CN114846071A - 交联聚烯烃弹性体泡沫 - Google Patents
交联聚烯烃弹性体泡沫 Download PDFInfo
- Publication number
- CN114846071A CN114846071A CN202080088754.0A CN202080088754A CN114846071A CN 114846071 A CN114846071 A CN 114846071A CN 202080088754 A CN202080088754 A CN 202080088754A CN 114846071 A CN114846071 A CN 114846071A
- Authority
- CN
- China
- Prior art keywords
- foam
- ethylene
- interpolymer
- weight percent
- olefin
- 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
Links
- 239000006260 foam Substances 0.000 title claims abstract description 70
- 229920006124 polyolefin elastomer Polymers 0.000 title description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 94
- 239000005977 Ethylene Substances 0.000 claims abstract description 94
- 239000000203 mixture Substances 0.000 claims abstract description 52
- 239000004711 α-olefin Substances 0.000 claims abstract description 40
- 229920001400 block copolymer Polymers 0.000 claims abstract description 32
- 239000004593 Epoxy Substances 0.000 claims abstract description 29
- 239000000178 monomer Substances 0.000 claims abstract description 29
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims abstract description 23
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000012190 activator Substances 0.000 claims abstract description 15
- 150000001336 alkenes Chemical class 0.000 claims abstract description 14
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical group CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims abstract description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 13
- 229920001577 copolymer Polymers 0.000 claims abstract description 13
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 5
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 5
- 239000000155 melt Substances 0.000 claims description 13
- 239000002666 chemical blowing agent Substances 0.000 claims description 11
- 239000002649 leather substitute Substances 0.000 claims description 8
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 7
- 150000002978 peroxides Chemical class 0.000 claims description 6
- 239000004156 Azodicarbonamide Substances 0.000 claims description 5
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical group NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims description 5
- 235000019399 azodicarbonamide Nutrition 0.000 claims description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical group [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 3
- 239000002480 mineral oil Substances 0.000 claims description 2
- 235000010446 mineral oil Nutrition 0.000 claims 1
- 239000004604 Blowing Agent Substances 0.000 abstract description 18
- 229920000642 polymer Polymers 0.000 description 33
- 230000000052 comparative effect Effects 0.000 description 32
- 238000005187 foaming Methods 0.000 description 22
- 230000032683 aging Effects 0.000 description 17
- 210000000497 foam cell Anatomy 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- 239000000126 substance Substances 0.000 description 14
- -1 Polyethylene Polymers 0.000 description 11
- 229920000098 polyolefin Polymers 0.000 description 11
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- 210000004027 cell Anatomy 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 4
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 4
- 230000000379 polymerizing effect Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000000113 differential scanning calorimetry Methods 0.000 description 3
- 229920001038 ethylene copolymer Polymers 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 239000010985 leather Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- JJRUAPNVLBABCN-UHFFFAOYSA-N 2-(ethenoxymethyl)oxirane Chemical compound C=COCC1CO1 JJRUAPNVLBABCN-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 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
- 239000008116 calcium stearate Substances 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 238000003490 calendering Methods 0.000 description 2
- 210000003850 cellular structure Anatomy 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 description 2
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 1
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 1
- XTFIVUDBNACUBN-UHFFFAOYSA-N 1,3,5-trinitro-1,3,5-triazinane Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)C1 XTFIVUDBNACUBN-UHFFFAOYSA-N 0.000 description 1
- UBRWPVTUQDJKCC-UHFFFAOYSA-N 1,3-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC(C(C)(C)OOC(C)(C)C)=C1 UBRWPVTUQDJKCC-UHFFFAOYSA-N 0.000 description 1
- 229940106006 1-eicosene Drugs 0.000 description 1
- FIKTURVKRGQNQD-UHFFFAOYSA-N 1-eicosene Natural products CCCCCCCCCCCCCCCCCC=CC(O)=O FIKTURVKRGQNQD-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
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- ZIDNXYVJSYJXPE-UHFFFAOYSA-N 2-methylbutan-2-yl 7,7-dimethyloctaneperoxoate Chemical compound CCC(C)(C)OOC(=O)CCCCCC(C)(C)C ZIDNXYVJSYJXPE-UHFFFAOYSA-N 0.000 description 1
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 1
- WPIYAXQPRQYXCN-UHFFFAOYSA-N 3,3,5-trimethylhexanoyl 3,3,5-trimethylhexaneperoxoate Chemical compound CC(C)CC(C)(C)CC(=O)OOC(=O)CC(C)(C)CC(C)C WPIYAXQPRQYXCN-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 1
- FSWNZCWHTXTQBY-UHFFFAOYSA-N 4,6-dimethylhept-1-ene Chemical compound CC(C)CC(C)CC=C FSWNZCWHTXTQBY-UHFFFAOYSA-N 0.000 description 1
- BBDKZWKEPDTENS-UHFFFAOYSA-N 4-Vinylcyclohexene Chemical compound C=CC1CCC=CC1 BBDKZWKEPDTENS-UHFFFAOYSA-N 0.000 description 1
- ICGLPKIVTVWCFT-UHFFFAOYSA-N 4-methylbenzenesulfonohydrazide Chemical compound CC1=CC=C(S(=O)(=O)NN)C=C1 ICGLPKIVTVWCFT-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 1
- 229920003314 Elvaloy® Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- HEAMQYHBJQWOSS-UHFFFAOYSA-N ethene;oct-1-ene Chemical compound C=C.CCCCCCC=C HEAMQYHBJQWOSS-UHFFFAOYSA-N 0.000 description 1
- BXOUVIIITJXIKB-UHFFFAOYSA-N ethene;styrene Chemical compound C=C.C=CC1=CC=CC=C1 BXOUVIIITJXIKB-UHFFFAOYSA-N 0.000 description 1
- LDLDYFCCDKENPD-UHFFFAOYSA-N ethenylcyclohexane Chemical compound C=CC1CCCCC1 LDLDYFCCDKENPD-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 210000004907 gland Anatomy 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- FRVCGRDGKAINSV-UHFFFAOYSA-L iron(2+);octadecanoate Chemical compound [Fe+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O FRVCGRDGKAINSV-UHFFFAOYSA-L 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 230000005226 mechanical processes and functions Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000005634 peroxydicarbonate group Chemical group 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 239000012451 post-reaction mixture Substances 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229920006029 tetra-polymer Polymers 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/14—Monomers containing five or more carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
- C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0023—Use of organic additives containing oxygen
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0869—Acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0869—Acids or derivatives thereof
- C08L23/0884—Epoxide containing esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
-
- 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
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
- C08J2201/026—Crosslinking before of after foaming
-
- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
-
- 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
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
-
- 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
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—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
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/019—Specific properties of additives the composition being defined by the absence of a certain additive
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/14—Applications used for foams
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/064—VLDPE
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Emergency Medicine (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
Abstract
泡沫由包含以下的组合物形成:至少50重量%的乙烯/α‑烯烃共聚物、烯烃嵌段共聚物或它们的共混物;30重量%至50重量%的E/X/Y/Z型含环氧基的乙烯互聚物,其中E是占互聚物的大于50重量%的乙烯单体,X是占互聚物的0重量%至40重量%的(甲基)丙烯酸酯、(甲基)丙烯酸烷基酯或乙酸乙烯酯,Y是甲基丙烯酸缩水甘油酯并且占互聚物的0.5重量%至13重量%,并且Z是衍生自选自由一氧化碳、二氧化硫和丙烯腈组成的组的共聚单体的共聚物单元并且占互聚物的0重量%至10重量%;0.5重量%至5重量%的发泡剂;0.1重量%至1重量%的活化剂:和小于0.05重量%的固化剂。
Description
相关申请的交叉引用
本申请要求于2019年12月24日提交的国际专利申请第PCT/CN2019/127943号的优先权,所述申请的全部公开内容据此通过引用并入。
技术领域
本公开的实施方案大体上涉及聚烯烃泡沫,并且更具体地涉及包含聚烯烃弹性体和含环氧基的乙烯互聚物的交联泡沫。
背景技术
人造皮革用作广泛应用方法中的天然皮革的替代物,该应用包括鞋类、服装、家具、汽车和其它应用。对于至少一些这些应用,耐热性可以是重要因素。例如,汽车座椅应用需要人造皮革在超过100℃的温度下热老化预定时间量后没有泡沫泡孔塌缩并且没有皮革的表面翘曲。
尽管丙烯基共聚物已经用于制备人造皮革,但组合物具有窄发泡窗口。因此,需要具有良好发泡和耐热性特性的替代性聚烯烃泡沫。
发明内容
本公开的实施方案通过提供表现出高于150℃的良好耐热性的聚烯烃弹性体交联泡沫来满足此需求。根据本文的一个或多个实施方案,泡沫由包含以下的组合物形成:至少50重量%的乙烯/α-烯烃共聚物、烯烃嵌段共聚物或它们的共混物;30重量%至50重量%的E/X/Y/Z型含环氧基的乙烯互聚物;0.5重量%至5重量%的发泡剂;0.1重量%至1重量%的活化剂:和小于0.05重量%的固化剂。乙烯/α-烯烃共聚物的密度为0.840g/cc至0.910g/cc,并且熔体指数(I2)为0.5g/10min至12.0g/10min。烯烃嵌段共聚物的密度为0.860g/cc至0.890g/cc,并且熔体指数(I2)为0.5g/10min至12g/10min。在E/X/Y/Z型含环氧基的互聚物中,E是占互聚物的大于50重量%的乙烯单体,X是占互聚物的0重量%至50重量%的(甲基)丙烯酸酯、(甲基)丙烯酸烷基酯或乙酸乙烯酯,Y是甲基丙烯酸缩水甘油酯并且占互聚物的0.5重量%至13重量%,并且Z是衍生自选自由一氧化碳、二氧化硫和丙烯腈组成的组的共聚单体的共聚物单元,并且占互聚物的0重量%至10重量%。
附图说明
图1A示出了在发泡之后比较实施例A的泡沫的扫描电子显微镜(SEM)图像;
图1B示出了在发泡之后比较实施例B的泡沫的扫描电子显微镜(SEM)图像;
图1C示出了在发泡之后比较实施例C的泡沫的扫描电子显微镜(SEM)图像;
图1D示出了在发泡之后比较实施例D的泡沫的扫描电子显微镜(SEM)图像;
图1E示出了在发泡之后比较实施例E的泡沫的扫描电子显微镜(SEM)图像;
图1F示出了在80℃下老化2小时后比较实施例B的泡沫的扫描电子显微镜(SEM)图像;
图1G示出了在125℃下老化2小时后比较实施例C的泡沫的扫描电子显微镜(SEM)图像;
图1H示出了在125℃下老化2小时后比较实施例D的泡沫的扫描电子显微镜(SEM)图像;
图1I示出了在125℃下老化2小时后比较实施例E的泡沫的扫描电子显微镜(SEM)图像;
图2A示出了根据在发泡之后本文示出和描述的一个或多个实施方案制备的实施例1的泡沫的扫描电子显微镜(SEM)图像;
图2B示出了根据在发泡之后本文示出和描述的一个或多个实施方案制备的实施例2的泡沫的扫描电子显微镜(SEM)图像;
图2C示出了根据在发泡之后本文示出和描述的一个或多个实施方案制备的实施例3的泡沫的扫描电子显微镜(SEM)图像;
图2D示出了根据在发泡之后本文示出和描述的一个或多个实施方案制备的实施例4的泡沫的扫描电子显微镜(SEM)图像;
图2E示出了根据在150℃下老化2小时后本文示出和描述的一个或多个实施方案制备的实施例1的泡沫的扫描电子显微镜(SEM)图像;
图2F示出了根据在150℃下老化2小时后本文示出和描述的一个或多个实施方案制备的实施例2的泡沫的扫描电子显微镜(SEM)图像;
图2G示出了根据在150℃下老化2小时后本文示出和描述的一个或多个实施方案制备的实施例3的泡沫的扫描电子显微镜(SEM)图像;并且
图2H示出了根据在150℃下老化2小时后本文示出和描述的一个或多个实施方案制备的实施例4的泡沫的扫描电子显微镜(SEM)图像。
具体实施方式
在本文所述的各种实施方案中,用于形成泡沫的组合物包含乙烯/α-烯烃共聚物、烯烃嵌段共聚物或它们的共混物;E/X/Y/Z型含环氧基的乙烯互聚合物;发泡剂;活化剂;和小于0.05重量%的固化剂。此类实施方案使得在不使用过氧化物的情况下能够形成具有良好耐热性和机械特性的泡沫,如下文将更详细地描述。
如本文所用,术语“组合物”和类似术语意指两种或更多种材料的混合物,如与其它聚合物共混的或含有添加剂、填充剂等的聚合物。组合物中包含反应前、反应和反应后混合物,其中后者将包含反应产物和副产物以及反应混合物的未反应组分和由反应前或反应混合物的一种或多种组分形成的分解产物(如果有的话)。
“聚合物”意指通过使不论相同类型或不同类型的单体聚合而制备的化合物。因此,通用术语聚合物涵盖通常用于指代仅由一种类型的单体制备的聚合物的术语均聚物和如下文所定义的术语互聚物。其还涵盖所有形式的互聚物,例如无规、嵌段等。术语“乙烯/α-烯烃聚合物”和“丙烯/α-烯烃聚合物”指示如下所述的互聚物。应注意,尽管聚合物通常被称为“由”单体“制成”、“基于”指定单体或单体类型、“含有”指定单体含量等,但是这显然被理解为是指指定单体的聚合残留物而不是未聚合物种。
“互聚物”意指通过使至少两种不同的单体聚合而制备的聚合物。此通用术语包含通常用于指由两种或更多种不同单体制备的聚合物的共聚物,并且包含由多于两种不同单体制备的聚合物,例如三元共聚物、四元共聚物等。
“聚烯烃”、“聚烯烃聚合物”、“聚烯烃树脂”和类似术语意指由作为单体的简单烯烃(也称为具有通式CnH2n的烯烃)生产的聚合物。聚乙烯通过使乙烯与或不与一种或多种共聚单体聚合来产生,聚丙烯通过使丙烯与或不与一种或多种共聚单体聚合来产生,等。因此,聚烯烃包含互聚物,例如乙烯-α-烯烃共聚物、丙烯-α-烯烃共聚物等。
“(甲基)丙烯酸”包含甲基丙烯酸和/或丙烯酸,并且“(甲基)丙烯酸酯”包含甲基丙烯酸酯和/或丙烯酸酯。
在本文所描述的各种实施方案的上下文中,“压延”和类似术语意指一种机械过程,其中熔融聚合物通过使熔融聚合物通过一系列辊以聚结、变平并将聚合物平滑成薄片或膜中而转化为薄片。
“层压”和类似术语意指将通常塑料或类似材料的膜施加到可以是另一膜的基材的过程。可以使用或不使用粘合剂将膜施加到基材上。如果没有粘合剂,可以加热膜和/或基材以促进热层压或熔融层压。层压物是层压过程的产品,并且这些产品是多层的,即,它们包括至少两层、与基底或基材层接触的膜层。
“泡沫”和类似术语意指通过在液体或固体中捕获许多气泡而形成的物质。
基于组合物,本文描述的各种实施方案包含至少50重量%、或50重量%到99重量%的乙烯/α-烯烃共聚物、烯烃嵌段共聚物或它们的共混物。
术语“乙烯/α-烯烃共聚物”通常是指包括乙烯和具有3个或更多个碳原子的α-烯烃共聚单体的聚合物。在实施方案中,乙烯占整个聚合物的大部分摩尔分数,即乙烯占整个聚合物的至少50摩尔%(mol%)。例如,乙烯可以占至少60mol%、至少70mol%或至少80mol%,其中整个聚合物的基本上其余部分包含至少一种其它共聚单体,其为具有3个或更多个碳原子的α-烯烃。对于多种乙烯/辛烯共聚物,组合物可以包含大于整个聚合物的80mol%的乙烯含量和整个聚合物的10mol%至20mol%或15mol%至20mol%的辛烯含量。
在各种实施方案中,烯烃嵌段共聚物是例如乙烯/α-烯烃嵌段共聚物。乙烯/α-烯烃嵌段共聚物的商业示例包括可购自密歇根州米德兰的陶氏化学公司(The Dow ChemicalCompany(Midland,MI))的以商品名INFUSETM获得的树脂。
在各种实施方案中,乙烯/α-烯烃嵌段共聚物可包含呈聚合形式的乙烯和一种或多种可共聚α-烯烃单体,其特征在于两种或更多种聚合单体单元的多个嵌段或链段在化学或物理特性方面不同。聚烯烃弹性体可为多嵌段共聚物。在一个或多个实施方案中,多嵌段共聚物可由式(AB)n表示,其中n为至少1,优选地为大于1的整数,如2、3、4、5、10、15、20、30、40、50、60、70、80、90、100或更大,“A”表示硬嵌段,并且“B”表示软嵌段。在实施方案中,A和B以与基本上支化或基本上星形方式相反的基本上线性方式键联。在一个或多个实施方案中,A嵌段和B嵌段沿聚合物链随机分布并且不具有如下结构:AAA-AA-BBB-BB。在一些实施方案中,嵌段共聚物不具有包含不同共聚单体的第三类型的嵌段。在实施方案中,嵌段A和嵌段B中的每一个具有基本上随机分布在嵌段内的单体或共聚单体,使得嵌段A和嵌段B都不包含具有不同组成的两个或更多个子链段,如末端链段,其具有与嵌段的其余部分基本上不同的组成。
乙烯/α-烯烃嵌段共聚物可包括不同量的“硬”和“软”嵌段。“硬”嵌段是指聚合单元的嵌段,其中乙烯以按聚合物的重量计大于约95重量%并且优选地大于约98重量%的量存在。换句话说,硬嵌段中的共聚单体含量,即除乙烯之外的单体的含量,按聚合物的重量计小于约5重量%并且优选地小于约2重量%。在一个或多个实施方案中,硬嵌段包含所有或基本上所有乙烯。另一方面,“软”嵌段是指聚合单元的嵌段,其中共聚单体含量,即除乙烯之外的单体的含量,大于约5重量%。举例来说,共聚单体含量按聚合物的重量计可大于约5重量%、大于约8重量%、大于约10重量%或大于约15重量%。在各种实施方案中,软嵌段中的共聚单体含量按聚合物的重量计可大于约20重量%、大于约25重量%、大于约30重量%、大于约35重量%、大于约40重量%、大于约45重量%、大于约50重量%或大于约60重量%。
在各种实施方案中,软嵌段以聚烯烃弹性体的总重量的约1重量%至约99重量%的量存在于乙烯/α-烯烃嵌段共聚物中。举例来说,软嵌段可以乙烯/α-烯烃嵌段共聚物的总重量的约5重量%至约95重量%、约10重量%至约90重量%、约15重量%至约85重量%、约20重量%至约80重量%、约25重量%至约75重量%、约30重量%至约70重量%、约35重量%至约65重量%、约40重量%至约60重量%、或约45重量%至约55重量%存在于乙烯/α-烯烃嵌段共聚物中。相反,硬嵌段可以类似的范围存在。软嵌段和硬嵌段重量百分比可基于从DSC或NMR获得的数据来计算。这类方法和计算公开在美国专利申请公开号2006/0199930中。
可用于形成乙烯/α-烯烃嵌段共聚物的α-烯烃共聚单体的示例包括借助于示例但不限于丙烯、异丁烯、1-丁烯、1-戊烯、1-己烯、1-庚烯、1-辛烯、1-壬烯、1-癸烯和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、3-甲基-1-丁烯、3-甲基-1-戊烯、4-甲基-1-戊烯、4,6-二甲基-1-庚烯、4-乙烯基环己烯、乙烯基环己烷、降冰片二烯、亚乙基降冰片烯、环戊烯、环己烯、二环戊二烯、环辛烯、C4-C40二烯、其它C4-C40α-烯烃等。在另外的实施方案中,α-烯烃共聚单体可包含C4-C8共聚单体。共聚单体含量可使用任何适合的技术如基于核磁共振(“NMR”)光谱法的技术以及例如通过如描述于美国专利号7,498,282中的13CNMR分析测量,所述专利以引用的方式并入本文中。
在各种实施方案中,如根据ASTM D1238(190℃;2.16kg)所确定,乙烯/α-烯烃嵌段共聚物的熔体指数(I2)为约0.5g/10min至约30.0g/10min。举例来说,乙烯/α-烯烃嵌段共聚物的熔体指数(I2)可为0.5g/10min至30.0g/10min、0.5g/10min至12g/10min、0.5g/10min至5.0g/10min、或3.0g/10min至7.0g/10min。
在各种实施方案中,乙烯/α-烯烃嵌段共聚物的密度为0.850g/cc至0.890g/cc。本文包括并且本文公开了0.850g/cc至0.890g/cc的所有个别值和子范围;例如乙烯/α-烯烃嵌段共聚物的密度可为0.850g/cc、0.855g/cc、0.860g/cc、0.865g/cc或0.870g/cc的下限至0.890g/cc、0.885g/cc、0.880g/cc或0.875g/cc的上限。在实施方案中,乙烯/α-烯烃嵌段共聚物的密度为0.860g/cc至0.890g/cc。
乙烯/α-烯烃嵌段共聚物的熔体温度(Tm)(DSC)为115℃至125℃。本文包括并且本文公开115℃到125℃的所有个别值和子范围;例如,乙烯/α-烯烃嵌段共聚物的熔点可为115℃、116℃、117℃、118℃、119℃或120℃的下限至125℃、124℃、123℃、122℃或121℃的上限。
在一些实施方案中,乙烯/α-烯烃嵌段共聚物的分子量分布(MWD)为3.5或更小。分子量分布(MWD)由重均分子量(Mw)除以数均分子量(Mn)定义。举例来说,一些实施方案的乙烯/α-烯烃嵌段共聚物的MWD为2至3。确定分子量(Mn和Mw)和MWD的技术可在美国专利号4,540,753中找到,所述专利以引用的方式并入本文中。
乙烯/α-烯烃嵌段共聚物可利用已知的聚合方法形成,如在PCT申请号PCT/US2005/008915、PCT申请号PCT/US2005/008916和PCT申请号PCT/US2005/008917中描述的那些,所述申请中的每一个都以引用的方式并入本文中。
附加地或另选地,各种实施方案包括乙烯/α-烯烃共聚物,诸如均匀支化的乙烯/α-烯烃共聚物。这些共聚物可以用单位点催化剂,诸如茂金属催化剂或限定几何构型催化剂制备,并且通常熔点小于105℃、小于90℃、小于85℃、小于80℃或小于75℃。熔点通过例如在美国专利号5,783,638中描述的差示扫描量热法(DSC)测量。在实施方案中,如上文所述,α-烯烃是C3-C20直链、支链或环状α-烯烃。
示例性均匀支化的乙烯/α-烯烃共聚物包含乙烯/丙烯、乙烯/丁烯、乙烯/1-己烯、乙烯/1-辛烯、乙烯/苯乙烯等。说明性三元共聚物包括乙烯/丙烯/1-辛烯、乙烯/丙烯/丁烯、乙烯/丁烯/1-辛烯、乙烯/丙烯/二烯单体(EPDM)和乙烯/丁烯/苯乙烯。共聚物可以是无规共聚物。
在各种实施方案中,如根据ASTM D1238(190℃;2.16kg)所确定,乙烯/α-烯烃共聚物的熔体指数(I2)为约0.5g/10min至约30.0g/10min。举例来说,乙烯/α-烯烃共聚物的熔体指数(I2)可为0.5g/10min至30.0g/10min、0.5g/10min至12g/10min、0.5g/10min至5.0g/10min、或3.0g/10min至7.0g/10min。
在各种实施方案中,乙烯/α-烯烃共聚物的密度为0.840g/cc至0.910g/cc。本文包括并且本文公开了0.840g/cc至0.910g/cc的所有个别值和子范围;例如,乙烯/α-烯烃共聚物的密度可为0.840g/cc、0.845g/cc、0.850g/cc、0.855g/cc、0.860g/cc、0.865g/cc或0.870g/cc的下限到为0.910g/cc、0.905g/cc、0.900g/cc、0.895g/cc、0.890g/cc、0.885g/cc、0.880g/cc、0.875g/cc的上限。在实施方案中,乙烯/α-烯烃共聚物的密度为0.860g/cc到0.900g/cc或0.860g/cc到0.890g/cc。
可商购获得的均匀支化的乙烯/α-烯烃共聚物的示例包括均匀支化的直链乙烯/α-烯烃共聚物(例如,可以商品名TAFMERTM从三井公司(Mitsui)获得和以商品名EXACTTM从埃克森美孚化工公司(Exxon Mobil Chemical Company)获得的那些),以及均匀支化的、基本上直链的乙烯/α-烯烃聚合物(例如,可以商品名AFFINITYTM和ENGAGETM聚乙烯从密歇根州米德兰的陶氏化学公司(The Dow Chemical Company,Midland,MI)获得的那些)。
在各种实施方案中,组合物还包含按组合物的总重量计30重量%到50重量%的E/X/Y/Z型含环氧基的乙烯互聚物,其中E为乙烯单体,其中E为乙烯单体,X为(甲基)丙烯酸酯、(甲基)丙烯酸烷基酯或乙酸乙烯酯,Y为甲基丙烯酸缩水甘油酯(GMA),Z为衍生自选自由一氧化碳、二氧化硫和丙烯腈组成的组的共聚单体的共聚物单元,并且占互聚物的0至10重量%。如本文所用,“含环氧基的乙烯互聚物”意指第一实施方案,其中环氧组合物可以例如通过含环氧基的单体如GMA与乙烯共聚成互聚物主链。另外,“含环氧基的乙烯互聚物”可以涵盖第二实施方案,其中环氧基被接枝到互聚物主链上。此外,“含环氧基的乙烯互聚物”可以涵盖第一实施方案和第二实施方案的组合。
乙烯可以按可聚合单体的总重量计大于50重量%的量存在。举例来说,含环氧基的乙烯互聚物可包含50重量%至99.5重量%的乙烯、55重量%至94重量%的乙烯、60重量%至90重量%的乙烯或65重量%至85重量%的乙烯。包括50重量%至99.5重量%的所有个别值和子范围。
在实施方案中,X组分可以按可聚合单体的总重量计0重量%至40重量%的量存在。举例来说,X组分可以按可聚合单体的总重量计1重量%至40重量%、12重量%至32重量%或13重量%至31重量%的量存在。包括0重量%至40重量%的所有个别值和子范围。在实施方案中,X可以是共聚物单元-(CH2CR1R2)-。在一些实施方案中,R1可以是氢、甲基或乙基。在一些实施方案中,R2是碳烷氧基、酰氧基或具有1至10个碳原子的烷氧基。如上所述,在各种实施方案中,X是(甲基)丙烯酸酯、(甲基)丙烯酸烷基酯或乙酸乙烯酯。合适的丙烯酸酯共聚单体包括丙烯酸甲酯(MA)、丙烯酸乙酯(EA)和丙烯酸丁酯(BA)。
在实施方案中,Y可以是共聚物单元-(CH2CR3R4)-。在一些实施方案中,R3可以是氢或甲基。在一些实施方案中,R4可以是碳环氧丙氧基(carboglycidoxy)或环氧丙氧基。在一些实施方案中,Y可选自缩水甘油基丙烯酸酯、缩水甘油基甲基丙烯酸酯、缩水甘油基丁基丙烯酸酯、缩水甘油基乙烯基醚,以及两种或两种以上缩水甘油基丙烯酸酯的组合、缩水甘油基甲基丙烯酸酯、缩水甘油基丁基丙烯酸酯和缩水甘油基乙烯基醚的所组成的组。各种实施方案的含环氧乙烯互聚物包含按可聚合单体的总重量计0.5重量%到13重量%或5重量%到10重量%的甲基丙烯酸缩水甘油酯(GMA)。不受理论的束缚,据信在GMA中存在的环氧单体具有发泡剂的偶氮基团或发泡剂的氨分解产物交联,以产生抵抗发泡膨胀的交联泡沫。另外,据信GMA与偶氮或氨基团之间的交联使得能够实现强交联泡沫,而无需过氧化物交联剂。
在实施方案中,Z可以是衍生自包括一氧化碳、二氧化硫、丙烯腈或其他单体的共聚单体的共聚物单元。在进一步的实施方案中,环氧官能化乙烯共聚物可包含按可聚合单体的总重量计约0重量%至约10重量%的Z、约0重量%至约8重量%的Z、约0重量%至约6重量%的Z、约0重量%至约4重量%的Z、约0重量%至约2重量%的Z、约2重量%至约10重量%的Z、约2重量%至约8重量%的Z、约2重量%至约6重量%的Z、约2重量%至约4重量%的Z、约4重量%至约10重量%的Z、约4重量%至约8重量%的Z、约4重量%至约6重量%的Z、约6重量%至约10重量%的Z、约6重量%至约8重量%的Z、或约8重量%至约10重量%的Z。
预期一些实施方案包括0重量%的Z。在此类实施方案中,含环氧基的乙烯互聚物可称为E/X/Y型含环氧基的乙烯互聚物。
含环氧基的乙烯互聚物的如根据ASTM D1238(190℃;2.16kg)确定的熔体指数(I2)可为4g/10min至20g/10min、4g/10min至15g/10min、4g/10min至12g/10min或5g/10min至10g/10min。可在一些实施方案中使用的可商购获得的共聚物树脂的示例包括以商品名ELVALOYTM从密歇根州米德兰的陶氏化学公司获得的那些。
根据各种实施方案,组合物还包含产生孔隙度以在加热时形成泡沫的化学发泡剂。化学发泡剂可以包含含氮组合物,其可以与含环氧基的乙烯互聚物的环氧基团交联。一般来讲,以有效于在泡沫中产生相当均匀的泡孔大小的量使用发泡剂。在各种实施方案中,发泡剂以按组合物的总重量计0.1重量%至30重量%、0.5重量%至5重量%或1重量%至3重量%的量存在。在各种实施方案中,发泡剂是分解以在吹塑工艺期间释放气体(例如,偶氮化合物或其它含氮化合物,诸如氨)以形成泡沫的化学发泡剂。通过化学发泡剂释放的一种或多种偶氮化合物或其它含氮化合物与含环氧基的乙烯互聚物的GMA反应以产生交联的含环氧基的乙烯互聚物。如上文和下文所,这种交联使得能够产生抵抗膨胀的强烈的泡沫,而无需使用过氧化物交联剂。
化学发泡剂包括偶氮二异丁腈(AIBN)、偶氮二甲酰胺、二亚硝基-五亚甲基-四胺、对甲苯磺酰肼、p,p'-氧基-双(苯磺酰肼)以及它们的组合。示例性偶氮化合物是偶氮二甲酰胺。适合使用的可商购获得的化学发泡剂包括购自海虹化学公司(Haihong Chemical)的偶氮二碳酰胺AC3000。为了调整膨胀-分解温度和发泡过程,发泡剂还可以是发泡剂的混合物或发泡剂和激活剂的混合物。
在各种实施方案中,用于生产泡沫的组合物包含按组合物的总重量计0.05重量%到5重量%、0.1重量%到1重量%或0.2重量%到0.4重量%的活化剂。活化剂降低了发泡剂的分解温度/轮廓。在各种实施方案中,活化剂是金属硬脂酸盐,诸如硬脂酸锌。在实施方案中,活化剂是一种或多种金属氧化物、金属盐或有机金属络合物或它们的组合。合适的活化剂的示例包括氧化锌、氧化镁、硬脂酸锌、硬脂酸钙、硬脂酸铁或它们的组合。合适的活化剂的其它示例包括咪唑、叔胺、路易斯酸、三氟化硼和适用于环氧-胺固化过程的其它众所周知的催化剂。不受理论的束缚,据信活化剂有助于调节发泡剂被活化以产生气体时的温度,该气体使组合物发泡到期望的厚度和/或密度降低。
在各种实施方案中,组合物包含按组合物的总重量计小于0.05重量%的固化剂。固化剂包括一种或多种有机过氧化物,包括二烷基过氧化物、过氧酯、过氧二碳酸酯、过氧缩酮、二酰基过氧化物或其两种或更多种的组合。过氧化物的示例包括过氧化二叔丁基、过氧化二枯基、二(3,3,5-三甲基己酰基)过氧化物、过氧新戊酸叔丁酯、过氧新癸酸叔丁酯、过氧二碳酸二(§-丁基)酯、过氧新癸酸叔戊酯、1,1-二叔丁基过氧基-3,3,5-三甲基环己烷、叔丁基-枯基过氧化物、2,5-二甲基-2,5-二(叔丁基-过氧基)己烷、1,3-双(叔丁基-过氧基-异丙基)苯或其组合。可商购获得的固化剂包括以商品名从阿克曼公司(Arkema)获得或以商品名从来自阿克苏诺贝尔(Akzo Nobel)获得的那些。然而,在其他实施方案中,组合物不含过氧化物。
在各种实施方案中,组合物可任选地包含矿物油,诸如链烷烃、环烷烃和其它烃或合成油。此类油可以按组合物的总重量计0重量%到40重量%、0重量%到30重量%、0重量%到20重量%、0.05重量%到40重量%、0.05重量%到30重量%或0.05重量%到20重量%的量存在。当包含时,油可用于调节最终产品的柔软性,诸如包括泡沫的人造皮革。
其它添加剂可以按组合物的总重量计0重量%到30重量%、0.1重量%到20重量%或0.1重量%到12重量%存在于组合物中,可以包括颜料(TiO2和其它相容有色颜料)、填料(例如,滑石、碳酸钙、硫酸钡和/或氧化硅)、稳定剂(例如,抗氧化剂、UV吸收剂和/或阻燃剂)和加工助剂(例如硬脂酸钙和/或硬脂酸钡)。抗氧化剂可以包括以商品名IRGANOXTM诸如IRGANOXTM1010和IRGANOXTM3114从巴斯夫公司(BASF)获得的那些。UV吸收剂可以包括以商品名TINUVINTM诸如TINUVINTM622从巴斯夫公司获得的那些。
在各种实施方案中,通过将聚合物与足以熔化聚合物的热量混合并且添加剩余成分(包括活化剂、发泡剂和任何添加剂)以形成均匀混合物来由组合物形成泡沫。然后将混合物加热至足以产生发泡的温度。
在各种实施方案中,所得泡沫具有均匀的闭合泡沫泡孔和几乎没有或甚至没有聚结/塌陷、高发泡效率(例如,当在230℃下发泡50秒时,泡沫膨胀比实现大于700%)、在210℃到230℃下30秒到200秒的发泡窗口以及出色的泡沫弹性。
根据各种实施方案,泡沫泡孔大小小于约400μm。例如,在实施方案中,泡沫泡孔大小大于或等于100μm并且小于或等于400μm。然而,考虑了其它泡孔大小,包括大小大于400μm的泡孔,这取决于有待采用泡沫的特定应用。因此,在一些实施方案中,泡沫可以具有微孔结构,其中泡孔小于100μm。在一些实施方案中,泡沫可具有泡孔小于1μm的纳米泡孔结构。
在各种实施方案中,泡沫用于制造人造皮革。人造皮革可以是无支撑的(例如,无额外的背衬,即,用于皮肤应用)或通过将其施加到基础层诸如织物(即,用于装饰应用)来支撑,并且可以通过压延工艺或本领域已知和使用的其它方法形成。合适的织物可以是织造物、非织造物、针织物、斜纹织物、汗织物(sweating)等。在各种实施方案中,通过任何合适的方法,例如通过喷涂将泡沫组合物施加到聚合物层,到期望的厚度和/或密度,并且向其施加加热。在活化时泡沫组合物中的发泡剂产生气体或气体混合物,这将诱导发泡以产生包含泡孔结构的泡沫层。
由此获得的人造皮革具有出色的触感、外观和与天然皮革相似的全手感,并且进一步具有出色的柔软性和表面强度。各种实施方案的人造皮革可用作汽车领域中的表皮或盖,包括例如座椅、仪器面板、控制台盒、臂托架、头枕、门托、后面板、柱托、防日管、顶部衬里和方向盘盖的内部表皮或覆盖材料;在体育用品领域中的表皮或盖,例如轴承压盖、运动鞋鞋面、托架把手、运动工具和货物、自行车、摩托车和三轮车的桨和手柄夹具的覆盖材料;在壳体和建筑物领域中的表皮或盖,例如家具包覆材料、墙壁装饰性材料、台面布、餐具垫和杯托;工业部件领域中的表皮或盖,电动工具的夹具和软管;以及在其它领域中的表皮或盖,例如袋的覆盖材料、公文包、手袋、衣服、文件、相册、玩具和模塑制品。
实施例
提供以下实施例以说明各种实施方式,但并不意图限制权利要求书的范围。除非另外指明,否则所有的份数和百分比均按重量计。下文提供关于各种工作实施例、比较实施例和在工作和比较实施例中使用的物质的近似特性、特征、参数等。此外,实施例中所使用的原材料的描述如下:
ENGAGETM8200为均匀支化的基本上直链的乙烯/α-烯烃聚合物,其如根据ASTMD792测量的密度为0.87g/cc,如根据ASTM D1238在190℃/2.16kg下测量的熔体指数(I2)为5.0g/10min,并且根据ASTM D2240,10s秒测量的肖氏A硬度为66,可从密歇根州米德兰的陶氏化学公司获得;
DE 2400.05是丙烯/乙烯共聚物,其如根据ASTM D792测量的密度为0.866g/cc并且根据ASTM D1238-03在230℃/2.16kg下测量的熔体流动速率(MFR)为2g/10min,可从密歇根州米德兰的陶氏化学公司获得;
INFUSETM9507是烯烃嵌段共聚物(OBC),其如根据ASTM D792测量的密度为0.866g/cc并且根据ASTM D1238在190℃/2.16kg下测量的熔体指数(I2)为5.0g/10min,可从密歇根州米德兰的陶氏化学公司获得;
E/X/Y/Z-1是E/X/Y/Z型含环氧基的互聚物,其nBA含量为21重量%并且GMA含量为9重量%,根据ASTM D1238在190℃/2.16kg下测量的熔体指数(I2)为8.0g/10min;
AC 3000是偶氮二甲酰胺发泡剂,其可从海虹化学公司获得;
滑石是SQ-1250滑石,可从中国辽宁的海城水泉矿物产品有限公司(HaiChengShuiquan Mineral Products Co.,Ltd(Liaoning,China))获得,具有1250网格直径;
IRGANOXTM168和IRGANOXTM1010均是可从巴斯夫公司获得的抗氧化剂;以及
TINUVINTM622是可从巴斯夫公司获得的UV稳定剂。
根据下表1中的配制品(以重量%提供)制备九种发泡组合物比较实施例A-E和实施例1-4。
表1:
通过将一种或多种聚合物(DE 2400.05、ENGAGETM8200、INFUSETM9507和/或E/X/Y/Z-1)添加到Brabender混合器的350mL混合碗中并在150℃的温度下混合来制备比较实施例A-E和实施例1-4。在聚合物完全熔融之后,将剩余的成分添加到碗中并且再混合5分钟。将混合组合物在150℃下进一步压缩模制成厚度为0.5mm的薄片,用于发泡测试。
为了测量发泡性能,将烘箱温度设置为210℃,并从压缩模制薄片切割30*30mm2的测试样本。每个测试样本由防粘纸支撑。通过快速打开门、将样本插入烘箱中并立即关闭烘箱的门来将样本放入烘箱中。启动定时器,并在180秒后将样本从烘箱中取出。
在发泡之后并在使样品经受老化之前,对每个测试样本的泡沫泡孔进行表征。为了表征泡沫泡孔,用刀片切割样品,将其安装在样品架上并用Emitech K575X涂覆机用Ir涂覆。将电流设置为20mA,并且将涂覆时间设置为60秒。在Nova 630SEM中对涂覆的样品进行成像,并使用Nova Nano630SEM使用ETD检测器在5KV的加速电压、5”的斑点尺寸和约12mm的工作距离下检查样品的形态。在表2中将在老化之前泡沫和平均泡沫泡孔大小的厚度报告为“初始”值。发泡后SEM的图像示出于图1A-1E(分别为比较实施例A-E)和图2A-2D(分别为实施例1-4)中。
表2:
然后将来自比较实施例B-E和实施例1-4的样品置于不同温度下的烘箱中2小时,以测试耐热性。特别地,在80℃、125℃和150℃下测试耐热性,并且根据上述方法再次对泡沫泡孔进行表征。结果报告于表2中。在图1F-1I(分别为比较实施例B-E)和图1F-1I(分别为实施例1-4)中示出了在老化后的SEM图像。
如表2和图1A所示,比较实施例A包含丙烯/乙烯共聚物不含E/X/Y/Z型含环氧基的乙烯互聚物,不能良好发泡并且泡沫泡孔塌陷。
比较实施例B包含不含E/X/Y/Z型含环氧基的乙烯互聚物的均匀支化的基本上直链的乙烯/α-烯烃聚合物。在80℃下老化2小时后,最初存在的泡沫泡孔(图1B)消失,如图1F所示,并且观察到厚度的明显收缩(816mm到500mm)。不受理论的束缚,据信这是因为老化温度(80℃)高于聚合物的熔点(约60℃),并且聚合物在老化过程中熔融。
比较实施例C、D和E在125℃下老化2小时。如图1G(比较实施例C)、1H(比较实施例D)和比较实施例1I(比较实施例E)中所示,最初在图1C(比较实施例C)、1D(比较实施例D)和1E(比较实施例E)中出现的泡沫泡孔消失了。还观察到这些泡沫的厚度的收缩。与比较实施例A相比,据信这是因为老化温度(125℃)大于构成在比较实施例C中的聚合物和比较实施例E中的大部分聚合物的INFUSETMOBC(120℃)的熔点。比较实施例D包括比较实施例A的均匀支化的基本上直链的乙烯/α-烯烃聚合物作为主要组分。两种比较实施例D和E均包括少量的E/X/Y/Z型含环氧基的乙烯互聚物,但其不以足够大以防止泡沫泡孔塌陷的量存在。
然而,实施例1-4包含较高负载量(35%和50%)的E/X/Y/Z型含环氧基的乙烯互聚物,并且证明了泡沫厚度和泡沫泡孔结构的良好保留,这表明配制品的耐热性改善。通过分别将图2E(实施例1)、2F(实施例2)、2G(实施例3)和2H(实施例4)与图2A(实施例1)、2B(实施例2)、2C(实施例3)和2D(实施例4)中初始泡沫泡孔结构的SEM图像进行比较,可以看到在150℃下老化2小时后保持的泡沫泡孔结构。
因此,本文的各种实施方案提供了表现出改善的耐热性(特别是超过150℃)的交联泡沫。各种实施方案的交联泡沫包括乙烯/α-烯烃共聚物、反应性环氧基团官能化互聚物、化学发泡剂(诸如AZO发泡剂)和活化剂。特别地,含环氧基的乙烯互聚物是通过使互聚物中的甲基丙烯酸缩水甘油酯和由发泡剂的分解形成的偶氮或含氮基团反应而产生的交联的含环氧基的乙烯互聚物。不受理论限制,泡沫的交联通过抵抗在较高温度下的泡沫塌陷来提供改进的稳定性。
还应注意,本文中不使用如“一般地”、“通常地”和“典型地”的术语来限制所要求保护的发明的范围或暗示某些特征对于所要求保护的发明的结构或功能是关键的、必要的或甚至至关重要的。相反,这些术语仅旨在突出在本公开特定实施方案中可利用或可不利用的替代或附加特征。
显而易见,在不脱离随附权利要求书中所定义的本公开案的范围的情况下的修改和变化为有可能的。更具体地说,尽管本公开的一些方面在本文中被标识为优选的或特别有利的,但经考虑本公开不必限于这些方面。
Claims (14)
1.一种由组合物形成的泡沫,其中所述组合物包含:
按所述组合物计,至少50重量%的密度为0.840g/cc至0.910g/cc并且溶体指数(I2)为0.5g/10min至12.0g/10min的乙烯/α-烯烃共聚物、密度为0.860g/cc至0.890g/cc并且溶体指数(I2)为0.5g/10min至12.0g/10min的烯烃嵌段共聚物或它们的共混物;
按所述组合物计,30重量%至50重量%的E/X/Y/Z型含环氧基的乙烯互聚物,其中E是乙烯单体并且占所述互聚物的大于50重量%,X是(甲基)丙烯酸酯、(甲基)丙烯酸烷基酯或乙酸乙烯酯并且占所述互聚物的0重量%至40重量%,Y是甲基丙烯酸缩水甘油酯并且占所述互聚物的0.5重量%至13重量%,并且Z是衍生自选自由一氧化碳、二氧化硫和丙烯腈组成的组的共聚单体的共聚物单元并且占所述互聚物的0重量%至10重量%,其中所述重量%是基于可聚合单体的总量;
按所述组合物计,0.5重量%至5重量%的化学发泡剂;
按所述组合物计,0.1重量%至1重量%的活化剂;以及
按所述组合物计,小于0.05重量%的固化剂。
2.根据权利要求1所述的泡沫,其中X占所述互聚物的1重量%至40重量%。
3.根据任一前述权利要求所述的泡沫,其中所述化学发泡剂分解以释放一种或多种偶氮或含氮化合物。
4.根据权利要求3所述的泡沫,其中所述含环氧基的乙烯互聚物是通过使所述甲基丙烯酸缩水甘油酯和由所述化学发泡剂释放的所述一种或多种偶氮或含氮化合物发生反应来产生的交联的含环氧基的乙烯互聚物。
5.根据任一前述权利要求所述的泡沫,其中所述化学发泡剂是偶氮二甲酰胺。
6.根据任一前述权利要求所述的泡沫,其中所述活化剂是金属硬脂酸盐。
7.根据权利要求6所述的泡沫,其中所述金属硬脂酸盐是硬脂酸锌。
8.根据任一前述权利要求所述的泡沫,其中所述乙烯/α-烯烃共聚物、所述烯烃嵌段共聚物或两者均为乙烯和C4-C8烯烃共聚单体的共聚物。
9.根据权利要求8所述的泡沫,其中所述C4-C8α-烯烃共聚单体为辛烯。
10.根据任一前述权利要求所述的泡沫,其中所述乙烯/α-烯烃共聚物、所述烯烃嵌段共聚物或两者的密度为0.860g/cc至0.890g/cc。
11.根据任一前述权利要求所述的泡沫,其中所述乙烯/α-烯烃共聚物、所述烯烃嵌段共聚物或两者的熔体指数(I2)为3.0g/10min至7.0g/10min。
12.根据任一前述权利要求所述的泡沫,其中所述组合物不含过氧化物。
13.根据任一前述权利要求所述的泡沫,其中所述组合物还包含至少一种矿物油。
14.一种人造皮革,所述人造皮革包括两层或更多层,其中一层是根据任一前述权利要求所述的泡沫。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2019127943 | 2019-12-24 | ||
CNPCT/CN2019/127943 | 2019-12-24 | ||
PCT/US2020/066293 WO2021133702A1 (en) | 2019-12-24 | 2020-12-21 | Cross-linked polyolefin elastomer foams |
Publications (1)
Publication Number | Publication Date |
---|---|
CN114846071A true CN114846071A (zh) | 2022-08-02 |
Family
ID=74191920
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202080088754.0A Pending CN114846071A (zh) | 2019-12-24 | 2020-12-21 | 交联聚烯烃弹性体泡沫 |
Country Status (7)
Country | Link |
---|---|
US (1) | US20230039470A1 (zh) |
EP (1) | EP4081589B1 (zh) |
JP (1) | JP2023508977A (zh) |
KR (1) | KR20220122674A (zh) |
CN (1) | CN114846071A (zh) |
BR (1) | BR112022012458A2 (zh) |
WO (1) | WO2021133702A1 (zh) |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4968747A (en) * | 1990-03-30 | 1990-11-06 | Arco Chemical Technology, Inc. | Compatibilized blends of crystalline propylene polymers and styrenic copolymers |
CN1447837A (zh) * | 2000-07-20 | 2003-10-08 | 陶氏环球技术公司 | 由烯基芳族聚合物和α-烯烃/乙烯基或亚乙烯基芳族共聚体的共混物得到的泡沫组合物 |
WO2004104087A2 (en) * | 2003-05-23 | 2004-12-02 | Du Pont-Mitsui Polychemicals Co., Ltd. | Polymer composition, process for producing the polymer composition, and molded articles for automobile exterior trim |
CN1852944A (zh) * | 2003-05-23 | 2006-10-25 | 三井-杜邦聚合化学株式会社 | 聚合物组合物及其制备方法,和汽车外部装饰用的模塑制品 |
CN1997693A (zh) * | 2004-06-21 | 2007-07-11 | 纳幕尔杜邦公司 | 聚烯烃泡沫材料及其应用 |
CN101443392A (zh) * | 2006-04-06 | 2009-05-27 | 陶氏环球技术公司 | 粘合改性的可膨胀聚烯烃组合物和含有膨胀的粘合改性聚烯烃组合物的隔绝车辆部件 |
CN109689751A (zh) * | 2016-09-30 | 2019-04-26 | Sika技术股份公司 | 具有伴随着膨胀和固化的热塑性泡沫 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4540753A (en) | 1983-06-15 | 1985-09-10 | Exxon Research & Engineering Co. | Narrow MWD alpha-olefin copolymers |
US5783638A (en) | 1991-10-15 | 1998-07-21 | The Dow Chemical Company | Elastic substantially linear ethylene polymers |
US7608668B2 (en) | 2004-03-17 | 2009-10-27 | Dow Global Technologies Inc. | Ethylene/α-olefins block interpolymers |
EP1951511B1 (en) | 2005-10-26 | 2018-09-12 | Dow Global Technologies LLC | Multi-layer, elastic articles |
-
2020
- 2020-12-21 KR KR1020227024989A patent/KR20220122674A/ko active Search and Examination
- 2020-12-21 US US17/788,134 patent/US20230039470A1/en active Pending
- 2020-12-21 WO PCT/US2020/066293 patent/WO2021133702A1/en unknown
- 2020-12-21 JP JP2022539051A patent/JP2023508977A/ja active Pending
- 2020-12-21 EP EP20842834.2A patent/EP4081589B1/en active Active
- 2020-12-21 BR BR112022012458A patent/BR112022012458A2/pt unknown
- 2020-12-21 CN CN202080088754.0A patent/CN114846071A/zh active Pending
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4968747A (en) * | 1990-03-30 | 1990-11-06 | Arco Chemical Technology, Inc. | Compatibilized blends of crystalline propylene polymers and styrenic copolymers |
CN1447837A (zh) * | 2000-07-20 | 2003-10-08 | 陶氏环球技术公司 | 由烯基芳族聚合物和α-烯烃/乙烯基或亚乙烯基芳族共聚体的共混物得到的泡沫组合物 |
WO2004104087A2 (en) * | 2003-05-23 | 2004-12-02 | Du Pont-Mitsui Polychemicals Co., Ltd. | Polymer composition, process for producing the polymer composition, and molded articles for automobile exterior trim |
CN1852944A (zh) * | 2003-05-23 | 2006-10-25 | 三井-杜邦聚合化学株式会社 | 聚合物组合物及其制备方法,和汽车外部装饰用的模塑制品 |
CN1997693A (zh) * | 2004-06-21 | 2007-07-11 | 纳幕尔杜邦公司 | 聚烯烃泡沫材料及其应用 |
CN101443392A (zh) * | 2006-04-06 | 2009-05-27 | 陶氏环球技术公司 | 粘合改性的可膨胀聚烯烃组合物和含有膨胀的粘合改性聚烯烃组合物的隔绝车辆部件 |
CN109689751A (zh) * | 2016-09-30 | 2019-04-26 | Sika技术股份公司 | 具有伴随着膨胀和固化的热塑性泡沫 |
Non-Patent Citations (2)
Title |
---|
KIM, JW: "Preparation and physical properties of rubber-modified epoxy resin using poly(urethane acrylate)/poly(glycidyl methacrylate-co-acrylonitrile) core-shell composite particles", JOURNAL OF APPLIED POLYMER SCIENCE, vol. 63, no. 12, pages 1589 - 1600 * |
陈挺;张广成;刘铁民;陈芳;陶利群;: "丙烯腈/甲基丙烯酸共聚物泡沫塑料的制备与表征", 中国塑料, no. 03, pages 70 - 74 * |
Also Published As
Publication number | Publication date |
---|---|
KR20220122674A (ko) | 2022-09-02 |
US20230039470A1 (en) | 2023-02-09 |
EP4081589B1 (en) | 2023-12-27 |
WO2021133702A1 (en) | 2021-07-01 |
JP2023508977A (ja) | 2023-03-06 |
BR112022012458A2 (pt) | 2023-03-14 |
EP4081589A1 (en) | 2022-11-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR102048446B1 (ko) | 에틸렌-기재 중합체 조성물 및 발포체 | |
KR20110065547A (ko) | 내마모성 발포체를 위한 조성물 및 그의 제조 방법 | |
KR20050034605A (ko) | 폴리올레핀 분말, 이의 제조 및 사용 방법, 및 이로부터제조된 슬러시 성형품 | |
CN108884257A (zh) | 交联聚烯烃系树脂发泡体及使用其的成型体 | |
JPH08277339A (ja) | ポリオレフィン系電子線架橋発泡体 | |
EP4081589B1 (en) | Cross-linked polyolefin elastomer foams | |
US11407875B2 (en) | Process for producing foam beads using a modified ethylene-based polymer | |
EP2346936A1 (en) | Highly filled, propylene-ethylene copolymer compositions | |
WO2020056678A1 (en) | Bonding method to attach ethylene-based polymer foam with vulcanized rubber | |
JP4254434B2 (ja) | 発泡体成形用エチレン・α−オレフィン・非共役ジエン共重合ゴム組成物及びそれよりなる過酸化物架橋発泡体 | |
JP3012277B2 (ja) | 部分架橋熱可塑性エラストマー発泡体およびその製造方法 | |
JP2665373B2 (ja) | 部分架橋熱可塑性エラストマー発泡体およびその製造方法 | |
CN116600673A (zh) | 鞋中底 | |
US20220332913A1 (en) | Silane Crosslinked Ethylene/a-Olefin Block Copolymer Bead Foam | |
JPH07173317A (ja) | 成形性に優れたポリプロピレン系電子線架橋発泡体 | |
JP2005220303A (ja) | 発泡体成形用ポリプロピレン系樹脂組成物及びそれよりなる過酸化物架橋発泡体 | |
JP7377047B2 (ja) | ポリオレフィン系樹脂発泡体シート、及びその製造方法 | |
JP3186800B2 (ja) | 発泡性ポリオレフィン系樹脂組成物 | |
TW200848454A (en) | Functionalized, crosslinked polyolefin foams and methods for making the same | |
WO2021127983A1 (en) | Cross-linked epoxy-containing ethylene interpolymer foams | |
JP3139789B2 (ja) | ポリオレフィン系発泡性樹脂組成物および架橋ポリオレフィン系樹脂発泡体 | |
EP3807366A1 (en) | Flame retardant composition | |
KR20220165263A (ko) | 중합체 조성물 및 중합체 조성물을 포함하는 발포체 | |
JPH04248847A (ja) | 発泡性ポリオレフィン系樹脂組成物 | |
JP2001098099A (ja) | ポリエチレン系架橋発泡体 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination |