CN101331185B - 用于生产含乙烯-乙烯醇共聚物的聚烯烃模制品的方法 - Google Patents
用于生产含乙烯-乙烯醇共聚物的聚烯烃模制品的方法 Download PDFInfo
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- CN101331185B CN101331185B CN2006800467898A CN200680046789A CN101331185B CN 101331185 B CN101331185 B CN 101331185B CN 2006800467898 A CN2006800467898 A CN 2006800467898A CN 200680046789 A CN200680046789 A CN 200680046789A CN 101331185 B CN101331185 B CN 101331185B
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- ethylene
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- polyolefin
- vinyl alcohol
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- 229920000098 polyolefin Polymers 0.000 title claims abstract description 44
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 13
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 23
- 239000000126 substance Substances 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Substances CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 10
- 239000003963 antioxidant agent Substances 0.000 claims description 9
- 230000003078 antioxidant effect Effects 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 7
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 229940059574 pentaerithrityl Drugs 0.000 claims description 5
- 239000002516 radical scavenger Substances 0.000 claims description 5
- 150000001336 alkenes Chemical group 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 4
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 4
- 229960001545 hydrotalcite Drugs 0.000 claims description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid group Chemical group C(C1=CC=CC=C1)(=O)O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 150000002632 lipids Chemical class 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 239000002530 phenolic antioxidant Substances 0.000 abstract 1
- 230000000087 stabilizing effect Effects 0.000 abstract 1
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 description 21
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 21
- 238000002156 mixing Methods 0.000 description 11
- -1 N-alkyl acrylamide Chemical compound 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 8
- 125000003710 aryl alkyl group Chemical group 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 230000004927 fusion Effects 0.000 description 6
- 239000003595 mist Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 5
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 238000007127 saponification reaction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 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 3
- 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 3
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 3
- 125000004416 alkarylalkyl group Chemical group 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 3
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- STLLXWLDRUVCHL-UHFFFAOYSA-N [2-[1-[2-hydroxy-3,5-bis(2-methylbutan-2-yl)phenyl]ethyl]-4,6-bis(2-methylbutan-2-yl)phenyl] prop-2-enoate Chemical compound CCC(C)(C)C1=CC(C(C)(C)CC)=CC(C(C)C=2C(=C(C=C(C=2)C(C)(C)CC)C(C)(C)CC)OC(=O)C=C)=C1O STLLXWLDRUVCHL-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- KEMQGTRYUADPNZ-UHFFFAOYSA-N heptadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)=O KEMQGTRYUADPNZ-UHFFFAOYSA-N 0.000 description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N pentadecanoic acid Chemical compound CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 2
- 150000008301 phosphite esters Chemical class 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- 229920001384 propylene homopolymer Polymers 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
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 2
- 235000010234 sodium benzoate Nutrition 0.000 description 2
- 239000004299 sodium benzoate Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- SZHOJFHSIKHZHA-UHFFFAOYSA-N tridecanoic acid Chemical compound CCCCCCCCCCCCC(O)=O SZHOJFHSIKHZHA-UHFFFAOYSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- FMZUHGYZWYNSOA-VVBFYGJXSA-N (1r)-1-[(4r,4ar,8as)-2,6-diphenyl-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol Chemical compound C([C@@H]1OC(O[C@@H]([C@@H]1O1)[C@H](O)CO)C=2C=CC=CC=2)OC1C1=CC=CC=C1 FMZUHGYZWYNSOA-VVBFYGJXSA-N 0.000 description 1
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- JEFSTMHERNSDBC-UHFFFAOYSA-N 1,2-dimethylcyclohexa-2,4-dien-1-ol Chemical compound CC1=CC=CCC1(C)O JEFSTMHERNSDBC-UHFFFAOYSA-N 0.000 description 1
- PRBHEGAFLDMLAL-UHFFFAOYSA-N 1,5-Hexadiene Natural products CC=CCC=C PRBHEGAFLDMLAL-UHFFFAOYSA-N 0.000 description 1
- ZZNRIAJJKFZXIX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)henicosane-1,3-diol dihydroxyphosphanyl dihydrogen phosphite Chemical class OP(O)OP(O)O.C(CCCCCCCCCCCCCCCCC)C(O)C(CO)(CO)CO ZZNRIAJJKFZXIX-UHFFFAOYSA-N 0.000 description 1
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 description 1
- BVUXDWXKPROUDO-UHFFFAOYSA-N 2,6-di-tert-butyl-4-ethylphenol Chemical compound CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 BVUXDWXKPROUDO-UHFFFAOYSA-N 0.000 description 1
- WUHPLKWATBYDFS-UHFFFAOYSA-N 2,6-ditert-butyl-4-(3-methylbutyl)phenol Chemical compound CC(C)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 WUHPLKWATBYDFS-UHFFFAOYSA-N 0.000 description 1
- SCXYLTWTWUGEAA-UHFFFAOYSA-N 2,6-ditert-butyl-4-(methoxymethyl)phenol Chemical compound COCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SCXYLTWTWUGEAA-UHFFFAOYSA-N 0.000 description 1
- KDHONNUUDHJCID-UHFFFAOYSA-N 2-cyclopentyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C2CCCC2)=C1 KDHONNUUDHJCID-UHFFFAOYSA-N 0.000 description 1
- WCRKLZYTQVZTMM-UHFFFAOYSA-N 2-octadecylphenol Chemical compound CCCCCCCCCCCCCCCCCCC1=CC=CC=C1O WCRKLZYTQVZTMM-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
- 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
- AIBRSVLEQRWAEG-UHFFFAOYSA-N 3,9-bis(2,4-ditert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP1OCC2(COP(OC=3C(=CC(=CC=3)C(C)(C)C)C(C)(C)C)OC2)CO1 AIBRSVLEQRWAEG-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- ZAAQJFLUOUQAOG-UHFFFAOYSA-N 4-benzyl-2,6-ditert-butylphenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC=2C=CC=CC=2)=C1 ZAAQJFLUOUQAOG-UHFFFAOYSA-N 0.000 description 1
- OJOWICOBYCXEKR-UHFFFAOYSA-N 5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical group C1C2C(=CC)CC1C=C2 OJOWICOBYCXEKR-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- 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 1
- FWCZRQWFFSGQBX-UHFFFAOYSA-N CCCCCCCCCCC(CC(CC(C)C(C)(C)C)[O])C(C)(C)C Chemical compound CCCCCCCCCCC(CC(CC(C)C(C)(C)C)[O])C(C)(C)C FWCZRQWFFSGQBX-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
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- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical group 0.000 description 1
- 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 1
- ZPFKRQXYKULZKP-UHFFFAOYSA-N butylidene Chemical group [CH2+]CC[CH-] ZPFKRQXYKULZKP-UHFFFAOYSA-N 0.000 description 1
- NDWWLJQHOLSEHX-UHFFFAOYSA-L calcium;octanoate Chemical compound [Ca+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O NDWWLJQHOLSEHX-UHFFFAOYSA-L 0.000 description 1
- 229910001748 carbonate mineral Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229940114081 cinnamate Drugs 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
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Abstract
一种用于生产聚烯烃制品的方法，所述制品包括乙烯-乙烯醇共聚物，其中在稳定组合物的存在下，聚烯烃组分被熔融并且与乙烯-乙烯醇共聚物混合，所述稳定组合物包括：a)一种或多种除酸剂，其数量等于或高于300ppm，按重量计算，相对于聚烯烃组分的重量；和b)一种或多种酚类抗氧化剂，其数量等于或高于1100ppm，按重量计算，相对于聚烯烃组分的重量。
Description
本发明涉及一种用于生产模制品的方法，所述模制品包括烯烃树脂和乙烯-乙烯醇共聚物(下文常称为“EVOH”)的混合物。
各种类型的制品可以通过模塑混合物而制备，所述混合物是通过熔融混合烯烃树脂(特别地聚丙烯或聚乙烯)和EVOH而获得的。特别地，EVOH用于多层包装应用以便获得食物容器的气障，例如美国专利6316114中所述的。
然而，所述制品的工业制备中所要解决的主要问题是EVOH的化学和热降解。
实际上，EVOH是非常反应性的。特别地，当与聚烯烃熔融混合时，它可以与(衍生于聚合过程的)催化剂残余物反应，特别是氯化物。这导致黑点形成。
此外，EVOH易于粘于熔融加工装置的套筒并开始降解。不久，其变为褐色/黑色并且其恢复成聚合物熔体，因此也导致黑点形成。
实际上，对这些斑点进行的研究显示存在着氧化EVOH的不相容薄层，因此证实了它们是由所述降解现象所引起的。
结果，物理和光学性质恶化，主要由于所述黑点的外观所引起的。
这种问题变得特别关键，当碎屑和其它回收材料，其已经包含EVOH，通常被称作“二次粉碎物料(regrind)”，用于制备所述制品时。
因此，非常需要一种技术解决方案，其能够防止/降低褐色斑点形成。
因此，本发明的目的在于提供一种用于生产聚烯烃模制品的方法，所述模制品包括乙烯-乙烯醇共聚物，其中在稳定组合物的存在下，聚烯烃组分被熔融并且与乙烯-乙烯醇共聚物混合，所述稳定组合物包括：
a)一种或多种除酸剂，其数量等于或高于300ppm，优选地600-1500ppm，按重量计算，相对于聚烯烃组分的重量；和
b)一种或多种酚类抗氧化剂，其数量等于或高于1100ppm，优选地1400-3000ppm，按重量计算，相对于聚烯烃组分的重量。
由于存在所述添加剂，避免了黑点的出现或者至少显著降低了黑点的出现，即使当通过使用含大量EVOH的二次粉碎材料来生产具有较大厚度(100-500μm或以上)的所述制品如瓶子、薄板和薄片时。
在除组分a)和b)之外的一种或多种含磷(phosporus)熔融稳定剂c)存在下进行本发明方法时，显著地提高了所述效果。
这种组分c)，任选地用于本发明方法的熔融和混合步骤中，的优选的量等于或高于1000ppm，更优选地1000-3000ppm，特别地1300-2500ppm，按重量计算，相对于聚烯烃组分的重量。
特别适合用于本发明方法的EVOH共聚物通常通过皂化乙烯-乙烯基酯共聚物，特别地通过皂化乙烯-醋酸乙烯酯共聚物，是可获得的。EVOH的乙烯含量优选为5-60mol％，更优选地15-55mol％。乙酸乙烯酯部分的皂化度优选是80-100mol％。为了获得高的气障性能，皂化度更优选地为95mol％或以上，仍更优选地为98mol％或以上，特别地99mol％或以上。EVOH还可包含烯键式不饱和单体如丙烯，1-丁烯，异丁烯，不饱和酸如丙烯酸，甲基丙烯酸，巴豆酸，邻苯二甲酸，马来酸，衣康酸或它们的衍生物，丙烯酰胺如丙烯酰胺，N-烷基丙烯酰胺，甲基丙烯酰胺如甲基丙烯酰胺，N-烷基甲基丙烯酰胺，N，N-二甲基甲基丙烯酰胺，2-甲基丙烯酰胺丙烷磺酸或其盐，甲基丙烯酰胺丙基二甲胺或其盐，N-乙烯基酰胺如N-乙烯基吡咯烷酮，N-乙烯基甲酰胺，N-乙烯基乙酰胺，氰化的乙烯基物质(cyanated vinyls)如丙烯腈，甲基丙烯腈，乙烯基醚如烷基乙烯基醚羟烷基乙烯基醚，烷氧基烷基乙烯基醚，卤代乙烯基物质(halogenated vinyls)。
EVOH还可以包含较小量的(通常高达0.5mol％)的乙烯基硅烷共聚单体，例如，乙烯基三甲氧基硅烷和乙烯基三乙氧基硅烷。
所述EVOH共聚物一般地具有约0.1-50g/10min的熔体指数，使用2.16kg的重量和230℃的温度，根据ASTM测试D-1238L测量的。
通常，可被用于本发明方法的聚烯烃是R-CH＝CH2烯烃，其中R是氢原子或C1-C8烷基，或芳基(特别地苯基)，例如，1-丁烯，1-己烯，1-辛烯，4-甲基-1-戊烯，的聚合物或共聚物，和它们的混合物。
特别优选的是下列聚合物：
A)全同立构的、主要地全同立构的或无规立构的丙烯均聚物，全同立构的均聚物优选地具有高于80的全同立构指数；
B)丙烯与乙烯和/或以上通式的C4-C10α-烯烃的结晶共聚物，其中R是C2-C8烷基或芳基(特别地苯基)，其中总共聚单体含量为0.05wt％-20wt％，或者所述共聚物与全同立构的或主要地全同立构的丙烯均聚物的混合物；
C)乙烯与丙烯和/或所述通式的C4-C10α-烯烃的弹性体共聚物，其通常包含20-80wt％的乙烯，和任选地包含较少量的(指示性地，0.5-15wt％)的二烯，如丁二烯，1，4-己二烯，1，5-己二烯，亚乙基-降冰片烯；
D)乙烯的均聚物和共聚物，特别地HDPE、LDPE、LLDPE；
E)苯乙烯聚合物。
对于所述烯烃聚合物和它们的混合物来说，熔体流动速率(MFR，根据规范ISO 1238L)和室温下(约25℃)可溶于二甲苯的级分的粘度[η]的优选值是：
MFR：0.05-3000g/10min.；
二甲苯可溶物的特性粘数[η]：0.5-7.5dl/g.
属于以上定义A)和B)的丙烯聚合物的特定实例表示为结晶丙烯均聚物和共聚物，其具有这样的挠曲模量(在23℃根据ASTM D 790测量的)，大于或等于1800MPa，优选地大于或等于1900MPa，最优选大于或等于2000MPa。这种均聚物和共聚物通常具有这样的全同立构指数，其大于或等于94％，更优选地大于或等于96％，在25℃在二甲苯中测量的。实际上，通过在一个或多个阶段中借助于高度立体特异性的齐格勒-纳塔催化剂进行聚合，可以获得结晶丙烯均聚物和共聚物，其具有甚至高于2000MPa的相应于上述全同立构指数值的挠曲模量值。此外，上述高模量丙烯聚合物的分子量分布通常是宽的，优选地，Mw/Mn值为7-30(其中Mw和Mn分别是指重均分子量和数均分子量，根据凝胶渗透色谱法测量的)。
为了维持高的挠曲模量值，较好的是，共聚物中的共聚单体的含量是低的，通常小于或等于10wt％，特别地小于或等于5wt％。
除所述聚烯烃之外，用于本发明方法的聚烯烃组分可以包含一部分(通常，当存在时，1-10wt％，相对于聚烯烃组分的总重量)的官能化聚烯烃，通常羧基改性的聚烯烃。
所述羧基改性的聚烯烃通常是接枝以前所述的聚烯烃与羧酸或其衍生物(特别地酸酐)的产物。所述羧酸和其衍生物包括，尤其，马来酸，丙烯酸，衣康酸，巴豆酸，马来酸酐和衣康酸酐。在这些当中，马来酸酐是特别优选的。
接枝反应通常是这样进行的：用自由基形成剂(有机过氧化物)和待接枝的单体化合物(羧酸或衍生物)处理熔融状态中的起始聚烯烃。优选地，接枝聚烯烃中的羧基含量为0.005％-1％，更优选地，为0.01％-0.6％，按重量计算。
使用这种官能化聚烯烃来改善EVOH共聚物在聚烯烃材料中的分散，和/或用于多层制品中的中间体连接层(tie layer)(一般地将含EVOH的层结合到聚烯烃层)，使得它们通常以上述量存在于二次粉碎物料中。
根据本发明方法，EVOH共聚物组分与聚烯烃组分混合，其重量为2-60％，优选地5-55％的EVOH共聚物，相对于两种组分的总重量。
任何本领域已知的化合物，其在中和塑料(特别地，聚烯烃)中存在的酸物质是有效的，因此降低或者避免了酸性残余物(通常衍生于聚合催化剂)的典型的影响，例如金属腐蚀，可被用作本发明方法中的组分a)。
优选地，用于本发明方法的除酸剂a)选自羧酸的金属盐和水滑石。
特别地，羧酸的金属盐可以选自丙酸、苯甲酸的金属盐和脂肪酸的金属盐。
所述盐的金属组分不是特别关键的，但是它通常选自碱金属，如钠和钾，碱土金属如镁，钙和钡，和锌。
除了丙酸之外的羧酸的实例包括正丁酸，异丁酸，戊酸，庚酸，辛酸，壬酸，十二烷酸，十三烷酸，十四烷酸，十五烷酸，十六烷酸，十七烷酸，十八烷酸，十九烷酸。
上述羧酸的金属盐的特定实例是辛酸钙，硬脂酸钙，硬脂酸锌和苯甲酸钠。
水滑石的实例包括水合的碳酸盐矿物，通常由以下通式表示：
Mg6Al2(OH)16CO3.4H2O
和合成水滑石，通常由以下通式表示：
M1-xAlx(OH)2(An-)x/n..mH2O
其中M是Mg、Ca或Zn，An-是n价阴离子，如，Cl-、Br-、I-、NO3 -、ClO4 2-、SO4 2-、CO3 2-、SiO3 2-、HPO4 2-和PO4 2-，x是0-0.5的数值，m是0-2的数值。
用于本发明方法的抗氧剂b)通常全部是本领域已知作为抗氧化剂的酚类稳定剂。这种酚类抗氧化剂通常特征在于，在其结构中，存在一个或多个空间位阻的酚基，即，在相对于羟基的邻位中具有至少一个非氢的取代基，优选地，C3-30支链烷基，的基团。
上述化合物的实例是以下通式的苯酚化合物：
其中R′是-CHR2或-OR基团；R基团，在通式(I)中和在R′中，相同或不同，是氢，或C1-30直链或支链烷基；C3-30环烷基；C6-30芳基，C7-30烷芳基或芳烷基；或C1-30烷氧基(alcoxyl)；所述R基团中的一个或多个可任选地包含官能团，特别地，哌啶或-COOR″；-O-；-S-；-NHR″；-NHR″-NHR″；-OH″基团，其中R″选自氢，或C1-30直链或支链烷基；C3-30环烷基；C6-30芳基，C7-30烷芳基或芳烷基；或R和R′基团中的两个或多个被结合而形成环状结构；条件是在通式(I)中在相对于-OH基团的邻位中的两个R基团中的至少一个不是氢；或者酚类抗氧化剂包括两个或多个通式(I)的结构单元，其中R和R′基团具有上述含义，区别在于，它们中的至少一个被以下所取代：直接的键，或-O-或-S-官能团，或多价的直链或支链C1-30烷基；C3-30环烷基；C6-30芳基；C7-30烷芳基或芳烷基，所述多价基团任选地包含上述的官能团，并且其中全部化合价被通式(I)的结构单元所饱和。
上述的酚类抗氧化剂的特定实例是：
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-异戊基苯酚；2，6-二环戊基-4-甲基苯酚；2-叔丁基-4，6-二异丙基苯酚；2-叔丁基-4，6-双十八烷基苯酚；2，6-二叔丁基-4-甲氧基甲基苯酚；2，5-二叔丁基氢醌；2，6-双环己基氢醌；2，6-二叔丁基-4-十六烷基氧基苯酚；4，4′-硫基双(6-叔丁基-2-甲基苯酚)；2，2’-亚甲基双(6-叔丁基-4-甲基苯酚)；4，4′-亚甲基双(2，6-二叔丁基苯酚)；1，1-双(5-叔丁基-4-羟基-2-甲基苯基)丁烷；十八烷基甲基的3(3，5-二叔丁基-4-羟苯基)丙酸酯；乙基或十八烷基的3(3，5-双环己基-4-羟苯基)丙酸酯；1，3，5-三甲基-2，4，6-三(3′，5′-二叔丁基-4-羟基苄基)苯；四[亚甲基(3，5-二叔丁基-4-羟基氢化肉桂酸酯(cinnamate))]甲烷；2，2-双[4-(2(3，5-二叔丁基-4-羟基肉桂酰氧基)乙氧苯基]丙烷；季戊四醇-四[3-(3，5-二叔丁基-4-羟苯基)丙酸酯，2-[1-(2-羟基-3，5-二叔戊基苯基)乙基)-4，6-二叔戊基苯基]-丙烯酸酯，由Sumitomo Chemical以商标Sumilizer GS出售。
优选的酚类抗氧化剂的实例是：2，6-二叔丁基-4-甲基苯酚，由Degussa以商标Ionol出售；2，2-双(4-(2-(3，5-二叔丁基-4-羟基氢化肉桂酰氧基))乙氧苯基)丙烷；3-(3，5-二叔丁基-4-羟苯基)-丙酸十八烷基酯，由Ciba Specialty Chemicals以商标Irganox 1076出售；和季戊四醇(pentaerytrityl)四3-(3，5-二叔丁基-4-羟苯基)丙酸酯(propanoate)，由Ciba Specialty Chemicals以Irganox 1010商标出售。
用于本发明方法的特别优选的是酚类抗氧化剂，其基本上显示了在炉内老化测试(oven ageing test)中其稳定作用，根据方法ASTM D3012，在高于120℃的温度下。
这种稳定剂的实例是季戊四醇(pentaerytrityl)四3-(3，5-二叔丁基-4-羟苯基)丙酸酯(propanoate)和3-(3，5-二叔丁基-4-羟苯基)-丙酸十八烷基酯。
任何含磷化合物，特别地选自有机磷酸酯(phosphate)和亚膦酸酯(phosphonite)，在本领域已知作为相对于聚合物的熔融降解的稳定剂，可被用作组分c)。
在本发明方法中可被用作组分c)的有机亚磷酸酯(phosphite)的实例，是具有如下通式的化合物：
其中R1、R2、R3，相同或不同，是烷基、芳基或芳烷基(arlakyl)，具有1-18个碳原子；
其中R1和R2，相同或不同，是具有如上所述的含义的基团；Q是四价烷基；
其中R1、R2、R3、R4，相同或不同，是具有已经对于R基团所指明的含义，X是二价烷基、芳基或芳烷基。
通式II中所含的有机亚磷酸酯的实例描述于美国专利4,187,212和4,290,941中。
通式II、III和IV中所含的化合物的特定实例是：
三(2，4-二叔丁基苯基)亚磷酸酯，由Ciba Specialty Chemicals以商标Irgafos 168销售；双十八烷基季戊四醇二亚磷酸酯，以商标Weston618销售；4，4′-亚丁基双(3-甲基-6-叔丁基苯基-双十三烷基)亚磷酸酯，由ADEKA PALMAROLE以商标Mark P销售；三(mononyl苯基)亚磷酸酯；双(2，4-二叔丁基)-季戊四醇(pentaerithritol)二亚磷酸酯，以商标Ultranox 626销售。
在本发明方法中可被用作组分c)的有机亚膦酸酯的实例，是如下通式的化合物：
其中R1、R2、R3，相同或不同，是烷基、芳基或芳烷基，具有1-18个碳原子。
接着，R3基团可以被以下基团取代
其中R4和R5，相同或不同，是具有以上对于R基团所指明的含义，X是二价烷基、芳基或芳烷基。
通式V中所含的有机亚膦酸酯的实例描述在GB专利1,372,528中。
通式V中所含的化合物的特定实例是四(2，4-二叔丁基苯基)4，4′-二亚苯基二亚膦酸酯。
能够以任何合适的方式添加所述组分a)、b)和c)。
特别地，在本发明方法的熔融和混合步骤前，它们能够以所述量(使用常规的混配技术)被添加到聚烯烃组分中。
例如，当使用二次粉碎物料时，所述组分可以存在于来自一层或多层的研磨制品(例如薄膜或瓶子)的二次粉碎级分中，它们包括聚烯烃材料，EVOH或这两者。
实际上，在生产所述制品的制造过程中，有可能的并且适宜的是添加所述稳定剂组分到聚烯烃材料中，即使当用于生产不包含EVOH共聚物的层时，以便来自碎屑的二次粉碎物料将已经包含本发明方法所需数量的a)、b)和c)，使得可以做到连续生产最终制品，而没有出现不期望数量的黑点。
因此，本发明的另一目的是通过用于本发明方法的聚烯烃组合物而构成的，所述聚烯烃组合物包括一种或多种具有通式R-CH＝CH2的烯烃的聚合物或共聚物和稳定组合物，其中R是氢，或者具有2-8个碳原子的直链或支链的烷基或者芳基(特别地苯基)，所述稳定组合物，以ppm按重量计算，相对于聚烯烃组合物，包括：
a)一种或多种除酸剂，其数量等于或高于300ppm，优选地600-1500ppm；
b)一种或多种酚类抗氧化剂，其数量等于或高于1100ppm，优选地1400-3000ppm；和任选地，
c)一种或多种含磷(phosporus)的熔融稳定剂，其数量等于或高于1000ppm，优选地1000-3000ppm，更优选地1300-2500ppm。
本发明方法可以通过使用加工聚合物领域中众所周知的方法和装置来进行。
因此，熔融和混合步骤可以在通常用于加工热塑性聚合物，特别地聚烯烃，的挤出机中进行。
通常本领域已知的合适的挤出机包括单螺杆挤出机、传统的与共捏和机(CoKneader)(例如Buss)，啮合同向双螺杆挤出机，混合器(连续和间歇)。这种挤出机优选装备有用于待进料的材料的单独的进料***(例如，二次粉碎物料和未用过的聚合物)。挤出机中的温度优选地为100℃-260℃，更优选地为160-230℃。通过在这种温度进行操作，实现了熔融和混合。
如果进行预混步骤的话，可以使用本领域中所用的任何装置，优选地中和高速混合器，例如Nauta混合器、Mixaco和叶轮式混合器(Turbomixer)。
在熔融和混合步骤的下游，根据已知的技术处理熔融聚合物，来制备期望的最终制品。
因此，挤出机可以例如装备有扁平的或环形的挤出模头，以生产薄膜、薄板和瓶子。
全部通常所使用的技术，例如共挤出和吹塑-模塑，可用于生产单和多层制品。
详细细节在以下实施例中给出，其用于举例说明本发明，但不限制本发明。
实施例1-3和对比例1
使用下列聚合物材料和添加剂。
聚合物材料
PP：含约0.4wt％乙烯的丙烯无规共聚物，其MFRL为4g/10min，全同立构(isotatcticity)指数为97.5％；
EVOH：乙烯-乙烯醇共聚物(EVAL T101B，由EVAL销售)，包含32mol％的乙烯，密度为1.17g/cm3，MFRL为10g/10min；
连接层：NF 518E，由Mitsui销售，包括羧基改性的聚烯烃。
添加剂(组分a)-c))
CaSt：硬脂酸钙，用作组分a)；
NaBz：苯甲酸钠，用作组分a)；
Irganox 1010：季戊四醇(pentaerytrityl)四3-(3，5-二叔丁基-4-羟苯基)丙酸酯(propanoate)，用作组分b)；
Sumilizer GS：2-[1-(2-羟基-3，5-二叔戊基苯基)乙基)-4，6-二叔戊基苯基]-丙烯酸酯，用作组分b)；
Irgafos 168：三(2，4-二叔丁基苯基)磷酸酯，用作组分c)；
Irganox B215：约34wt％的Irganox 1010和约66wt％的Irgafos 168的共混物；
Irganox B225：50wt％的Irganox 1010和50wt％的Irgafos 168的共混物；
OB 30：石蜡油，密度为0.842kg/l，20℃，根据ASTM D 1298，流点(flow point)为-10℃，根据ASTM D 97；
DBS：二亚苄基山梨糖醇。
在转筒中将上述的聚合物材料和添加剂混合在一起。
然后，如此获得的混合材料熔融共混在双螺杆挤出机Berstorff ZE25(螺杆的长度/直径比为33)中并且在以下条件下在氮气氛下挤出：
转速： 250rpm；
挤出机输出： 6-20kg/时；
熔融温度： 200-250℃。
进行两个挤出过程，其后测量MFRL，在由各个过程的产物制备的雾度板上测量雾度和黑点含量，而对同样由所述产物制备的粒料(直径为约3mm和长度为约5mm)测量黄度指数。结果，以及进行熔融-混合的组分的量报道于表1中。
测试方法
通过注塑来制备用于雾度测量的所述板，1mm厚，注射时间为1秒，温度为230℃，模塑温度为40℃。
注射压机是BattenfeldTM型BA 500CD，夹持力为50吨。***物模具导致两个板的模塑(每一个55×60×1mm)。
雾度
在R.H.为50±5％和23±1℃，调节所述板12-48小时。
所用的装置是HunterTM D25P-9色度计。测量和计算原理在规范ASTM-D1003中给出。
在没有样品的条件下，校准装置，用雾度标准物检查校准。在五个板上进行雾度测量。
黑点
目测。确定5个板上的黑点数目/100cm2。所报道的值是5次计数的平均值。
黄度指数
根据方法ASTM D1925进行测量。
表1
注：*＝在100cm2上大于40个黑点；**＝在100cm2上10-40个斑点(在表中未呈现)；***＝在100cm2上4-10个斑点；****＝在100cm2上0-3个斑点；ppm数量是按重量计算的，相对于整个组合物。
Claims (10)
1.一种用于生产聚烯烃制品的方法，所述制品包括乙烯-乙烯醇共聚物，其中在稳定组合物的存在下，聚烯烃组分被熔融并且与乙烯-乙烯醇共聚物混合，所述稳定组合物包括：
a)一种或多种除酸剂，其数量等于或高于300ppm，按重量计算，相对于聚烯烃组分的重量；和
b)一种或多种酚类抗氧化剂，其数量等于或高于1100ppm，按重量计算，相对于聚烯烃组分的重量；
c)一种或多种含磷熔融稳定剂，所述含磷熔融稳定剂的数量等于或高于1000ppm，按重量计算，相对于聚烯烃组分的重量。
2.权利要求1的方法，其中稳定组合物的组分a)选自羧酸的金属盐和水滑石。
3.权利要求2的方法，其中组分a)选自苯甲酸的金属盐，脂肪酸的金属盐。
4.权利要求1的方法，其中稳定组合物的组分b)是空间位阻的酚类化合物。
5.权利要求4的方法，其中所述的位阻的酚类化合物是季戊四醇四3-(3，5-二叔丁基-4-羟苯基)丙酸酯或3-(3，5-二叔丁基-4-羟苯基)-丙酸十八烷基酯。
6.权利要求1的方法，其中乙烯-乙烯醇共聚物组分与聚烯烃组分混合，重量为2-60％的乙烯-乙烯醇共聚物，相对于两种组分的总重量。
7.权利要求1的方法，其中乙烯-乙烯醇共聚物以二次粉碎物料的形式使用。
8.用于权利要求1的方法的聚烯烃组合物，其包括一种或多种具有通式R-CH＝CH2的烯烃的聚合物和稳定组合物，其中R是氢，或者具有2-8个碳原子的直链或支链的烷基或者芳基，所述稳定组合物，以ppm按重量计算，相对于聚烯烃组合物，包括：
a)一种或多种除酸剂，其数量等于或高于300ppm；
b)一种或多种酚类抗氧化剂，其数量等于或高于1100ppm；
c)一种或多种含磷熔融稳定剂，所述含磷熔融稳定剂的数量等于或高于1000ppm。
9.通过权利要求1的方法获得的模制品。
10.权利要求9的模制品，其形式为多层容器，薄膜或者薄板。
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| Application Number | Priority Date | Filing Date | Title |
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| EP05112096.2 | 2005-12-14 | ||
| EP05112096 | 2005-12-14 | ||
| US80060106P | 2006-05-16 | 2006-05-16 | |
| US60/800,601 | 2006-05-16 | ||
| PCT/EP2006/068185 WO2007068536A1 (en) | 2005-12-14 | 2006-11-07 | A process for producing polyolefin molded articles comprising an ethylene-vinyl alcohol copolymer |
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| CN101331185A CN101331185A (zh) | 2008-12-24 |
| CN101331185B true CN101331185B (zh) | 2012-09-05 |
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| US (1) | US8153714B2 (zh) |
| EP (1) | EP1960466B1 (zh) |
| JP (1) | JP2009519361A (zh) |
| CN (1) | CN101331185B (zh) |
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| CA2694586A1 (en) * | 2007-07-31 | 2009-02-05 | Dow Global Technologies Inc. | Polymeric compositions having an improved whitness index, process of producing the same, and articles made therefrom |
| MX354678B (es) | 2011-07-08 | 2018-03-15 | Dow Global Technologies Llc | Composicion de mezcla de polietileno adecuada para pelicula soplada, metodo para producir la misma y peliculas hechas a partir de la misma. |
| JP7425394B2 (ja) * | 2017-06-27 | 2024-01-31 | 三菱ケミカル株式会社 | 樹脂組成物、溶融成形用材料および多層構造体 |
| CN108164908A (zh) * | 2017-12-19 | 2018-06-15 | 会通新材料股份有限公司 | 一种高强度、高韧性、高阻隔聚丙烯复合材料及其制备方法 |
| JP7356296B2 (ja) * | 2019-09-04 | 2023-10-04 | 株式会社クラレ | 樹脂組成物及びそれを用いた多層構造体 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5260371A (en) * | 1991-07-23 | 1993-11-09 | E. I. Du Pont De Nemours And Company | Process for making melt stable ethylene vinyl alcohol polymer compositions |
| EP1033080A2 (en) * | 1999-03-03 | 2000-09-06 | Kuraray Co., Ltd. | Oxygen absorptive resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4075163A (en) | 1970-10-22 | 1978-02-21 | Sandoz Ltd. | Benzene phosphonous acid compounds, their production and use as stabilizers for organic materials |
| GB1372528A (en) | 1970-10-22 | 1974-10-30 | Sandoz Ltd | Benzene phosphonous acid compounds their production and use as stabilizers for organic materials |
| US3962175A (en) | 1970-10-22 | 1976-06-08 | Sandoz Ltd. | Benzene phosphonous acid compounds, their production and use as stabilizers for organic materials |
| US3954847A (en) | 1970-10-22 | 1976-05-04 | Sandoz Ltd. | New benzene phosphonous acid compounds, their production and use as stabilizers for organic materials |
| US3928510A (en) | 1970-10-22 | 1975-12-23 | Sandoz Ltd | Benzene phosphonic acid esters |
| US4182725A (en) * | 1974-02-11 | 1980-01-08 | Exxon Research & Engineering Co. | Novel bisphenol derivatives and uses thereof |
| CA1078991A (en) * | 1975-02-20 | 1980-06-03 | Hans J. Lorenz | Stabilization systems from triarylphosphites and phenols |
| US4187212A (en) | 1975-02-20 | 1980-02-05 | Ciba-Geigy Corporation | Stabilization systems from triarylphosphites and phenols |
| US4600746A (en) * | 1984-02-08 | 1986-07-15 | Norchem, Inc. | Polyvinyl alcohol alloys and method of making the same |
| DE69017085T2 (de) | 1989-05-30 | 1995-06-14 | Kuraray Co | Kunststoff-Zusammensetzung. |
| AU655497B2 (en) | 1991-07-23 | 1994-12-22 | E.I. Du Pont De Nemours And Company | Improved processing stability of ethylene vinyl alcohol polymer compositions |
| US6316114B1 (en) | 1996-10-07 | 2001-11-13 | Applied Extrusion Technologies, Inc. | Barrier films based on blends of polypropylene and ethylene-vinyl alcohol copolymer |
| US20080003390A1 (en) * | 2005-04-27 | 2008-01-03 | Nahoto Hayashi | Multi-Layer Structure and Process for Production Thereof |
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2006
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- 2006-11-07 CN CN2006800467898A patent/CN101331185B/zh not_active Expired - Fee Related
- 2006-11-07 US US12/086,365 patent/US8153714B2/en active Active
- 2006-11-07 AT AT06819304T patent/ATE499410T1/de not_active IP Right Cessation
- 2006-11-07 EP EP06819304A patent/EP1960466B1/en not_active Not-in-force
- 2006-11-07 JP JP2008544914A patent/JP2009519361A/ja not_active Withdrawn
- 2006-11-07 DE DE602006020334T patent/DE602006020334D1/de active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5260371A (en) * | 1991-07-23 | 1993-11-09 | E. I. Du Pont De Nemours And Company | Process for making melt stable ethylene vinyl alcohol polymer compositions |
| EP1033080A2 (en) * | 1999-03-03 | 2000-09-06 | Kuraray Co., Ltd. | Oxygen absorptive resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1960466B1 (en) | 2011-02-23 |
| DE602006020334D1 (de) | 2011-04-07 |
| WO2007068536A1 (en) | 2007-06-21 |
| JP2009519361A (ja) | 2009-05-14 |
| EP1960466A1 (en) | 2008-08-27 |
| ATE499410T1 (de) | 2011-03-15 |
| US8153714B2 (en) | 2012-04-10 |
| CN101331185A (zh) | 2008-12-24 |
| US20100266797A1 (en) | 2010-10-21 |
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