)亚磷酸酯]、2-乙基己基(3,3′,5,5′-四-叔丁基-1,1′-联苯-2,2′-二基)亚磷酸酯。
尤其优选如下亚磷酸酯:
5.羟胺,例如N,N-二苄基羟胺、N,N-二乙基羟胺、N,N-二辛基羟胺、N,N-二月桂基羟胺、N,N-二-十四烷基羟胺、N,N-二-十六烷基羟胺、N,N-二-十八烷基羟胺、N-十六烷基-N-十八烷基羟胺、N-十七烷基-N-十八烷基羟胺、N-甲基-N-十八烷基羟胺和衍生自氢化牛脂胺的N,N-二烷基羟胺。
6.硝酮,例如N-苄基-α-苯基硝酮、N-乙基-α-甲基硝酮、N-辛基-α-庚基硝酮、N-月桂基-α-十一烷基硝酮、N-十四烷基-α-十三烷基硝酮、N-十六烷基-α-十五烷基硝酮、N-十八烷基-α-十七烷基硝酮、N-十六烷基-α-十七烷基硝酮、N-十八烷基-α-十五烷基硝酮、N-十七烷基-α-十七烷基硝酮、N-十八烷基-α-十六烷基硝酮、N-甲基-α-十七烷基硝酮和衍生自衍生自氢化牛脂胺的N,N-二烷基羟胺的硝酮。
7.氧化胺,例如如美国专利Nos.5,844,029和5,880,191所公开的氧化胺衍生物,十二烷基甲基氧化胺、十三烷基氧化胺、三-十二烷基氧化胺和三-十六烷基氧化胺。
8.苯并呋喃酮和吲哚啉酮,例如美国专利Nos.4,325,863、4,338,244、5,175,312、5,216,052、5,252,643、5,369,159、5,356,966、5,367,008、5,428,177或5,428,162所公开的那些,或3-[4-(2-乙酰氧基乙氧基)苯基]-5,7-二-叔丁基-苯并呋喃-2-酮、5,7-二-叔丁基-3-[4-(2-硬脂酰氧基乙氧基)苯基]苯并呋喃-2-酮、3,3’-双[5,7-二-叔丁基-3-(4-[2-羟基乙氧基]苯基)苯并呋喃-2-酮]、5,7-二-叔丁基-3-(4-乙氧基苯基)苯并呋喃-2-酮、3-(4-乙酰氧基-3,5-二甲基苯基)-5,7-二-叔丁基-苯并呋喃-2-酮、3-(3,5-二甲基-4-新戊酰氧基苯基)-5,7-二-叔丁基-苯并呋喃-2-酮、3-(3,4-二甲基苯基)-5,7-二-叔丁基-苯并呋喃-2-酮,IrganoxHP-136,Ciba Specialty Chemicals Corp.,和3-(2,3-二甲基苯基)-5,7-二-叔丁基-苯并呋喃-2-酮。
9.硫协合剂,例如硫代二丙酸二月桂酯或硫代二丙酸二硬脂酯。
10.过氧化物清除剂,例如β-硫代二丙酸的酯,例如月桂基、硬脂基、肉豆蔻基或十三烷基酯、巯基苯并咪唑或2-巯基苯并咪唑的锌盐、二丁基二硫代氨基甲酸锌、二-十八烷基二硫醚、季戊四醇四(β-十二烷基巯基)丙酸酯。
11.聚酰胺稳定剂,例如与碘和/或磷化合物组合的铜盐和二价锰的盐。
12.碱性助稳定剂,例如三聚氰胺、聚乙烯吡咯烷酮、双氰胺、氰脲酸三烯丙酯、脲衍生物、肼衍生物、胺、聚酰胺、聚氨酯、较高脂肪酸的碱金属盐和碱土金属盐,例如硬脂酸钙、硬脂酸锌、山萮酸镁、硬脂酸镁、蓖麻醇酸钠和棕榈酸钾、焦儿茶酸锑或焦儿茶酸锌。
13.其它成核剂,例如无机物质如滑石、金属氧化物如二氧化钛或氧化镁、优选碱土金属的磷酸盐、碳酸盐和硫酸盐;有机化合物如单-或聚羧酸及其盐,例如4-叔丁基苯甲酸、己二酸、二苯基乙酸、琥珀酸钠或苯甲酸钠;聚合化合物如离子共聚物(离聚物)。
14.填料和增强剂,例如碳酸钙、硅酸盐、玻璃纤维、玻璃球、石棉、滑石、高岭土、云母、硫酸钡、金属氧化物和氢氧化物、炭黑、石墨、木粉和其它天然产品的粉或纤维、合成纤维。
本发明配制剂有利地包含填料,例如涂覆或未涂覆的滑石。
填料也可例如为天然或合成页硅酸盐或这类页硅酸盐的混合物。尤其重要的填料例如为层状硅酸盐粘土。非常尤其重要的为蒙脱石、膨润土、贝得石、云母、锂蒙脱石、皂石、绿脱石、锌蒙脱石、蛭石、伊利石、magadite、水羟硅钠石、硅镁石、铬岭石、水滑石、伊来石、高岭石、硅灰石、绿坡缕石、滑石或硅石或其混合物。
填料以基于聚丙烯的重量约1重量%至约50重量%存在。例如,填料以基于聚丙烯的重量约5%、约10%、约15%、约20%或约25%和所有这些可能范围内存在。
15.分散剂,例如聚氧化乙烯蜡或矿物油。
16.其它添加剂,例如增塑剂、润滑剂、乳化剂、颜料、染料、荧光增白剂、流变添加剂、催化剂、流量控制剂、增滑剂、交联剂、交联助剂、卤素清除剂、抑烟剂、防火剂、抗静电剂、澄清剂如取代和未被取代的二亚苄基山梨醇、苯并嗪酮UV吸收剂如2,2’-对-亚苯基-双(3,1-苯并嗪-4-酮),Cyasorb3638(CAS#18600-59-4),和发泡剂。
本发明聚丙烯组合物显示出良好耐气候性(对热、氧和光的稳定性)、耐划痕性、良好可加工性、良好机械强度、良好保光性,且为非粘性的。聚丙烯模制品例如适于汽车应用,即保险杠面板等。
实施例
以下实施例阐述本发明。实施例不意欲限制本发明的范围。除非另外指出,所有百分数为重量份。
实施例1热塑性烯烃(TPO)
试验配制剂在未填充TPO中借助熔体化合制备。TPO为含有约8-10重量%弹性体与2重量%炭黑的聚丙烯。将TPO和添加剂在18mm双螺杆挤出机中在204-230℃下混合。将团粒在80℃下干燥过夜。将TPO配制剂在450℉的温度,1000psi的注射和保持压力,50psi的背压,螺杆速度150rpm,设置为287.5mm的夹具装置,注射量70和45℉的冷却器温度下注塑,以提供4英寸×6英寸的光滑扁平板。
根据五指刮痕试验测试板。
标准五指刮痕试验方针(Daimler Chrysler Corporation Test NumberLP-463DD-18-1,日期2002-07-24)。
刮痕试验在0分钟(恰离开模具)、5分钟、10分钟、20分钟和过夜(24小时)在10牛顿下进行。将试样储存在环境条件下。
制备以下配制剂(重量%):
在10牛顿下的耐划痕性结果如下:
配制剂1显示出在10N下无耐划痕性。
不具有成核剂的配制剂2显示出在时间0下差的划痕性能。经储存24小时获得一定水平的耐划痕性。
在含有耐划痕添加剂和成核剂的配制剂3-8中,在时间0,恰离开模具时实现良好耐划痕性。该耐划痕性在24小时以后比配制剂2更好。在储存24小时以后观察到同样好的划痕性能。即,用本发明组合物不经调节、不在室温或升高的温度下储存或固化而实现耐划痕性。
耐划痕添加剂为马来酸化聚丙烯与硬脂基芥酸酰胺的2∶1重量共混物。
NU1为苯甲酸钠。NU2为2,2-亚甲基-双(4,6-二-叔丁基苯基)磷酸酯。NU3为甘油锌。
实施例2填充的热塑性烯烃(TPO)
试验配制剂在TPO中借助熔体化合制备。TPO为含有约8-10重量%弹性体与2重量%炭黑的聚丙烯。将TPO和添加剂在18mm双螺杆挤出机中在204-230℃下混合。还加入基于TPO的重量为30重量%的未涂覆滑石填料。将团粒在80℃下干燥过夜。将TPO配制剂在450℉的温度,1000psi的注射和保持压力,50psi的背压,螺杆速度150rpm,设置为287.5mm的夹具装置,注射量70和45℉的冷却器温度下注塑,以提供4英寸×6英寸的光滑扁平板。
在储存24小时以后根据五指刮痕试验测试板。
在20、15和10牛顿下耐划痕性结果如下:
耐划痕添加剂如实施例1中。
配制剂12和13为本发明的,且根据五指刮痕试验显示出显著降低的变白。
配制剂12和13与配制剂10、14和15相比显示出协同结果。
Claims (8)
1.一种聚丙烯模制品,其包含:
a)聚丙烯基质,和
掺入其中的如下组分的组合:
b)α,β-不饱和羧酸试剂官能化烯烃聚合物或共聚物,
c)伯或仲脂肪酸酰胺,和
d)选自如下的成核剂:苯甲酸钠、2,2’-亚甲基-双(4,6-二-叔丁基苯基)磷酸酯、甘油锌、1,2-二羧酸环己烷的钙盐和1,2-二羧酸降冰片烷的钠盐,
其中组分b)为与α,β-不饱和羧酸试剂接枝的聚丙烯聚合物或共聚物或为α-烯烃与α,β-不饱和羧酸试剂的反应产物。
2.根据权利要求1的模制品,其中所述聚丙烯基质为聚丙烯均聚物或为热塑性聚丙烯。
3.根据前述权利要求中任一项的模制品,其中α,β-不饱和羧酸试剂为丙烯酸、甲基丙烯酸、丙烯酸甲酯、甲基丙烯酸甲酯、甲基丙烯酸2-羟基丙酯、丙烯酸丁酯或马来酸酐。
4.根据前述权利要求中任一项的模制品,其中脂肪酸酰胺为硬脂基芥酸酰胺或油基棕榈酰胺。
5.根据前述权利要求中任一项的模制品,其中官能化烯烃聚合物或共聚物与伯或仲脂肪酸酰胺的重量比为约1∶1至约20∶1或约1∶1至约5∶1。
6.根据前述权利要求中任一项的模制品,其中官能化烯烃聚合物或共聚物和脂肪酸酰胺的总量基于聚丙烯基质的重量为约1重量%至约5重量%。
7.根据前述权利要求中任一项的模制品,其中成核剂以基于聚丙烯基质的重量约10至约20,000重量ppm,约100至约10,000ppm,或约1000至约5000ppm存在。
8.一种给聚丙烯模制品提供耐划痕性的方法,所述方法包括向所述聚丙烯制品中掺入:
b)α,β-不饱和羧酸试剂官能化烯烃聚合物或共聚物,
c)伯或仲脂肪酸酰胺,和
d)选自如下的成核剂:苯甲酸钠、2,2’-亚甲基-双(4,6-二-叔丁基苯基)磷酸酯、甘油锌、1,2-二羧酸环己烷的钙盐和1,2-二羧酸降冰片烷的钠盐,
其中组分b)为与α,β-不饱和羧酸试剂接枝的聚丙烯聚合物或共聚物或为α-烯烃与α,β-不饱和羧酸试剂的反应产物。
9.根据权利要求1-7中任一项的聚丙烯模制品,其进一步包含:
e)填料。
10.根据权利要求8的方法,其进一步包括掺入:
e)填料。
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