WO2014181991A1 - Method for preparing ethylene-vinyl acetate with low melt index - Google Patents
Method for preparing ethylene-vinyl acetate with low melt index Download PDFInfo
- Publication number
- WO2014181991A1 WO2014181991A1 PCT/KR2014/003731 KR2014003731W WO2014181991A1 WO 2014181991 A1 WO2014181991 A1 WO 2014181991A1 KR 2014003731 W KR2014003731 W KR 2014003731W WO 2014181991 A1 WO2014181991 A1 WO 2014181991A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- vinyl acetate
- ethylene
- resin composition
- acetate resin
- melt index
- Prior art date
Links
- 239000005038 ethylene vinyl acetate Substances 0.000 title claims abstract description 147
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 title claims abstract description 144
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000010894 electron beam technology Methods 0.000 claims abstract description 57
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000011342 resin composition Substances 0.000 claims abstract description 36
- 239000000155 melt Substances 0.000 claims abstract description 28
- 229920005989 resin Polymers 0.000 claims abstract description 14
- 239000011347 resin Substances 0.000 claims abstract description 14
- 238000012856 packing Methods 0.000 claims description 26
- 239000003963 antioxidant agent Substances 0.000 claims description 17
- 230000003078 antioxidant effect Effects 0.000 claims description 17
- -1 polypropylene Polymers 0.000 claims description 12
- 238000009826 distribution Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000002981 blocking agent Substances 0.000 claims description 8
- 229920001903 high density polyethylene Polymers 0.000 claims description 8
- 239000004700 high-density polyethylene Substances 0.000 claims description 8
- 229920001684 low density polyethylene Polymers 0.000 claims description 8
- 239000004702 low-density polyethylene Substances 0.000 claims description 8
- 229940099514 low-density polyethylene Drugs 0.000 claims description 8
- 239000012963 UV stabilizer Substances 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- 229920000034 Plastomer Polymers 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 6
- 229920001971 elastomer Polymers 0.000 claims description 6
- 239000000806 elastomer Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- 229920001155 polypropylene Polymers 0.000 claims description 6
- 229920000098 polyolefin Polymers 0.000 claims description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 4
- 229920001169 thermoplastic Polymers 0.000 claims description 4
- 239000004416 thermosoftening plastic Substances 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- 238000003892 spreading Methods 0.000 claims description 3
- 230000007480 spreading Effects 0.000 claims description 3
- 239000004712 Metallocene polyethylene (PE-MC) Substances 0.000 claims description 2
- 229920010346 Very Low Density Polyethylene (VLDPE) Polymers 0.000 claims description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 claims description 2
- 229920001038 ethylene copolymer Polymers 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- 125000005397 methacrylic acid ester group Chemical group 0.000 claims description 2
- 239000012748 slip agent Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims 1
- 150000001991 dicarboxylic acids Chemical class 0.000 claims 1
- 239000002952 polymeric resin Substances 0.000 claims 1
- 229920003002 synthetic resin Polymers 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 14
- 238000012986 modification Methods 0.000 description 13
- 230000004048 modification Effects 0.000 description 13
- 150000002978 peroxides Chemical class 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 238000001125 extrusion Methods 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 7
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical class N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 241001643597 Evas Species 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 238000010097 foam moulding Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000002715 modification method Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 238000012857 repacking Methods 0.000 description 3
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000012796 inorganic flame retardant Substances 0.000 description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 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
- 238000012545 processing Methods 0.000 description 2
- ILUAAIDVFMVTAU-OLQVQODUSA-N (1s,2r)-cyclohex-4-ene-1,2-dicarboxylic acid Chemical compound OC(=O)[C@H]1CC=CC[C@H]1C(O)=O ILUAAIDVFMVTAU-OLQVQODUSA-N 0.000 description 1
- OXDXXMDEEFOVHR-CLFAGFIQSA-N (z)-n-[2-[[(z)-octadec-9-enoyl]amino]ethyl]octadec-9-enamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)NCCNC(=O)CCCCCCC\C=C/CCCCCCCC OXDXXMDEEFOVHR-CLFAGFIQSA-N 0.000 description 1
- IGSAVPVCQHAPSM-UHFFFAOYSA-N 1,2-dichloro-4,5-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC(Cl)=C(Cl)C=C1[N+]([O-])=O IGSAVPVCQHAPSM-UHFFFAOYSA-N 0.000 description 1
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- GDOBGDUGIFUCJV-UHFFFAOYSA-N 2,2-dimethylbutane;2-methylprop-2-enoic acid Chemical compound CCC(C)(C)C.CC(=C)C(O)=O.CC(=C)C(O)=O.CC(=C)C(O)=O GDOBGDUGIFUCJV-UHFFFAOYSA-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
- 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
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 1
- FEUFEGJTJIHPOF-UHFFFAOYSA-N 2-butyl acrylic acid Chemical compound CCCCC(=C)C(O)=O FEUFEGJTJIHPOF-UHFFFAOYSA-N 0.000 description 1
- KRDXTHSSNCTAGY-UHFFFAOYSA-N 2-cyclohexylpyrrolidine Chemical compound C1CCNC1C1CCCCC1 KRDXTHSSNCTAGY-UHFFFAOYSA-N 0.000 description 1
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 description 1
- JJYWRQLLQAKNAD-UHFFFAOYSA-N 2-methylpent-2-enoic acid Chemical compound CCC=C(C)C(O)=O JJYWRQLLQAKNAD-UHFFFAOYSA-N 0.000 description 1
- HXIQYSLFEXIOAV-UHFFFAOYSA-N 2-tert-butyl-4-(5-tert-butyl-4-hydroxy-2-methylphenyl)sulfanyl-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1SC1=CC(C(C)(C)C)=C(O)C=C1C HXIQYSLFEXIOAV-UHFFFAOYSA-N 0.000 description 1
- HCILJBJJZALOAL-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)-n'-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyl]propanehydrazide Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 HCILJBJJZALOAL-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- DFGKGUXTPFWHIX-UHFFFAOYSA-N 6-[2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]acetyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)C1=CC2=C(NC(O2)=O)C=C1 DFGKGUXTPFWHIX-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- UIERETOOQGIECD-UHFFFAOYSA-N Angelic acid Natural products CC=C(C)C(O)=O UIERETOOQGIECD-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 description 1
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 description 1
- BGHBLQKNCVRIKV-UHFFFAOYSA-N OP(O)OP(O)O.OCC(CO)(CO)CO.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)O Chemical compound OP(O)OP(O)O.OCC(CO)(CO)CO.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)O BGHBLQKNCVRIKV-UHFFFAOYSA-N 0.000 description 1
- 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 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- 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 1
- FSMUEPJYPIBVIN-UHFFFAOYSA-H [Sb+3].[OH-].[Al+3].[OH-].[OH-].[OH-].[OH-].[OH-] Chemical compound [Sb+3].[OH-].[Al+3].[OH-].[OH-].[OH-].[OH-].[OH-] FSMUEPJYPIBVIN-UHFFFAOYSA-H 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 1
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical compound OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 description 1
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- 238000007796 conventional method Methods 0.000 description 1
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- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
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- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 210000003411 telomere Anatomy 0.000 description 1
- 102000055501 telomere Human genes 0.000 description 1
- 108091035539 telomere Proteins 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- UIERETOOQGIECD-ONEGZZNKSA-N tiglic acid Chemical compound C\C=C(/C)C(O)=O UIERETOOQGIECD-ONEGZZNKSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/50—Partial depolymerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
-
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/123—Treatment by wave energy or particle radiation
-
- 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
Definitions
- the present invention relates to a method for preparing an ethylene-vinyl acetate with a low melt index, and more particularly, to a method for preparing an ethylene-vinyl acetate with a low melt index that includes a simple process of modifying ethylene-vinyl acetate to prepare an ethylene-vinyl acetate having a high vinyl acetate content to acquire good properties with regard to transparency, elasticity, or the like, and consequently has high processability and good mechanical properties to make it applicable to a variety of industrial uses, thereby improving productivity and economic feasibility.
- Ethylene-vinyl acetate is a thermoplastic resin that is applied to various industrial uses, such as footwear, adhesives, coatings, electric wires, flame retardant compounds, photovoltaic applications, and so forth.
- the ethylene-vinyl acetate with a vinyl acetate content of at least 18 wt% secures good elasticity, dispersability in inorganic additives, and high transparency, and has been thus increasingly used in many applications such as footwear foams, electric wires, flame retardant compounds, and photovoltaic encapsulation materials.
- ethylene-vinyl acetate In the field of footwear foams that particularly need to have high elasticity, low specific gravity, and high flexibility, the use of ethylene-vinyl acetate is essential in order to secure good properties such as high elasticity, low specific gravity, and high flexibility, as well as a competitive price. Further, the vinyl acetate content of the ethylene-vinyl acetate is on an increasing trend, since a higher vinyl acetate content results in more excellence in those properties.
- the content of a flame retardant is necessarily increased with a view to enhancing the flame resistance of flame retardant compounds.
- the content of the inorganic flame retardant such as magnesium hydroxide, aluminum hydroxide antimony trioxide, etc., has to be at least 40 %.
- the compatibility of ethylene-vinyl acetate with inorganic substances increases with an increasing vinyl acetate content, it is desirable to increase the vinyl acetate content in order to use a higher amount of the inorganic flame retardant.
- An ethylene-vinyl acetate sheet used as an encapsulation material for photovoltaic modules has increasing transparency with an increase in the vinyl acetate content, thereby securing higher module efficiency. For that reason, the vinyl acetate content is generally given as 26 % or greater.
- the ethylene-vinyl acetate can be prepared by adding ethylene and vinyl acetate at an appropriate mixing ratio into an autoclave or tubular reactor and conducting polymerization under high temperature and high pressure conditions.
- part of the vinyl acetate acts as a telomere to terminate the reaction, possibly lowering the molecular weight of the ethylene-vinyl acetate.
- the lower molecular weight of the ethylene-vinyl acetate leads to a higher melt index and lower melt strength.
- An ethylene-vinyl acetate with a vinyl acetate content of 33 wt%, for example, has a melt index of about 10 and melt strength of about 30 mN.
- the higher melt index as a result of increasing the vinyl acetate content can lead to deterioration in the mechanical properties and processability.
- the use of the conventional ethylene-vinyl acetate having a high vinyl acetate content can offer excellences in flexibility, elasticity, etc., but deterioration in mechanical properties and processability.
- An approach to overcoming the limitations of the ethylene-vinyl acetate involves conducting a post reaction of the prepared ethylene-vinyl acetate in a reactor to enhance the mechanical properties and processability of the ethylene-vinyl acetate.
- the modification method using peroxides which is a method primarily used for the post reaction, is an extrusion reaction process that involves adding an ethylene-vinyl acetate resin and peroxides to an extruder and then lowering the melt index and raising the melt strength.
- the modification method using peroxides can modify the ethylene- vinyl acetate in a manner of different combinations but results in many problems, including a great work loss, contamination, repacking, processing defects, etc.
- the present invention is to provide a method for preparing an ethylene-vinyl acetate with a low melt index that includes a simple modification process to prepare an ethylene-vinyl acetate having a high vinyl acetate content to acquire good properties with regard to transparency, elasticity, etc., consequently having high processability and good mechanical properties to make it applicable to a variety of industrial uses, thereby improving productivity and economic feasibility.
- a method for preparing an ethylene-vinyl acetate having a melt index of 10 g/lOmin or less includes: applying an electron beam with an exposure dose of 1 to 25 kGy to an ethylene-vinyl acetate resin composition including an ethylene-vinyl acetate resin having a vinyl acetate content of 15 to 50 wt%.
- a method for preparing an ethylene-vinyl acetate having a melt index of 10 g/10 min or less includes: applying an electron beam with an exposure dose of 1 to 25 kGy to an ethylene-vinyl acetate resin composition including an ethylene-vinyl acetate resin having a vinyl acetate content of 15 to 50 wt%.
- the inventors of the present invention studied the preparation of an ethylene- vinyl acetate having good properties with regard to transparency, flexibility, elasticity, etc. and good mechanical properties and processability, based on the fact that the ethylene-vinyl acetate with a high vinyl acetate content tends to have low melt strength and a high melt index, consequently having deterioration in mechanical properties and processability.
- an ethylene-vinyl acetate resin composition including an ethylene-vinyl acetate resin having a high vinyl acetate content results in preparation of an ethylene-vinyl acetate with a low melt index of 10 g/10 min or less, thereby completing the present invention.
- the above-described preparation method for ethylene-vinyl acetate causes less contamination or processing defects during the preparation process and considerably less work loss. Further, the preparation method according to one exemplary embodiment can skip the step of opening the package and repacking it, thereby preparing an ethylene-vinyl acetate with high vinyl acetate content and a low melt index in a simple and economically feasible way.
- the preparation method can produce an ethylene-vinyl acetate with excellent mechanical properties, with regard to melt strength, melt index, shear thinning index, molecular weight distribution, etc., that are improved only by employing a simple modification process that involves applying an electron beam with a defined exposure dose to an ethylene-vinyl acetate resin composition.
- the ethylene-vinyl acetate provided by the preparation method according to one exemplary embodiment of the present invention has high vinyl acetate content and a low melt index, making it applicable to film forming, extrusion molding, foam molding, etc., and shows a high shear thinning index to maintain its shape under low shear stress and also reduce extrusion load, power consumption, pressure, etc. under high shear stress, consequently with good mechanical properties and processability.
- the preparation method according to one exemplary embodiment of the present invention may further include, prior to the step of applying an electron beam, spreading the ethylene-vinyl acetate resin composition to a thickness of 1 to 16 cm on an auxiliary mold, or packing the ethylene-vinyl acetate resin composition in a packing bag.
- the ethylene-vinyl acetate resin composition is spread to a thickness of 1 to 16 cm on an auxiliary mold and then exposed to an electron beam with an exposure dose of 1 to 25 kGy; or the ethylene-vinyl acetate resin composition is packed in a packing paper and then exposed to an electron beams with an exposure dose of 1 to 25 kGy.
- the term "thickness" as used herein means the bottom-to-top height of the ethylene-vinyl acetate resin composition spread on the bottom of the auxiliary mold.
- the auxiliary mold may be any known mold generally used in the related art, including, for example, metal, paper, a polymer film, wood, plastic, etc.
- the packing paper may be any known material generally used in the related art without specific limitation, including, for example, a polyolefin film, woven yarn, paper, coated paper, paper with a liner film, fabric, etc.
- the polyolefin film may be prepared from, for example, low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), very low density polyethylene (VLDPE), high-density polyethylene (HDPE), polypropylene (PP), an ethylene-based elastomer, an ethylene-based plastomer, a propylene-based elastomer, a propylene-based plastomer, or mixtures thereof.
- LDPE low-density polyethylene
- LLDPE linear low-density polyethylene
- VLDPE very low density polyethylene
- HDPE high-density polyethylene
- PP polypropylene
- an ethylene-based elastomer an ethylene-based plastomer
- propylene-based elastomer a propylene-based elastomer
- propylene-based plastomer a propylene-based plastomer
- the step of applying an electron beam to the packing bag can be accomplished by positioning the packing bag on a conveyer in the form of a metal roll or a metal mold and passing the conveyer through an exposure region of an electron beam. As the irradiation of electron beams continues, the temperature of the metal roll or mold is raised to make the packing bag melt, with the contents flowing into the packing bag, or stuck on the conveyer. To avoid this problem, it is desirable to use a material formed from a principal material that is stable at a high temperature.
- the total weight of the packing bag is not specifically limited, but it may be 1000 kg or less for the sake of convenience in conveying.
- the packing bag may be conveyed by manpower or machinery. In this regard, the total weight of the packing bag may be limited depending on the type of conveyance.
- the term "the total weight of the bag” as used herein refers to the weight of the ethylene-vinyl acetate resin composition plus the weight of the packing bag.
- an ethylene-vinyl acetate resin composition having a weight of about 1000 kg or less, preferably about 500 to 600 kg or less, may be packed in a Flecon or Carton bag.
- the total weight of the packing bag may be about 50 kg or less, preferably about 5 to 50 kg, and more preferably about 10 to 40 kg.
- the auxiliary mold or the packing bag is not specifically limited in size and shape.
- the height is constant at 1 cm or greater, and the shape is designed to allow the ethylene-vinyl acetate resin composition spread to a predetermined thickness or be packed in.
- the preparation method for ethylene-vinyl acetate involves spreading the ethylene-vinyl acetate resin composition on an auxiliary mold or packing it in a packing bag and then applying an electron beam to the ethylene-vinyl acetate resin composition by passing the auxiliary mold or the packing bag through an electron beam exposure device, thereby improving the properties of the ethylene-vinyl acetate without a specific additional step such as wrapping or the use of a modifier such as peroxides. This enables it to prepare an ethylene-vinyl acetate in an easy and economically feasible way.
- the preparation method of the present invention causes much less work loss and improves the work rate to as high as at least 700 kg per hour.
- the ethylene-vinyl acetate resin composition is fed into an electron beam exposure device and exposed to an electron beam.
- the packing bag may be either stood upright or laid on the side, depending on the shape and position of the electron beam exposure device; preferably, the bag may be laid on the side to pass under the electron beam.
- the electron beam may be applied to the one side or both sides of the ethylene- vinyl acetate resin composition. It is preferable to apply the electron beam to one side of the ethylene-vinyl acetate resin composition when the ethylene-vinyl acetate resin composition is thin, or to both sides of the ethylene-vinyl acetate resin composition when the ethylene-vinyl acetate resin composition is thick.
- the exposure to the electron beam may be conducted on both sides or on the one side of the ethylene-vinyl acetate resin composition one or more times.
- the ethylene-vinyl acetate resin having a vinyl acetate content of 15 to 50 wt% may have Rheotens melt strength of 1 to 30 mN.
- the ethylene-vinyl acetate resin having a vinyl acetate content of 15 to 50 wt% may also have a melt index (190 °C, 2.16 kg) of at least 15 g/10 min, preferably at least 20 g/10 min.
- the ethylene-vinyl acetate resin has extremely low melt strength and an extremely high melt index, consequently having poor processability and formability, but it can be modified by exposure to the electron beam with a defined range of exposure dose to secure good properties.
- the ethylene-vinyl acetate (EVA) thus obtained may have a melt index (190 °C, 2.16 kg) of 10 g/10 min or less, preferably 0.01 to .5 g/10 min.
- a melt index of EVA preferably 0.01 to .5 g/10 min.
- the melt index of EVA is less than 0.01 g/ 10 min, it has such high strength in the melt state so as to greatly increase the extrusion torque and becomes hard to draw, which possibly increases the difficulty in performing foaming, film molding, sheet molding, compounding, etc.
- the melt index is relevant to the molecular weight.
- the vinyl acetate acts as a telomer (i.e., reaction terminator) to lower the molecular weight of the ethylene-vinyl acetate having a high vinyl acetate content and to increase the melt index.
- the ethylene-vinyl acetate obtained by the preparation method according to the exemplary embodiment of the present invention can have a low melt index of 10 g/10 min or less even with a high vinyl acetate content of 15 to 50 wt%. This can overcome the aforementioned limitation with regard to mechanical properties and processability.
- the ethylene-vinyl acetate thus obtained may have a Rheotens® melt strength (170 °C) of at least 30 mN, preferably 30 to 150 mN.
- the ethylene-vinyl acetate having a melt strength of less than 30 mN is poor in elasticity and strength in the melted state, hard of forming and growing bubbles during the foam molding process, thus making it impossible to sufficiently form a sponge, and poor in shape retentiveness at a high temperature during the injection/extrusion molding process, so it cannot be molded in a desired shape.
- the prepared ethylene-vinyl acetate thus may have an ARES (150 °C, 15 % strain) shear thinning index of 4 to 25.
- the shear thinning index is defined as the ratio of a viscosity at 1 rad/sec to a viscosity at 100 rad/sec. A higher shear thinning index indicates higher viscosity at a lower shear stress and a lower viscosity at a higher shear stress.
- the ethylene-vinyl acetate having an ARES shear thinning index within the above-defined range has such a high viscosity at a relatively low shear stress so as to maintain its shape without distortion and low viscosity at a relatively high shear stress, thereby reducing extrusion load and power consumption.
- the prepared ethylene-vinyl acetate may have a molecular weight distribution of at least 10, preferably 10 to 50.
- the molecular weight distribution in the defined range is considerably higher than the molecular weight distribution of the ethylene-vinyl acetate resin having a vinyl acetate content of 15 to 50 wt% before exposure to the electron beam. This demonstrates that the modification using exposure to the electron beam can lead to the production of an ethylene-vinyl acetate having a wide range of molecular weight distribution that secures appropriately high mechanical strength and processability.
- the ethylene-vinyl acetate resin composition may further include additives, such as a photoreactive monomer, an antioxidant, a slip agent, an anti-blocking agent, a UV stabilizer, a reaction auxiliary, or mixtures thereof.
- additives such as a photoreactive monomer, an antioxidant, a slip agent, an anti-blocking agent, a UV stabilizer, a reaction auxiliary, or mixtures thereof.
- the antioxidant can increase the thermal stability and oxidation stability of the prepared ethylene-vinyl acetate. More specifically, the antioxidant may be a phenol- based antioxidant, a non-phenol-based antioxidant, or a mixture thereof. Preferably, a non-phenol-based antioxidant is used with a view to reducing a drop of complex viscosity and shear thinning index and minimizing discoloration.
- the phenol-based antioxidant as used herein is a known antioxidant generally used in the related art without any limitation.
- Specific examples of the phenol-based antioxidant may include octadecyl-3-(3,5-di-tert.butyl-4-hydroxyphenyl)-propionate, butylated hydroxytoluene, pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate), 2', 3-bis [[3-[3, 5-di-tert-butyl-4-hydroxyphenyl]propionyl]] propionohydrazide, or mixtures thereof.
- the non-phenol-based antioxidant as used herein is a known antioxidant generally used in the related art without any limitation.
- Specific examples of the non- phenol-based antioxidant may include tris(2,4-ditert-butylphenyl)phosphite, 4,4'- thiobis(6-tert-butyl-m-cresol), bis-(2, 4-di-t-butylphenol) pentaerythritol diphosphite, 2- (tert-butyl)-6-methyl-4-(3-((2,4,8, 10-tetrakis(tert- butyl)dibenzo[d,fj[ l ,3,2]dioxaphosphepin-6-yl)oxy)propyl)phenol, bis(2,4-di-tert.- butyl-6-methylphenyl)-ethyl-phosphite, tris(nonylphenyl) phosphite, or mixtures thereof.
- the antioxidant may be used in an amount of 0.01 to 0.5 part by weight with respect to 100 parts by weight of the ethylene-vinyl acetate resin composition.
- An extremely low content of the antioxidant results in preparation of ethylene-vinyl acetate with poor oxidation stability, and an extremely high content of the antioxidant greatly deteriorates the efficiency of modification using electron beams and possibly causes discoloration of the ethylene-vinyl acetate.
- the ethylene-vinyl acetate resin composition may further include a UV stabilizer that not only maintains the thermal stability and oxidation stability of the prepared ethylene-vinyl acetate, but also prevents deterioration in the efficiency of modification using electron beams.
- the UV stabilizer as used herein is preferably a hindered amine-based UV stabilizer, as known to be generally used in the related art.
- the hindered amine-based UV stabilizer can excellently maintain the effect of modification of ethylene-vinyl acetate using electron beams and thus keep the low exposure dose of electron beams required to meet the desired properties. This allows it to prepare an ethylene-vinyl acetate with economic efficiency.
- UV stabilizer may include a polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl- l -piperidine ethanol, bis(2,2,6,6- tetramethyl-4-piperidinyl) sebacate, bis(l ,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, poly[6-[(l , l ,3,3-tetramethylbutyl)amino]- l ,3,5-triazine-2,4-dinyl][(2,2,6,6-tetramethyl- 4-piperidinyl)imino]hexamethylene[2,2,6,6-tetramethyl-4-piperidinyl)imino]], or mixtures thereof.
- the UV antioxidant may be contained in an amount of 0.01 to 0.5 part by weight with respect to 100 parts by weight of the ethylene-vinyl acetate resin composition.
- the anti-blocking agent as used herein may be a known compound generally used in the related art to control the viscosity of the ethylene-vinyl acetate pellets without any limitation.
- Specific examples of the anti-blocking agent may include oleamide, stearamide, erucamide, ethylene bis-stearamide, ethylene bis-oleamide, or mixtures thereof.
- the anti-blocking agent may be contained in an amount of 0.02 to 0.5 part by weight with respect to 100 parts by weight of the ethylene-vinyl acetate resin composition.
- An extremely high content of the anti-blocking agent possibly results in a change of color in the course of the modification process using electron beams, and an extremely low content of the anti-blocking agent causes the pellets to stick together. Therefore, the anti-blocking agent is preferably contained in the above- defined range of amount.
- the photoreactive monomer plays a role as an auxiliary for modification using electron beams that helps the modification process using electron beams to be accomplished with efficiency.
- Specific examples of the photoreactive monomer may include acrylic acid, acrylic acid esters, methacrylic acid, methacrylic acid esters, dicarboxylic acid with double bonds, dicarboxylic acid esters with double bonds, dicarboxylic acid anhydrides with double bonds, silane coupling agents, or mixtures thereof.
- the dicarboxylic acid may be maleic acid, phthalic acid, itaconic acid, citraconic acid, alkenyl succinic acid, cis- 1 ,2,3,6-tetrahydrophthalic acid, or 4-methyl- l ,2,3,6-tetrahydrophthalic acid;
- (meth)acrylic acid compound may be acrylic acid, methacrylic acid, vinyl acetic acid, vinyl acetate, methyl-acrylic acid, ethyl-acrylic acid, butyl-acrylic acid, methyl- methacrylic acid, ethyl-methacrylic acid, glycidyl acrylate, or glycidyl methacrylate; and the silane coupling agent may be vinyltrimethoxy silane, vinyltriethoxy silane, gamma-methacroxy propyltrimethoxy si lane, gamma-acroxy propyltrimethoxy silane, or acroxy methyltrimethoxy silane.
- the ethylene-vinyl acrylate resin composition can improve the efficiency of electron beam irradiation by containing the auxiliary for modification using electron beams. This allows it to prepare ethylene-vinyl acetate having polar groups introduced to enhance adhesiveness and improved mechanical properties with regard to melt strength or shear thinning index.
- the photoreactive monomer may be contained in an amount of 0.1 to 3 parts by weight with respect to 100 parts by weight of the ethylene- vinyl acetate resin composition.
- the reaction auxiliary as used herein may include a peroxide type of cross- linking agent and a cross-linking auxiliary.
- the peroxide cross- linking agent may include dicumyl peroxide, l , l-di-(tert-butyl peroxy)-3,3,5- trimethylcyclohexane, di-(2-tert-butyl-peroxyisopropyl)-benzene, butyl-4,4-bis(tert- butyldioxy)valerate, di-(2,4-dichlorobenzoyl)-peroxide, di-(2,4-dichlorobenzoyl)- peroxide, dibenzoyl peroxide, tert-butyl peroxybenzoate, tert-butylcumyl peroxide, 2,5- dimethyl-2,5-di-(tert-butylperoxy)-hexane, di-tert-butylperoxide, 2,5-dimethyl
- cross- linking auxiliary may include triethyleneglycol dimethacry!ate, tetraethylglycol dimethacrylate, trimethylpropane trimethacrylate, divinylbenzene, ethyleneglycol dimethacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, triacrylisocyanurate, or mixtures thereof.
- the ethylene-vinyl acetate resin composition may further include, in addition to the ethylene-vinyl acetate resin, an ethylene copolymer including an ethylene-vinyl acetate copolymer, metallocene polypropylene, metallocene polyethylene, Ziegler-Natta polyethylene, low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), high-density polyethylene (HDPE), thermoplastic polyethylene elastomer, thermoplastic polyethylene plastomer, or mixtures thereof.
- an ethylene copolymer including an ethylene-vinyl acetate copolymer, metallocene polypropylene, metallocene polyethylene, Ziegler-Natta polyethylene, low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), high-density polyethylene (HDPE), thermoplastic polyethylene elastomer, thermoplastic polyethylene plastomer, or mixtures thereof.
- FIG. 1 is a graph showing the molecular weight distribution as a function of the exposure dose of electron beams in Example 5.
- Electron beam energy of 2.5 MeV or 10 MeV is applied in the vertical direction with a scanning width up to 60 kW. Then the actual exposure dose of electron beam is measured as a function of the penetration depth based on the reference exposure dose for the electron beam energy of 25 KGy. The measurement results are presented in Table 1 .
- the maximum penetration depth is 3.2 cm at 2.5 MeV and 8 cm at 10 MeV. It is therefore demonstrated that the double-sided exposure of the electron beam can be achieved to a depth of 6.4 cm at 2.5 MeV and 16 cm at 10
- EVA ethylene-vinyl acetate
- VA vinyl acetate
- VA ethylene-vinyl acetate
- Table 2 An ethylene-vinyl acetate (EVA) with a melt index of 60 g/10 min (at 190 °C, 2.16 kg) and a vinyl acetate (VA) content of 40 %, and an EVA with a melt index of 30 g/10 min (at 190 °C, 2.16 kg) and a VA content of 33 %, are spread on a metal tray (100 cm x 100 cm x 10 cm) to a uniform thickness of 3 to 4 cm. Then, the melt index depending on the exposure dose of electron beam is measured. The measurement results are presented in Table 2.
- a 2.096 mm-diameter orifice is set into a cylinder of the melt index measurer at 190 °C, and the cylinder is filled with 4 to 5 g of EVA.
- a weight of 2.16 kg is put on the piston to impose a load on the EVA.
- the EVA in the cylinder is preheated for about 5 minutes and the amount of the EVA passing down the cylinder in one minute is measured. This amount of EVA is reduced to the amount of EVA passing down the cylinder for 10 minutes.
- EVA ethylene-vinyl acetate
- VA vinyl acetate
- VA ethylene-vinyl acetate
- an EVA with a melt index of 30 g/10 min (at 190 °C, 2.16 kg) and a VA content of 33 % are packed in a polyolefin packing bag primarily made of LLDPE to a thickness and a weight as given in Table 3. Then, the melt index of the EVA is measured.
- the thickness of the EVA composition is given as 12 cm after double-sided exposure on the EVA composition at 6.3 cm thick.
- the EVA with a VA content of 40 % is exposed to the electron beam with different exposure doses and then measured with regard to the melt strength (Rheotens®, 170 °C). The measurement results are presented in Table 4.
- the melt strength is measured with Rheotens 71 .97 equipment connected to a capillary rheometer.
- Ethylene-vinyl acetate is melted at 170 °C in a 15 mm-diameter capillary barrel for about 4 minutes, and the capillary at 32 mm long and 1.0 mm in diameter is passed by a piston descending at a rate of 3 mm per minute.
- the melted ethylene-vinyl acetate resin passing through the orifice is then passed between two wheels that are located 150 mm thereunder and that rotate in engagement with each other at an acceleration of 3 mm/s 2 .
- the EVA of Comparative Example 3-1 not exposed to the electron beam has a melt strength of only 4.2mN, which is not high enough to allow the EVA for the use in extrusion molding, injection molding, foam molding, etc.
- the EVAs of Examples 3- 1 , 3-2, and 3-3 exposed to the electron beam with exposure doses of 5 kGy, 10 kGy, or 15 kGy have a melt strength of at least 30 mN, which is high enough to make the EVAs available for film molding, extrusion molding, foam molding, etc.
- Example 4 Change of Shear Thinning Index of EVA Depending on Exposure Dose of Electron Beam
- the EVA with a VA content of 40 % is exposed to the electron beam and then measured with regard to the shear thinning index (ARES®, 170 °C, 15 % strain).
- the measurement results are presented in Table 5.
- the shear thinning index is defined as the ratio of viscosity at 1 rad/sec to viscosity at 100 rad/sec. A higher shear thinning index indicates higher viscosity at a lower shear stress and lower viscosity at a high shear stress.
- Shear thinning index (Viscosity at 1 rad/sec) / (Viscosity at 100 rad/sec) [Table 5]
- the EVA with a VA content of 40 % is exposed to the electron beam and then measured with regard to the molecular weight to calculate the molecular weight distribution.
- the measurement results are presented in Table 6 and FIG. 1.
- the molecular weight distribution is defined as the number average molecular weight with respect to the weight average molecular weight divided by the weight average molecular weight.
- the EVAs of Examples 5- 1 , 5-2, and 5-3 exposed to the electron beam show higher PDI values and wider molecular weight distributions, thereby securing appropriate mechanical strengths and processability.
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Abstract
The present invention relates to a method for preparing an ethylene-vinyl acetate (EVA) having a melt index of 10 g/10min or less that includes: applying an electron beam with an exposure dose of 1 to 25 kGy to an ethylene-vinyl acetate resin composition including an ethylene-vinyl acetate resin having a vinyl acetate content of 15 to 50 wt%. The ethylene-vinyl acetate prepared has a high vinyl acetate content to secure good properties with regard to transparency, elasticity, or the like, consequently having high processability and good mechanical properties such as a low melt index and thus can be applied to various industrial uses.
Description
[DESCRIPTION]
[INVENTION TITLE]
METHOD FOR PREPARING ETHYLENE-VINYL ACETATE WITH LOW MELT INDEX
[TECHNICAL FIELD ]
The present invention relates to a method for preparing an ethylene-vinyl acetate with a low melt index, and more particularly, to a method for preparing an ethylene-vinyl acetate with a low melt index that includes a simple process of modifying ethylene-vinyl acetate to prepare an ethylene-vinyl acetate having a high vinyl acetate content to acquire good properties with regard to transparency, elasticity, or the like, and consequently has high processability and good mechanical properties to make it applicable to a variety of industrial uses, thereby improving productivity and economic feasibility.
[BACKGROUND OF ART]
Ethylene-vinyl acetate is a thermoplastic resin that is applied to various industrial uses, such as footwear, adhesives, coatings, electric wires, flame retardant compounds, photovoltaic applications, and so forth. Particularly, the ethylene-vinyl acetate with a vinyl acetate content of at least 18 wt% secures good elasticity, dispersability in inorganic additives, and high transparency, and has been thus increasingly used in many applications such as footwear foams, electric wires, flame retardant compounds, and photovoltaic encapsulation materials.
In the field of footwear foams that particularly need to have high elasticity, low specific gravity, and high flexibility, the use of ethylene-vinyl acetate is essential in order to secure good properties such as high elasticity, low specific gravity, and high flexibility, as well as a competitive price. Further, the vinyl acetate content of the
ethylene-vinyl acetate is on an increasing trend, since a higher vinyl acetate content results in more excellence in those properties.
In addition, the content of a flame retardant is necessarily increased with a view to enhancing the flame resistance of flame retardant compounds. In order for the ethylene-vinyl acetate to have higher flame resistance, the content of the inorganic flame retardant, such as magnesium hydroxide, aluminum hydroxide antimony trioxide, etc., has to be at least 40 %. As the compatibility of ethylene-vinyl acetate with inorganic substances increases with an increasing vinyl acetate content, it is desirable to increase the vinyl acetate content in order to use a higher amount of the inorganic flame retardant.
An ethylene-vinyl acetate sheet used as an encapsulation material for photovoltaic modules has increasing transparency with an increase in the vinyl acetate content, thereby securing higher module efficiency. For that reason, the vinyl acetate content is generally given as 26 % or greater.
On the other hand, the ethylene-vinyl acetate can be prepared by adding ethylene and vinyl acetate at an appropriate mixing ratio into an autoclave or tubular reactor and conducting polymerization under high temperature and high pressure conditions. In this regard, when the amount of vinyl acetate added to the reactor increases, part of the vinyl acetate acts as a telomere to terminate the reaction, possibly lowering the molecular weight of the ethylene-vinyl acetate. The lower molecular weight of the ethylene-vinyl acetate leads to a higher melt index and lower melt strength. An ethylene-vinyl acetate with a vinyl acetate content of 33 wt%, for example, has a melt index of about 10 and melt strength of about 30 mN.
The higher melt index as a result of increasing the vinyl acetate content can lead to deterioration in the mechanical properties and processability. Hence, the use of the conventional ethylene-vinyl acetate having a high vinyl acetate content can offer excellences in flexibility, elasticity, etc., but deterioration in mechanical properties and processability. This imposes some limitations in using the ethylene-vinyl acetate alone for footwear foams, electric wires, flame retardant compounds, and so forth.
An approach to overcoming the limitations of the ethylene-vinyl acetate involves conducting a post reaction of the prepared ethylene-vinyl acetate in a reactor to enhance the mechanical properties and processability of the ethylene-vinyl acetate. The modification method using peroxides, which is a method primarily used for the post reaction, is an extrusion reaction process that involves adding an ethylene-vinyl acetate resin and peroxides to an extruder and then lowering the melt index and raising the melt strength. The modification method using peroxides can modify the ethylene- vinyl acetate in a manner of different combinations but results in many problems, including a great work loss, contamination, repacking, processing defects, etc.
Work loss and repacking caused by the modification process using peroxides are main factors of cost increases, which become limitations in commercialization of the ethylene-vinyl acetate. Further, the contaminants that are introduced or generated during the modification process may cause quality problems of the final ethylene-vinyl acetate product.
This means there still remains a need of developing a simple and economically feasible method for preparing an ethylene-vinyl acetate that has a high vinyl acetate content to acquire good properties with regard to transparency and elasticity and secures high melt strength and good mechanical properties through a simple process of post reaction, making it applicable to a wide range of industrial uses, such as footwear foams, adhesives, etc.
[ DETAILED DESCRIPTION OF THE INVENTION]
[Technical Problem]
Accordingly, the present invention is to provide a method for preparing an ethylene-vinyl acetate with a low melt index that includes a simple modification process to prepare an ethylene-vinyl acetate having a high vinyl acetate content to acquire good properties with regard to transparency, elasticity, etc., consequently having high processability and good mechanical properties to make it applicable to a variety of industrial uses, thereby improving productivity and economic feasibility.
[Technical Solution]
According to the present invention, a method for preparing an ethylene-vinyl acetate having a melt index of 10 g/lOmin or less is provided, that includes: applying an electron beam with an exposure dose of 1 to 25 kGy to an ethylene-vinyl acetate resin composition including an ethylene-vinyl acetate resin having a vinyl acetate content of 15 to 50 wt%.
Hereinafter, a further detailed description will be given as to a method for preparing an ethylene-vinyl acetate (EVA) having a low melt index according to exemplary embodiments of the present invention.
In accordance with one exemplary embodiment of the present invention, a method for preparing an ethylene-vinyl acetate having a melt index of 10 g/10 min or less is provided, that includes: applying an electron beam with an exposure dose of 1 to 25 kGy to an ethylene-vinyl acetate resin composition including an ethylene-vinyl acetate resin having a vinyl acetate content of 15 to 50 wt%.
The inventors of the present invention studied the preparation of an ethylene- vinyl acetate having good properties with regard to transparency, flexibility, elasticity, etc. and good mechanical properties and processability, based on the fact that the ethylene-vinyl acetate with a high vinyl acetate content tends to have low melt strength and a high melt index, consequently having deterioration in mechanical properties and processability. Subsequently, the inventors of the present invention found that irradiation of electron beams with a defined exposure dose to an ethylene-vinyl acetate resin composition including an ethylene-vinyl acetate resin having a high vinyl acetate content results in preparation of an ethylene-vinyl acetate with a low melt index of 10 g/10 min or less, thereby completing the present invention.
Particularly, compared to the conventional modification method using peroxides, the above-described preparation method for ethylene-vinyl acetate causes less contamination or processing defects during the preparation process and
considerably less work loss. Further, the preparation method according to one exemplary embodiment can skip the step of opening the package and repacking it, thereby preparing an ethylene-vinyl acetate with high vinyl acetate content and a low melt index in a simple and economically feasible way.
Furthermore, the preparation method can produce an ethylene-vinyl acetate with excellent mechanical properties, with regard to melt strength, melt index, shear thinning index, molecular weight distribution, etc., that are improved only by employing a simple modification process that involves applying an electron beam with a defined exposure dose to an ethylene-vinyl acetate resin composition.
Therefore, the ethylene-vinyl acetate provided by the preparation method according to one exemplary embodiment of the present invention has high vinyl acetate content and a low melt index, making it applicable to film forming, extrusion molding, foam molding, etc., and shows a high shear thinning index to maintain its shape under low shear stress and also reduce extrusion load, power consumption, pressure, etc. under high shear stress, consequently with good mechanical properties and processability.
On the other hand, the preparation method according to one exemplary embodiment of the present invention may further include, prior to the step of applying an electron beam, spreading the ethylene-vinyl acetate resin composition to a thickness of 1 to 16 cm on an auxiliary mold, or packing the ethylene-vinyl acetate resin composition in a packing bag.
In other words, the ethylene-vinyl acetate resin composition is spread to a thickness of 1 to 16 cm on an auxiliary mold and then exposed to an electron beam with an exposure dose of 1 to 25 kGy; or the ethylene-vinyl acetate resin composition is packed in a packing paper and then exposed to an electron beams with an exposure dose of 1 to 25 kGy. The term "thickness" as used herein means the bottom-to-top height of the ethylene-vinyl acetate resin composition spread on the bottom of the auxiliary mold.
The auxiliary mold may be any known mold generally used in the related art, including, for example, metal, paper, a polymer film, wood, plastic, etc.
The packing paper may be any known material generally used in the related art without specific limitation, including, for example, a polyolefin film, woven yarn, paper, coated paper, paper with a liner film, fabric, etc.
The polyolefin film may be prepared from, for example, low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), very low density polyethylene (VLDPE), high-density polyethylene (HDPE), polypropylene (PP), an ethylene-based elastomer, an ethylene-based plastomer, a propylene-based elastomer, a propylene-based plastomer, or mixtures thereof.
On the other hand, the step of applying an electron beam to the packing bag can be accomplished by positioning the packing bag on a conveyer in the form of a metal roll or a metal mold and passing the conveyer through an exposure region of an electron beam. As the irradiation of electron beams continues, the temperature of the metal roll or mold is raised to make the packing bag melt, with the contents flowing into the packing bag, or stuck on the conveyer. To avoid this problem, it is desirable to use a material formed from a principal material that is stable at a high temperature.
The total weight of the packing bag is not specifically limited, but it may be 1000 kg or less for the sake of convenience in conveying. The packing bag may be conveyed by manpower or machinery. In this regard, the total weight of the packing bag may be limited depending on the type of conveyance. The term "the total weight of the bag" as used herein refers to the weight of the ethylene-vinyl acetate resin composition plus the weight of the packing bag. In the case of conveying a packing bag with machinery, an ethylene-vinyl acetate resin composition having a weight of about 1000 kg or less, preferably about 500 to 600 kg or less, may be packed in a Flecon or Carton bag. When conveying a packing bag with manpower, the total weight of the packing bag may be about 50 kg or less, preferably about 5 to 50 kg, and more preferably about 10 to 40 kg.
The auxiliary mold or the packing bag is not specifically limited in size and shape. Preferably, the height is constant at 1 cm or greater, and the shape is designed to allow the ethylene-vinyl acetate resin composition spread to a predetermined thickness or be packed in.
The preparation method for ethylene-vinyl acetate according to one exemplary embodiment of the present invention involves spreading the ethylene-vinyl acetate resin composition on an auxiliary mold or packing it in a packing bag and then applying an electron beam to the ethylene-vinyl acetate resin composition by passing the auxiliary mold or the packing bag through an electron beam exposure device, thereby improving the properties of the ethylene-vinyl acetate without a specific additional step such as wrapping or the use of a modifier such as peroxides. This enables it to prepare an ethylene-vinyl acetate in an easy and economically feasible way.
Particularly, compared to the conventional method for preparing an ethylene- vinyl acetate using peroxides, the preparation method of the present invention causes much less work loss and improves the work rate to as high as at least 700 kg per hour.
The ethylene-vinyl acetate resin composition is fed into an electron beam exposure device and exposed to an electron beam. In the case that the ethylene-vinyl acetate resin composition packed in a packing bag is exposed to an electron beam, the packing bag may be either stood upright or laid on the side, depending on the shape and position of the electron beam exposure device; preferably, the bag may be laid on the side to pass under the electron beam.
The electron beam may be applied to the one side or both sides of the ethylene- vinyl acetate resin composition. It is preferable to apply the electron beam to one side of the ethylene-vinyl acetate resin composition when the ethylene-vinyl acetate resin composition is thin, or to both sides of the ethylene-vinyl acetate resin composition when the ethylene-vinyl acetate resin composition is thick. The exposure to the electron beam may be conducted on both sides or on the one side of the ethylene-vinyl acetate resin composition one or more times.
The ethylene-vinyl acetate resin having a vinyl acetate content of 15 to 50 wt% may have Rheotens melt strength of 1 to 30 mN. The ethylene-vinyl acetate resin having a vinyl acetate content of 15 to 50 wt% may also have a melt index (190 °C, 2.16 kg) of at least 15 g/10 min, preferably at least 20 g/10 min. The ethylene-vinyl acetate resin has extremely low melt strength and an extremely high melt index, consequently having poor processability and formability, but it can be modified by exposure to the electron beam with a defined range of exposure dose to secure good properties.
The ethylene-vinyl acetate (EVA) thus obtained may have a melt index (190 °C, 2.16 kg) of 10 g/10 min or less, preferably 0.01 to .5 g/10 min. Particularly, when the melt index of EVA is less than 0.01 g/ 10 min, it has such high strength in the melt state so as to greatly increase the extrusion torque and becomes hard to draw, which possibly increases the difficulty in performing foaming, film molding, sheet molding, compounding, etc.
The melt index is relevant to the molecular weight. Hence, the vinyl acetate acts as a telomer (i.e., reaction terminator) to lower the molecular weight of the ethylene-vinyl acetate having a high vinyl acetate content and to increase the melt index. This may lead to deterioration in mechanical properties and processability. Contrarily, the ethylene-vinyl acetate obtained by the preparation method according to the exemplary embodiment of the present invention can have a low melt index of 10 g/10 min or less even with a high vinyl acetate content of 15 to 50 wt%. This can overcome the aforementioned limitation with regard to mechanical properties and processability.
The ethylene-vinyl acetate thus obtained may have a Rheotens® melt strength (170 °C) of at least 30 mN, preferably 30 to 150 mN. The ethylene-vinyl acetate having a melt strength of less than 30 mN is poor in elasticity and strength in the melted state, hard of forming and growing bubbles during the foam molding process, thus making it impossible to sufficiently form a sponge, and poor in shape retentiveness at a high temperature during the injection/extrusion molding process, so it cannot be molded in a desired shape.
In addition, the prepared ethylene-vinyl acetate thus may have an ARES (150 °C, 15 % strain) shear thinning index of 4 to 25. The shear thinning index is defined as the ratio of a viscosity at 1 rad/sec to a viscosity at 100 rad/sec. A higher shear thinning index indicates higher viscosity at a lower shear stress and a lower viscosity at a higher shear stress. The ethylene-vinyl acetate having an ARES shear thinning index within the above-defined range has such a high viscosity at a relatively low shear stress so as to maintain its shape without distortion and low viscosity at a relatively high shear stress, thereby reducing extrusion load and power consumption.
Further, the prepared ethylene-vinyl acetate may have a molecular weight distribution of at least 10, preferably 10 to 50. The molecular weight distribution in the defined range is considerably higher than the molecular weight distribution of the ethylene-vinyl acetate resin having a vinyl acetate content of 15 to 50 wt% before exposure to the electron beam. This demonstrates that the modification using exposure to the electron beam can lead to the production of an ethylene-vinyl acetate having a wide range of molecular weight distribution that secures appropriately high mechanical strength and processability.
On the other hand, the ethylene-vinyl acetate resin composition may further include additives, such as a photoreactive monomer, an antioxidant, a slip agent, an anti-blocking agent, a UV stabilizer, a reaction auxiliary, or mixtures thereof.
The antioxidant can increase the thermal stability and oxidation stability of the prepared ethylene-vinyl acetate. More specifically, the antioxidant may be a phenol- based antioxidant, a non-phenol-based antioxidant, or a mixture thereof. Preferably, a non-phenol-based antioxidant is used with a view to reducing a drop of complex viscosity and shear thinning index and minimizing discoloration.
The phenol-based antioxidant as used herein is a known antioxidant generally used in the related art without any limitation. Specific examples of the phenol-based antioxidant may include octadecyl-3-(3,5-di-tert.butyl-4-hydroxyphenyl)-propionate, butylated hydroxytoluene, pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-
hydroxyphenyl)propionate), 2', 3-bis [[3-[3, 5-di-tert-butyl-4-hydroxyphenyl]propionyl]] propionohydrazide, or mixtures thereof.
The non-phenol-based antioxidant as used herein is a known antioxidant generally used in the related art without any limitation. Specific examples of the non- phenol-based antioxidant may include tris(2,4-ditert-butylphenyl)phosphite, 4,4'- thiobis(6-tert-butyl-m-cresol), bis-(2, 4-di-t-butylphenol) pentaerythritol diphosphite, 2- (tert-butyl)-6-methyl-4-(3-((2,4,8, 10-tetrakis(tert- butyl)dibenzo[d,fj[ l ,3,2]dioxaphosphepin-6-yl)oxy)propyl)phenol, bis(2,4-di-tert.- butyl-6-methylphenyl)-ethyl-phosphite, tris(nonylphenyl) phosphite, or mixtures thereof.
The antioxidant may be used in an amount of 0.01 to 0.5 part by weight with respect to 100 parts by weight of the ethylene-vinyl acetate resin composition. An extremely low content of the antioxidant results in preparation of ethylene-vinyl acetate with poor oxidation stability, and an extremely high content of the antioxidant greatly deteriorates the efficiency of modification using electron beams and possibly causes discoloration of the ethylene-vinyl acetate.
The ethylene-vinyl acetate resin composition may further include a UV stabilizer that not only maintains the thermal stability and oxidation stability of the prepared ethylene-vinyl acetate, but also prevents deterioration in the efficiency of modification using electron beams. The UV stabilizer as used herein is preferably a hindered amine-based UV stabilizer, as known to be generally used in the related art. The hindered amine-based UV stabilizer can excellently maintain the effect of modification of ethylene-vinyl acetate using electron beams and thus keep the low exposure dose of electron beams required to meet the desired properties. This allows it to prepare an ethylene-vinyl acetate with economic efficiency.
Specific examples of the UV stabilizer may include a polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl- l -piperidine ethanol, bis(2,2,6,6- tetramethyl-4-piperidinyl) sebacate, bis(l ,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, poly[6-[(l , l ,3,3-tetramethylbutyl)amino]- l ,3,5-triazine-2,4-dinyl][(2,2,6,6-tetramethyl-
4-piperidinyl)imino]hexamethylene[2,2,6,6-tetramethyl-4-piperidinyl)imino]], or mixtures thereof. The UV antioxidant may be contained in an amount of 0.01 to 0.5 part by weight with respect to 100 parts by weight of the ethylene-vinyl acetate resin composition.
The anti-blocking agent as used herein may be a known compound generally used in the related art to control the viscosity of the ethylene-vinyl acetate pellets without any limitation. Specific examples of the anti-blocking agent may include oleamide, stearamide, erucamide, ethylene bis-stearamide, ethylene bis-oleamide, or mixtures thereof. The anti-blocking agent may be contained in an amount of 0.02 to 0.5 part by weight with respect to 100 parts by weight of the ethylene-vinyl acetate resin composition. An extremely high content of the anti-blocking agent possibly results in a change of color in the course of the modification process using electron beams, and an extremely low content of the anti-blocking agent causes the pellets to stick together. Therefore, the anti-blocking agent is preferably contained in the above- defined range of amount.
The photoreactive monomer plays a role as an auxiliary for modification using electron beams that helps the modification process using electron beams to be accomplished with efficiency. Specific examples of the photoreactive monomer may include acrylic acid, acrylic acid esters, methacrylic acid, methacrylic acid esters, dicarboxylic acid with double bonds, dicarboxylic acid esters with double bonds, dicarboxylic acid anhydrides with double bonds, silane coupling agents, or mixtures thereof.
Among the examples of the photoreactive monomer, the dicarboxylic acid may be maleic acid, phthalic acid, itaconic acid, citraconic acid, alkenyl succinic acid, cis- 1 ,2,3,6-tetrahydrophthalic acid, or 4-methyl- l ,2,3,6-tetrahydrophthalic acid; the
(meth)acrylic acid compound may be acrylic acid, methacrylic acid, vinyl acetic acid, vinyl acetate, methyl-acrylic acid, ethyl-acrylic acid, butyl-acrylic acid, methyl- methacrylic acid, ethyl-methacrylic acid, glycidyl acrylate, or glycidyl methacrylate; and the silane coupling agent may be vinyltrimethoxy silane, vinyltriethoxy silane,
gamma-methacroxy propyltrimethoxy si lane, gamma-acroxy propyltrimethoxy silane, or acroxy methyltrimethoxy silane.
The ethylene-vinyl acrylate resin composition can improve the efficiency of electron beam irradiation by containing the auxiliary for modification using electron beams. This allows it to prepare ethylene-vinyl acetate having polar groups introduced to enhance adhesiveness and improved mechanical properties with regard to melt strength or shear thinning index. The photoreactive monomer may be contained in an amount of 0.1 to 3 parts by weight with respect to 100 parts by weight of the ethylene- vinyl acetate resin composition.
The reaction auxiliary as used herein may include a peroxide type of cross- linking agent and a cross-linking auxiliary. Specific examples of the peroxide cross- linking agent may include dicumyl peroxide, l , l-di-(tert-butyl peroxy)-3,3,5- trimethylcyclohexane, di-(2-tert-butyl-peroxyisopropyl)-benzene, butyl-4,4-bis(tert- butyldioxy)valerate, di-(2,4-dichlorobenzoyl)-peroxide, di-(2,4-dichlorobenzoyl)- peroxide, dibenzoyl peroxide, tert-butyl peroxybenzoate, tert-butylcumyl peroxide, 2,5- dimethyl-2,5-di-(tert-butylperoxy)-hexane, di-tert-butylperoxide, 2,5-dimethyl-2,5- di(tert-butylperoxy)hexim-3, or mixtures thereof. Specific examples of the cross- linking auxiliary may include triethyleneglycol dimethacry!ate, tetraethylglycol dimethacrylate, trimethylpropane trimethacrylate, divinylbenzene, ethyleneglycol dimethacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, triacrylisocyanurate, or mixtures thereof.
Additionally, the ethylene-vinyl acetate resin composition may further include, in addition to the ethylene-vinyl acetate resin, an ethylene copolymer including an ethylene-vinyl acetate copolymer, metallocene polypropylene, metallocene polyethylene, Ziegler-Natta polyethylene, low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), high-density polyethylene (HDPE), thermoplastic polyethylene elastomer, thermoplastic polyethylene plastomer, or mixtures thereof.
[ADVANTAGEOUS EFFECTS ]
According to the present invention, it is possible to provide a preparation method for ethylene-vinyl acetate with a low melt index that raises productivity and economic feasibility by including a simple step of modification in the preparation of ethylene-vinyl acetate having a high vinyl acetate content to secure good properties with regard to transparency, elasticity, etc. and allow good processability and also showing good mechanical properties, which render the ethylene-vinyl acetate applicable to various industrial uses.
[BRIEF DESCRIPTION OF DRAWINGS ]
FIG. 1 is a graph showing the molecular weight distribution as a function of the exposure dose of electron beams in Example 5.
[DETAILED DESCRIPTION OF THE EMBODIMENTS ]
Hereinafter, the present invention will be described in further detail with reference to the following examples, which are given for exemplary illustrations of the present invention and are not intended to limit the scope of the present invention.
[Experimental Example 1] Measurement of Penetration Depth of Electron Beam Depending on Electron Beam Energy
Electron beam energy of 2.5 MeV or 10 MeV is applied in the vertical direction with a scanning width up to 60 kW. Then the actual exposure dose of electron beam is measured as a function of the penetration depth based on the reference exposure dose for the electron beam energy of 25 KGy. The measurement results are presented in Table 1 .
[Table 1]
2.40 18.10 2.40 25.00
3.20 1.08 3.20 24.00
4.00 0 4.00 23.80
4.80 0 4.80 20.60
5.60 0 5.60 18.10
6.40 0 6.40 13.60
7.20 0 7.20 8.12
8.00 0 8.00 1.52
8.80 0 8.80 0
9.60 0 9.60 0
10.40 0 10.40 0
1 1.20 0 1 1.20 0
12.00 0 12.00 0
As can be seen from Table 1 , the maximum penetration depth is 3.2 cm at 2.5 MeV and 8 cm at 10 MeV. It is therefore demonstrated that the double-sided exposure of the electron beam can be achieved to a depth of 6.4 cm at 2.5 MeV and 16 cm at 10
MeV.
[Example 1] Melt Index Depending on Vinyl Acetate Content and Exposure Dose of Electron Beam
An ethylene-vinyl acetate (EVA) with a melt index of 60 g/10 min (at 190 °C, 2.16 kg) and a vinyl acetate (VA) content of 40 %, and an EVA with a melt index of 30 g/10 min (at 190 °C, 2.16 kg) and a VA content of 33 %, are spread on a metal tray (100 cm x 100 cm x 10 cm) to a uniform thickness of 3 to 4 cm. Then, the melt index depending on the exposure dose of electron beam is measured. The measurement results are presented in Table 2.
[Table 2]
Example EVA Thickness(cm) E-beam exposure Melt index after exposure dose (kGy) (g/10 min, @190 °C , 2.16 kg)
1 -1 60MI/40VA% 3~4cm 5 9.73
1 -2 10 1.99
1 -3 15 0.5
1-4 30MI/33VA% 3~4cm 5 4.2
1-5 10 1.0
As can be seen from Table 2, the melt index of ethylene-vinyl acetate (EVA) decreases with an increase in the exposure dose of the electron beam.
* Measurement procedures for melt index:
A 2.096 mm-diameter orifice is set into a cylinder of the melt index measurer at 190 °C, and the cylinder is filled with 4 to 5 g of EVA. With a piston in the cylinder, a weight of 2.16 kg is put on the piston to impose a load on the EVA. The EVA in the cylinder is preheated for about 5 minutes and the amount of the EVA passing down the cylinder in one minute is measured. This amount of EVA is reduced to the amount of EVA passing down the cylinder for 10 minutes.
[Example 2] Melt index Depending on Vinyl Acetate Content and Thickness of EVA Composition
An ethylene-vinyl acetate (EVA) with a melt index of 60 g/10 min (at 190 °C, 2. 16 kg) and a vinyl acetate (VA) content of 40 %, and an EVA with a melt index of 30 g/10 min (at 190 °C, 2.16 kg) and a VA content of 33 %, are packed in a polyolefin packing bag primarily made of LLDPE to a thickness and a weight as given in Table 3. Then, the melt index of the EVA is measured. The thickness of the EVA composition is given as 12 cm after double-sided exposure on the EVA composition at 6.3 cm thick.
[Table 3]
[Example 3] Change of Melt Strength of EVA Depending on Exposure Dose of Electron Beam
The EVA with a VA content of 40 % is exposed to the electron beam with different exposure doses and then measured with regard to the melt strength (Rheotens®, 170 °C). The measurement results are presented in Table 4.
[Table 4]
* Measurement procedures for melt strength (Rheotens®, 170 °C):
The melt strength is measured with Rheotens 71 .97 equipment connected to a capillary rheometer. Ethylene-vinyl acetate is melted at 170 °C in a 15 mm-diameter capillary barrel for about 4 minutes, and the capillary at 32 mm long and 1.0 mm in diameter is passed by a piston descending at a rate of 3 mm per minute. The melted ethylene-vinyl acetate resin passing through the orifice is then passed between two wheels that are located 150 mm thereunder and that rotate in engagement with each other at an acceleration of 3 mm/s2.
As can be seen from Table 4, the EVA of Comparative Example 3-1 not exposed to the electron beam has a melt strength of only 4.2mN, which is not high enough to allow the EVA for the use in extrusion molding, injection molding, foam molding, etc. Contrarily, the EVAs of Examples 3- 1 , 3-2, and 3-3 exposed to the electron beam with exposure doses of 5 kGy, 10 kGy, or 15 kGy have a melt strength of at least 30 mN, which is high enough to make the EVAs available for film molding, extrusion molding, foam molding, etc.
[Example 4] Change of Shear Thinning Index of EVA Depending on Exposure Dose of Electron Beam
The EVA with a VA content of 40 % is exposed to the electron beam and then measured with regard to the shear thinning index (ARES®, 170 °C, 15 % strain). The measurement results are presented in Table 5. The shear thinning index is defined as the ratio of viscosity at 1 rad/sec to viscosity at 100 rad/sec. A higher shear thinning index indicates higher viscosity at a lower shear stress and lower viscosity at a high shear stress.
* Shear thinning index = (Viscosity at 1 rad/sec) / (Viscosity at 100 rad/sec) [Table 5]
shear thinning index of 2.6, hardly showing a shear thinning effect, while the EVAs of Examples 4-1 , 4-2, and 4-3 subjected to exposure to electron beams with an exposure dose of 5 to 15 kGy have a shear thinning index of 4.9 to 10.2, which demonstrates good processability.
[Example 5] PDI Change Depending on Exposure Dose of Electron Beam
The EVA with a VA content of 40 % is exposed to the electron beam and then measured with regard to the molecular weight to calculate the molecular weight distribution. The measurement results are presented in Table 6 and FIG. 1. The molecular weight distribution is defined as the number average molecular weight with respect to the weight average molecular weight divided by the weight average molecular weight.
[Table 6]
E-beam exposure dose (kGy) PDI
Example 5- 1 5 1 1.2
Example 5-2 10 22.9
Example 5-3 15 14.3
Comparative Example 5- 1 0 4.8
As can be seen from Table 6 and FIG. 1 , compared to the EVA not exposed to the electron beam, the EVAs of Examples 5- 1 , 5-2, and 5-3 exposed to the electron beam show higher PDI values and wider molecular weight distributions, thereby securing appropriate mechanical strengths and processability.
Claims
[Claim 1 ]
A method for preparing an ethylene-vinyl acetate (EVA) having a melt index of 10 g/10 min or less, comprising:
applying an electron beam with an exposure dose of 1 to 25 kGy to an ethylene-vinyl acetate resin composition comprising an ethylene-vinyl acetate resin having a vinyl acetate content of 15 to 50 wt%.
[Claim 2]
The method as claimed in claim 1 , further comprising, prior to the step of applying an electron beam,
spreading the ethylene-vinyl acetate resin composition to a thickness of 1 to 16 cm on an auxiliary mold, or
packing the ethylene-vinyl acetate resin composition in a packing bag.
[Claim 3 ]
The method as claimed in claim 2, wherein the packing bag is selected from a group consisting of a polyolefin film, woven yarn, paper, coated paper, paper comprising a liner film, and a fabric.
[Claim 4]
The method as claimed in claim 3, wherein the polyolefin film is made using at least one selected from low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), very low density polyethylene (VLDPE), high-density polyethylene (HDPE), polypropylene (PP), an ethylene-based elastomer, an ethylene- based plastomer, a propylene-based elastomer, and a propylene-based plastomer.
[Claim 5 ]
The method as claimed in claim 2, wherein the total weight of the packing bag is 1000 kg or less.
[Claim 6]
The method as claimed in claim 1 , wherein the electron beam is applied to one side or both sides of the ethylene-vinyl acetate resin composition.
[Claim 7]
The method as claimed in claim I , wherein the ethylene-vinyl acetate resin with a vinyl acetate content of 15 to 50 wt% has a Rheotens melt strength of 1 to 30 mN.
[Claim 8]
The method as claimed in claim 1 , wherein the ethylene-vinyl acetate resin with a vinyl acetate content of 15 to 50 wt% has a melt index (190 °C, 2. 16 kg) of at least 15 g/10 min.
[Claim 9]
The method as claimed in claim 1 , wherein the prepared ethylene-vinyl acetate has a melt index of 0.01 to 5 g/10 min.
[Claim 10]
The method as claimed in claim 1 , wherein the prepared ethylene-vinyl acetate has a Rheotens melt strength of at least 30 mN.
[Claim 1 1 ]
The method as claimed in claim 1 , wherein the prepared ethylene-vinyl acetate has an ARES shear thinning index of 4 to 25.
[Claim 12]
The method as claimed in claim 1, wherein the prepared ethylene-vinyl acetate has a molecular weight distribution of at least 10.
[Claim 13 ]
The method as claimed in claim 1 , wherein the ethylene-vinyl acetate resin composition further comprises at least one additive selected from the group consisting of a photoreactive monomer, an antioxidant, a slip agent, an anti-blocking agent, a UV stabilizer, and a reaction auxiliary.
[Claim 14]
The method as claimed in claim 13, wherein the photoreactive monomer comprises at least one selected from the group consisting of acrylic acid, acrylic acid esters, methacrylic acid, methacrylic acid esters, dicarboxylic acid with double bonds, dicarboxylic acid esters with double bonds, dicarboxylic acid anhydrides with double bonds, and a silane coupling agent.
[Claim 15 ]
The method as claimed in claim 1 , wherein the ethylene-vinyl acetate resin composition further comprises at least one polymer resin selected from the group consisting of an ethylene copolymer including an ethylene-vinyl acetate copolymer, metal locene polypropylene, metallocene polyethylene, Ziegler-Natta polyethylene, low- density polyethylene (LDPE), linear low-density polyethylene (LLDPE), high-density polyethylene (HDPE), a thermoplastic polyethylene elastomer, and a thermoplastic polyethylene plastomer.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201480025338.0A CN105189579A (en) | 2013-05-08 | 2014-04-28 | Method for preparing ethylene-vinyl acetate with low melt index |
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| Application Number | Priority Date | Filing Date | Title |
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| KR20130052122 | 2013-05-08 | ||
| KR10-2013-0052122 | 2013-05-08 | ||
| KR10-2014-0032236 | 2014-03-19 | ||
| KR1020140032236A KR20140132667A (en) | 2013-05-08 | 2014-03-19 | Method for ethylenevinylacetate with low melt index |
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| WO2014181991A1 true WO2014181991A1 (en) | 2014-11-13 |
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| Application Number | Title | Priority Date | Filing Date |
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| PCT/KR2014/003731 WO2014181991A1 (en) | 2013-05-08 | 2014-04-28 | Method for preparing ethylene-vinyl acetate with low melt index |
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| WO (1) | WO2014181991A1 (en) |
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| RU2714445C2 (en) * | 2015-02-25 | 2020-02-17 | Юнион Карбайд Кемикалз Энд Плэстикс Текнолоджи Ллк | Polyolefin compounds for cable coatings |
| CN113715453A (en) * | 2021-09-02 | 2021-11-30 | 四川厚诚新材料有限公司 | Anti-freezing casting PE film and preparation method thereof |
| US11292857B2 (en) | 2019-10-31 | 2022-04-05 | Exxonmobil Chemical Patents Inc. | Methods and systems for the production of high molecular weight ethylene-based polymers |
| US11584814B2 (en) | 2018-11-26 | 2023-02-21 | Lg Chem, Ltd. | Ethylene-vinyl acetate copolymer and preparation method thereof |
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