WO2019136823A1 - 一种低水汽透过率聚烯烃弹性体胶膜及制备方法 - Google Patents
一种低水汽透过率聚烯烃弹性体胶膜及制备方法 Download PDFInfo
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- WO2019136823A1 WO2019136823A1 PCT/CN2018/079449 CN2018079449W WO2019136823A1 WO 2019136823 A1 WO2019136823 A1 WO 2019136823A1 CN 2018079449 W CN2018079449 W CN 2018079449W WO 2019136823 A1 WO2019136823 A1 WO 2019136823A1
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- polyolefin elastomer
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- 229920006124 polyolefin elastomer Polymers 0.000 title claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title abstract description 4
- 239000002313 adhesive film Substances 0.000 title abstract 5
- 230000035699 permeability Effects 0.000 title abstract 3
- 229920005989 resin Polymers 0.000 claims abstract description 50
- 239000011347 resin Substances 0.000 claims abstract description 50
- 238000004132 cross linking Methods 0.000 claims abstract description 14
- 239000011159 matrix material Substances 0.000 claims abstract description 14
- 239000000945 filler Substances 0.000 claims abstract description 13
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 11
- 150000001451 organic peroxides Chemical class 0.000 claims abstract description 10
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 7
- 239000004611 light stabiliser Substances 0.000 claims abstract description 7
- 239000000155 melt Substances 0.000 claims description 26
- 230000005540 biological transmission Effects 0.000 claims description 21
- -1 amino, carboxyl Chemical group 0.000 claims description 14
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000002808 molecular sieve Substances 0.000 claims description 11
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 11
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 10
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 10
- NZYMWGXNIUZYRC-UHFFFAOYSA-N hexadecyl 3,5-ditert-butyl-4-hydroxybenzoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NZYMWGXNIUZYRC-UHFFFAOYSA-N 0.000 claims description 10
- 239000013543 active substance Substances 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000001110 calcium chloride Substances 0.000 claims description 7
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000004806 packaging method and process Methods 0.000 claims description 7
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical group CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 6
- 239000005977 Ethylene Substances 0.000 claims description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- 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 claims description 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 6
- 239000011203 carbon fibre reinforced carbon Chemical group 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 6
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 6
- NXKLCUUCUOEFII-UHFFFAOYSA-N 3-[tert-butylperoxy-(1-tert-butylperoxy-2-ethylhexyl)peroxymethyl]heptane Chemical compound C(C)(C)(C)OOC(C(CCCC)CC)OOC(C(CCCC)CC)OOC(C)(C)C NXKLCUUCUOEFII-UHFFFAOYSA-N 0.000 claims description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- 238000007334 copolymerization reaction Methods 0.000 claims description 5
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 claims description 4
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 claims description 4
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 claims description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 4
- 230000000903 blocking effect Effects 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 3
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 150000008065 acid anhydrides Chemical group 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims description 3
- 150000002367 halogens Chemical group 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 239000004711 α-olefin Substances 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- VMJIDDGLSSJEFK-UHFFFAOYSA-N 1,1,5-trimethyl-3,3-bis(2-methylbutan-2-ylperoxy)cyclohexane Chemical compound CCC(C)(C)OOC1(OOC(C)(C)CC)CC(C)CC(C)(C)C1 VMJIDDGLSSJEFK-UHFFFAOYSA-N 0.000 claims description 2
- IMYCVFRTNVMHAD-UHFFFAOYSA-N 1,1-bis(2-methylbutan-2-ylperoxy)cyclohexane Chemical compound CCC(C)(C)OOC1(OOC(C)(C)CC)CCCCC1 IMYCVFRTNVMHAD-UHFFFAOYSA-N 0.000 claims description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 2
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 claims description 2
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 claims description 2
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 claims description 2
- IQQVCMQJDJSRFU-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO IQQVCMQJDJSRFU-UHFFFAOYSA-N 0.000 claims description 2
- PFRLCKFENIXNMM-UHFFFAOYSA-N 3-trimethylsilylpropan-1-amine Chemical compound C[Si](C)(C)CCCN PFRLCKFENIXNMM-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Chemical group 0.000 claims description 2
- 239000005909 Kieselgur Substances 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- XLXOGJYARRBRPZ-UHFFFAOYSA-N [2,3-di(prop-2-enoyloxy)-3-propoxypropyl] prop-2-enoate Chemical compound CCCOC(OC(=O)C=C)C(OC(=O)C=C)COC(=O)C=C XLXOGJYARRBRPZ-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- XRMBQHTWUBGQDN-UHFFFAOYSA-N [2-[2,2-bis(prop-2-enoyloxymethyl)butoxymethyl]-2-(prop-2-enoyloxymethyl)butyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(CC)COCC(CC)(COC(=O)C=C)COC(=O)C=C XRMBQHTWUBGQDN-UHFFFAOYSA-N 0.000 claims description 2
- VLVZXTNDRFWYLF-UHFFFAOYSA-N [2-ethyl-2-(prop-2-enoyloxymethyl)hexyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CC)(CCCC)COC(=O)C=C VLVZXTNDRFWYLF-UHFFFAOYSA-N 0.000 claims description 2
- KNSXNCFKSZZHEA-UHFFFAOYSA-N [3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical class C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C KNSXNCFKSZZHEA-UHFFFAOYSA-N 0.000 claims description 2
- FHLPGTXWCFQMIU-UHFFFAOYSA-N [4-[2-(4-prop-2-enoyloxyphenyl)propan-2-yl]phenyl] prop-2-enoate Chemical class C=1C=C(OC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OC(=O)C=C)C=C1 FHLPGTXWCFQMIU-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- QUZSUMLPWDHKCJ-UHFFFAOYSA-N bisphenol A dimethacrylate Chemical class C1=CC(OC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OC(=O)C(C)=C)C=C1 QUZSUMLPWDHKCJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
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- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- BWOVZCWSJFYBRM-UHFFFAOYSA-N carbononitridic isocyanate Chemical group O=C=NC#N BWOVZCWSJFYBRM-UHFFFAOYSA-N 0.000 claims description 2
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- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 claims description 2
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 2
- 229920000578 graft copolymer Polymers 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- MWHNJARVACPRAF-UHFFFAOYSA-N hydroxy 2-methylbutan-2-yl carbonate Chemical compound CCC(C)(C)OC(=O)OO MWHNJARVACPRAF-UHFFFAOYSA-N 0.000 claims description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 2
- OTRIMLCPYJAPPD-UHFFFAOYSA-N methanol prop-2-enoic acid Chemical compound OC.OC.OC(=O)C=C.OC(=O)C=C OTRIMLCPYJAPPD-UHFFFAOYSA-N 0.000 claims description 2
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 claims description 2
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
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- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
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- HQOVXPHOJANJBR-UHFFFAOYSA-N 2,2-bis(tert-butylperoxy)butane Chemical compound CC(C)(C)OOC(C)(CC)OOC(C)(C)C HQOVXPHOJANJBR-UHFFFAOYSA-N 0.000 claims 1
- YIJYFLXQHDOQGW-UHFFFAOYSA-N 2-[2,4,6-trioxo-3,5-bis(2-prop-2-enoyloxyethyl)-1,3,5-triazinan-1-yl]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCN1C(=O)N(CCOC(=O)C=C)C(=O)N(CCOC(=O)C=C)C1=O YIJYFLXQHDOQGW-UHFFFAOYSA-N 0.000 claims 1
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- CSGAUKGQUCHWDP-UHFFFAOYSA-N 1-hydroxy-2,2,6,6-tetramethylpiperidin-4-ol Chemical compound CC1(C)CC(O)CC(C)(C)N1O CSGAUKGQUCHWDP-UHFFFAOYSA-N 0.000 description 13
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 9
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- C08J2423/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
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- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
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- C08K5/00—Use of organic ingredients
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- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
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- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
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- C08L2201/00—Properties
- C08L2201/14—Gas barrier composition
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- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
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- C—CHEMISTRY; METALLURGY
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- C08L2312/06—Crosslinking by radiation
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2423/00—Presence of polyolefin
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Definitions
- the invention belongs to the field of photovoltaic packaging materials, and relates to a polyolefin elastomer film with low water vapor transmission rate for electronic device packaging and a preparation method thereof.
- Photovoltaic power generation is a process of converting solar energy into electrical energy. It has the three advantages of permanentness, cleanliness and flexibility. Compared with traditional thermal power generation, hydroelectric power generation and nuclear power generation, its preparation process is simple and reproducible. Has a good development prospects.
- the packaging materials for photovoltaic modules mainly use ethylene vinyl acetate copolymer (EVA).
- EVA ethylene vinyl acetate copolymer
- the molecular structure of the EVA material determines the low water vapor transmission rate and poor weather resistance of the EVA film.
- various new high-efficiency battery sheets such as N-type batteries, PERC batteries, double-sided batteries, etc. have been successively introduced, which puts higher requirements on the performance of packaging materials.
- the working environment of the components is very humid, and packaging materials with lower water vapor transmission rate are needed to protect the long-term and efficient operation of the components.
- These new high-efficiency cells or special water vapor environments place higher demands on the moisture barrier properties of the packaging materials. How to reduce the moisture barrier performance of packaging materials to improve the life of photovoltaic modules is a problem that the industry needs to solve.
- the barrier property of the encapsulating material can be correspondingly increased as the proportion of the polar functional group decreases, but the problem of lowering the transmittance is brought about, which is disadvantageous for the photovoltaic cell power generation. Improvement.
- the polar monomer copolymer is not used as the matrix resin, such as the patent CN106752997A (publication number), the patent CN102863916B (publication number), etc., using metallocene-catalyzed ethylene and ⁇ -olefin monomers such as butene, pentene.
- the polymer obtained by copolymerization of octene or the like is encapsulated as a matrix resin. Since there is no unsaturated bond in the molecular chain, all weather resistance and water repellency are significantly better than EVA, but this modification can only be realized in the polymerization process. , but can not be improved in the process of packaging film production
- a common method is to add a water absorbing agent to the film to slow the diffusion of water vapor in the film by physical adsorption or chemical reaction.
- a water absorbing agent for example, the patent CN103756579A is added with an ionic polymer, and the patent CN104962216A (publication number) is added with dicyclohexylcarbodiimide and 1-ethyl-(3-dimethylaminopropyl)carbodiimide.
- This method has a limited effect on the water-blocking performance of the film, and when the water-absorbing agent is saturated or completely reacted with water, the water-blocking effect is lost, and the reliability of the component for long-term use cannot be completely ensured.
- the object of the present invention is to remedy the deficiencies of the prior art and to provide a crosslinked low water vapor transmission rate polyolefin elastomer encapsulating film.
- the peroxide and the co-crosslinking agent can initiate cross-linking of the polyolefin elastomer, and further increase the cross-linking density and cross-linking degree of the film by adding the polyolefin elastomer and the activator containing the active group, and then cooperate with the water-blocking filler.
- the invention is applicable not only to a transparent olefin film but also to a colored film.
- the film in addition to the peroxide crosslinking system, the film can be pretreated by ultraviolet radiation, electron radiation crosslinking, etc., to improve the crosslinking degree and crosslink density of the film, and further improve the resistance of the film.
- the polyolefin elastomer encapsulating film prepared by the invention has ultra-low water vapor transmission rate and excellent weather resistance, and can provide reliable guarantee for long-term efficient operation of components in the outdoor.
- a low water vapor transmission rate polyolefin elastomer film for electronic device packaging comprising: 50 to 100 parts by mass of a matrix resin, 0 to 40 parts by mass Modified resin, 0.001 to 2 parts by mass of active agent, 0.1 to 3 parts by mass of organic peroxide, 0.02 to 5 parts by mass of a crosslinking agent, 0.02 to 2 parts by mass of a silane coupling agent, 0.005 to 2 mass Parts of the light stabilizer, 0 to 20 parts by mass of the water blocking filler.
- the film has a thickness of 0.01 to 1 mm.
- the matrix resin is composed of one or more kinds of polymers formed by copolymerization of ethylene and propylene, butene, pentene, hexene and octene, respectively, in any ratio, and the melt index of the matrix resin. It is 0.5 to 45 g/10 min.
- modified resin is composed of one or more of a modified resin having the following structural formula (1) to a modified resin having the structural formula (14) in an arbitrary ratio:
- a, b, c, and d are natural numbers, and X 1 is selected from the group consisting of methyl, ethyl, propyl, butyl, and hexyl; and R 1 , R 2 and R 3 are each independently 1 to 10 carbon atoms.
- the alkyl group; X 2 and X 3 are reactive groups which can participate in the crosslinking reaction, and the polyolefin elastomer is introduced by copolymerization of a monomer containing X 2 and X 3 groups or by a radical-initiated graft reaction.
- the X 2 is selected from the group consisting of halogen, amino, carboxyl, hydroxy, aldehyde, decyl, acid anhydride, acrylamide, sulfonate, epoxy, cyano, isocyanate, carbon-carbon double bond, carbon A triple bond or an acid chloride group in an amount of from 0.05% to 15% by weight.
- the X 3 is selected from the group consisting of an imino group, a phosphodiester group, a carbon-carbon double bond, and a carbon-carbon triple bond in an amount of 0.05% to 15% by weight.
- the active agent contains two or more reactive groups selected from the group consisting of halogen, carboxyl, amino, hydroxyl, thiol, acid anhydride, acrylamide, isocyanate, aldehyde, sulfonic acid.
- Base silane coupling group, acid chloride group.
- the organic peroxide is composed of isopropyl t-butyl peroxycarbonate, 2,5-dimethyl-2,5-(di-tert-butylperoxy)hexane, t-butyl peroxycarbonate- 2-ethylhexyl ester, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-amylperoxy)-3,3, 5-trimethylcyclohexane, 1,1-bis(tert-amylperoxy)cyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, 2,2-bis(tert-butyl) Peroxy)butane, 2-ethylhexylcarbonate t-amyl ester, 2,5-dimethyl 2,5-dimethyl 2,5-dimethyl 2,5-bis(benzoyl peroxyl) - one or more of hexane,
- the water absorbing filler is a porous adsorbing material or a compound capable of adsorbing water vapor to form crystal water.
- the water absorbing filler is composed of molecular sieve, zeolite, diatomaceous earth, activated carbon, porous silica, porous alumina, carbon black, calcium oxide, calcium carbonate, calcium chloride, magnesium sulfate, magnesium chloride, copper sulfate, One or more of sodium sulfate, calcium sulfate, zinc sulfate, and calcium hydroxide are mixed in any ratio.
- a method for preparing a low water vapor transmission rate polyolefin elastomer film which comprises: 50 to 100 parts by mass of a matrix resin, 0 to 40 parts by mass of a modified resin, and 0.001 to 2 parts by mass of an activity
- the agent 0.1 to 3 parts by mass of the organic peroxide, 0.02 to 5 parts by mass of the co-crosslinking agent, 0.02 to 2 parts by mass of the silane coupling agent, 0.005 to 2 parts by mass of the light stabilizer, and 0 to 20 parts by mass
- the water-blocking filler is taken, and all the components are mixed and added to the extruder, and cast into a film through a T-die to obtain an ultra-low water vapor transmission rate polyolefin elastomer film.
- the film is irradiated by ultraviolet light having an irradiation dose of 0.01 to 0.1 kWh/m 2 or an electron beam having an irradiation dose of 0.2 to 100 KGY, thereby modifying the matrix resin.
- the resin is cross-linked, grafted, etc. with an active agent, an organic peroxide, and a co-crosslinking agent.
- the invention has the beneficial effects that the content of the invention is not limited to the polyolefin elastomer system, and is equally applicable to the EVA film, the PE film, and the EMMA film.
- the modified resin and the active agent By adding the modified resin and the active agent, the crosslink density and cross-linking degree of the film can be improved, and the water-blocking property of the polymer material can be greatly improved by the combination of the appropriate water-blocking filler.
- two or more of a matrix resin, an activator, a crosslinking agent, and an organic peroxide may undergo a chemical reaction that increases barrier properties.
- the following parts by mass are included: 80 parts of polyolefin elastomer having a melt index of 5 g/10 min, grade C5070D (SABIC Innovative Plastics), 20 parts of ethylene octene copolymer modified resin containing 2.5% amino group, 0.26 parts of ethylene Acid, 0.65 parts of isopropyl butyl peroxycarbonate, 0.6 parts of triallyl isocyanurate, 0.5 parts of vinyltriethoxysilane, 0.04 parts of 3,5-di-tert-butyl-4-hydroxyl - Cetyl benzoate, 0.2 part molecular sieve, designated S-1.
- the following parts by mass are included: 65 parts of polyolefin elastomer having a melt index of 15 g/10 min, grade C13060D (SABIC Innovative Plastics), 35 parts of ethylene and pentene copolymer modified resin containing 1.0% carboxyl group, 0.20 parts 1 , 4-butanediamine, 0.40 peroxybutyl 3,3,5-trimethylhexanoate, 0.35 triallyl isocyanurate B, 0.5 parts of vinyltrimethoxysilane, 0.08 parts of 4-hydroxyl -2,2,6,6-tetramethyl-1-piperidinol, 0.25 part of silica, designated S-2.
- the following parts by mass are included: 80 parts of polyolefin elastomer having a melt index of 30 g/10 min, grade C30070D (SABIC Innovative Plastics), 20 parts of ethylene butene copolymer modified resin containing 2.0% isocyanate group, 0.22 parts 1 , 3-propanediol, 0.65 parts of 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 0.6 parts of triallyl isocyanurate, 0.5 parts of vinyl three Ethoxysilane, 0.02 parts of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol, 0.2 parts of magnesium sulfate, designated as S-3.
- the following parts by mass are included: 60 parts of a polyolefin elastomer having a melt index of 0.5 g/10 min, grade 8150 (Dow), 40 parts of an ethylene and hexene copolymer modified resin containing 0.2% of an isocyanate group, 0.30 parts of 1, 4-succinic acid, 0.35 parts of 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 0.3 trimethylolpropane triacrylate, 0.5 parts of vinyltrimethoxy Base silane, 0.005 parts of cetyl 3,5-di-tert-butyl-4-hydroxy-benzoate, 0.2 parts of calcium chloride, designated S-4.
- the following parts by mass are included: 60 parts of a polyolefin elastomer having a melt index of 5 g/10 min, grade 8200 (Dow), 40 parts of a vinyl pentene copolymer modified resin containing 1.0% of a hydroxyl group, 2.0 parts of 1,5- Pentasulfonic acid, 0.1 part of 2-tert-butylperoxy-2-ethylhexyl peroxide, 0.02 parts of pentaerythritol tetraacrylate, 0.8 part of vinyltriacetoxysilane, 0.5 part of molecular sieve, 0.02 part of 3,5-di-union Cetyl butyl-4-hydroxy-benzoate, designated S-5.
- the following parts by mass are included: 60 parts of a polyolefin elastomer having a melt index of 5 g/10 min, grade 8200 (Dow), 40 parts of a vinyl pentene copolymer modified resin containing 1.0% of a hydroxyl group, 0.22 parts of toluene diisocyanate, 0.55 parts of tert-butyl 3,3,5-trimethylhexanoate, 0.5 parts of trimethylolpropane triacrylate, 1.0 part of vinyltrimethoxysilane, 0.07 parts of 4-hydroxy-2,2,6,6- Tetramethyl-1-piperidinol, 0.5 parts of calcium sulfate, designated S-6.
- the following parts by mass are included: 70 parts of a mixture of polyolefin elastomer 8200 (Dow) and C30070D (SABIC Innovative Plastics) having a melt index of 20 g/10 min, and 30 parts of an ethylene-butene copolymer modified resin containing 1.5% of a hydroxyl group.
- the following parts by mass are included: 60 parts of a mixture of polyolefin elastomers 8402 (Dow) and 8200 (Dow) having a melt index of 15 g/10 min, and 40 parts of an ethylene octene copolymer modified resin containing 1.5% of a sulfonic acid group.
- the following parts by mass are included: 70 parts of a mixture of polyolefin elastomers 8402 (Dow) and 8200 (Dow) having a melt index of 10 g/10 min, and 30 parts of an ethylene octene copolymer modified resin containing 1.5% of a sulfonic acid group.
- the following parts by mass are included: 95 parts of a mixture of polyolefin elastomers 8402 (Dow) and 8200 (Dow) having a melt index of 10 g/10 min, and 5 parts of an ethylene octene copolymer modified resin containing 2.0% of a sulfonic acid group. 0.001 parts of 1,4-hexanedithiol, 0.5 parts of 1,1-bis(tert-butylperoxy)cyclohexane, 0.5 ethoxylated triallyl isocyanurate, 0.3 parts of vinyltrimethoxy Silane, 0.09 parts of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol, 0.2 parts of calcium chloride, designated S-10.
- the following parts by mass are included: 90 parts of a mixture of polyolefin elastomer 8200 (Dow) and C30070D (SABIC Innovative Plastics) having a melt index of 20 g/10 min, and 10 parts of ethylene octene copolymer containing 0.1% acid chloride group.
- Resin 0.08 parts 4-amino-1-butyric acid, 0.5 parts t-butyl peroxycarbonate 2-ethylhexyl ester, 0.5 parts trimethylolpropane trimethacrylate, 0.2 parts vinyl triethoxy Silane, 0.08 parts of cetyl 3,5-di-tert-butyl-4-hydroxy-benzoate, 0.1 part of calcium chloride, 0.1 part of magnesium sulfate, designated S-11.
- the following parts by mass are included: 60 parts of a mixture of polyolefin elastomers 8200 (Dow) and 8402 (Dow) having a melt index of 10 g/10 min, and 40 parts of an ethylene octene copolymer modified resin containing 0.1% acid chloride groups. , 0.95 parts of oxalic acid, 0.5 parts of tert-butylperoxy-2-ethylhexyl peroxide, 0.5 parts of trimethylolpropane trimethacrylate, 2.0 parts of vinyltrimethoxysilane, 1.2 parts of 3,5 - Cetyl di-tert-butyl-4-hydroxy-benzoate, designated S-12.
- the following parts by mass are included: 70 parts of polyolefin elastomer having a melt index of 5 g/10 min, grade 8200 (Dow), 30 parts of ethylene octene copolymer modified resin containing 3.0% anhydride groups, 0.65 parts 1, 4-butanediol, 0.5 parts of tert-butylperoxy-2-ethylhexyl peroxide, 0.5 parts of trimethylolpropane trimethacrylate, 0.6 parts of vinyltriacetoxysilane, 1.0 part of 4-hydroxyl -2,2,6,6-tetramethyl-1-piperidinol, 0.1 part calcium carbonate, 0.1 part magnesium sulfate, designated S-13.
- the following parts by mass are included: 70 parts of polyolefin elastomer having a melt index of 5 g/10 min, grade 8200 (Dow), 30 parts of ethylene octene copolymer modified resin containing 3.0% anhydride groups, 0.65 parts 4 Amino-1-butanol, 0.5 parts of 2-ethylhexyl butylperoxyperoxide, 0.5 parts of trimethylolpropane trimethacrylate, 0.3 parts of vinyltriacetoxysilane, 0.02 parts of 4- Hydroxy-2,2,6,6-tetramethyl-1-piperidinol, 0.2 part of molecular sieve is referred to as S-14.
- the following parts by mass are included: 70 parts of a mixture of polyolefin elastomers 8200 (Dow) and 8402 (Dow) having a melt index of 15 g/10 min, and 30 parts of ethylene octene copolymer modified with 3.0% sulfonic acid groups. Resin, 0.65 parts terephthalamide, 0.5 parts t-butyl 2-ethylhexyl peroxycarbonate, 0.5 parts trimethylolpropane trimethacrylate, 0.3 parts vinyl triacetoxysilane, 0.02 parts 4-Hydroxy-2,2,6,6-tetramethyl-1-piperidinol, 0.2 part of molecular sieve is referred to as S-15.
- the following parts by mass are included: 60 parts of a mixture of polyolefin elastomer 8200 (Dow) and C30070D (SABIC Innovative Plastics) having a melt index of 20 g/10 min, and 30 parts of ethylene octene copolymer containing 3.0% anhydride groups.
- the following parts by mass are included: 50 parts of polyolefin elastomer having a melt index of 5 g/10 min, grade 8200 (Dow), 40 parts of ethylene octene copolymer modified resin containing 1.5% isocyanate groups, 0.25 parts 1, 6-hexanedithiol, 0.5 part t-butyl peroxycarbonate 2-ethylhexyl ester, 0.5 part trimethylolpropane trimethacrylate, 0.2 part vinyltrimethoxysilane, 0.08 part 3,5 - Cetyl di-tert-butyl-4-hydroxy-benzoate, 10 parts of silica, 5 parts of calcium chloride, 5 parts of calcium carbonate, designated S-17.
- the following parts by mass are included: 70 parts of a mixture of polyolefin elastomer 8200 (Dow) and C30070D (SABIC Innovative Plastics) having a melt index of 20 g/10 min, and 30 parts of ethylene octene copolymer containing 3.0% sulfonic acid groups. Modified resin, 0.50 parts of 1,4-butanediamine, 0.3 parts of tert-butylperoxy-2-ethylhexyl peroxide, 0.3 parts of trimethylolpropane trimethacrylate, 0.2 parts of vinyltrimethoxy Silane, 0.09 parts of cetyl 3,5-di-tert-butyl-4-hydroxy-benzoate, 0.5 part of carbon black, designated S-18.
- the following parts by mass are included: 100 parts of polyolefin elastomer having a melt index of 5 g/10 min, grade 8200 (Dow), 0.26 parts of oxalic acid, 0.65 parts of t-butyl peroxycarbonate, 0.6 parts of triene Propyl isocyanurate, 0.5 parts of vinyltriethoxysilane, 0.06 parts of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol, 0.2 parts of molecular sieve, denoted as S- 19.
- the following parts by mass are included: 100 parts of polyolefin elastomer having a melt index of 5 g/10 min, grade 8200 (Dow), 0.26 parts of 1,3-propanediol, 0.65 parts of isopropyl butyl peroxycarbonate, 0.6 parts Triallyl isocyanurate, 0.5 parts of vinyltriacetoxysilane, 0.05 parts of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol, 0.2 parts of molecular sieve, recorded as S-20.
- the following parts by mass are included: 100 parts of polyolefin elastomer having a melt index of 5 g/10 min, grade C5070D (SABIC Innovative Plastics) 0.65 parts of isopropyl butyl peroxycarbonate, 0.6 parts of triallyl isocyanuric acid The acid ester, 0.5 part of vinyltrimethoxysilane, 0.08 part of cetyl 3,5-di-tert-butyl-4-hydroxy-benzoate, 0.2 part of molecular sieve, designated C-1.
- the following parts by mass are included: 80 parts of polyolefin elastomer having a melt index of 5 g/10 min, grade 8200 (Dow), 20 parts of ethylene-butene copolymer modified resin containing 2.5% amino group, 0.65 parts of t-butyl group Isopropyl oxycarbonate, 0.6 parts of triallyl isocyanurate, 0.5 parts of vinyltriethoxysilane, 0.05 parts of cetyl 3,5-di-tert-butyl-4-hydroxy-benzoate , 0.2 parts of molecular sieve, denoted as C-2.
- the following parts by mass are included: 90 parts of ethylene vinyl acetate having a melt index of 25 g/10 min, 0.65 parts of isopropyl t-butyl peroxycarbonate, 0.6 parts of triallyl isocyanurate, 0.5 parts of vinyl Triethoxysilane, 0.07 parts of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol, 4 parts of titanium dioxide, 6 parts of calcium chloride, designated C-6.
- the components in the above examples and comparative examples were mixed in proportion and then added to an extruder, and precision extruded through a screw, and cast into a film through a T-die.
- the film thickness of the casting film was uniformly 0.5. Mm.
- the encapsulation film obtained by the above examples was applied to the packaging of the solar cell module, and was evaluated by the following test methods. The evaluation results are shown in Table 1:
- the test method refers to the standard GB/T 29848 "ethylene-vinyl acetate copolymer (EVA) film for photovoltaic module packaging".
- EVA ethylene-vinyl acetate copolymer
- the test method refers to the standard GB/T 29848 "Ethylene-vinyl acetate copolymer (EVA) film for photovoltaic module packaging"
- the test method refers to the standard GB/T 29848 "ethylene-vinyl acetate copolymer (EVA) film for photovoltaic module packaging", the test temperature is 85 ° C, the test relative humidity is 85%, and the aging time is 1000 h. Before and after the test, the yellowing index ( ⁇ YI) was determined according to the national standard GB 2409 "Plastic Yellow Index Test Method".
- EVA ethylene-vinyl acetate copolymer
- the test results show that the polyolefin elastomer film prepared according to the invention has low water vapor transmission rate and excellent weather resistance, and is an ideal polymer packaging material, which can be used for photovoltaic modules and electronic devices. Display devices and other packages.
- the results prove that by introducing an active resin with an active group and an active agent, initiating reactive group reaction, increasing the crosslinking density and crosslinking degree of the film, is a good method for improving the water blocking property of the material. Combined with a suitable water-blocking filler, a packaging material with excellent water-blocking properties can be obtained.
- This method is not only suitable for polyolefin elastomer film, but also for EVA, EMMA and other materials. It improves the water barrier properties of the material while also improving the weatherability of the material. It can be used to prepare transparent film, or it can be used without preparing colored film, such as black, white, etc.
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Abstract
一种低水汽透过率聚烯烃弹性体胶膜及制备方法,它包括 50~100 质量份的基体树脂、0~40 质量份的改性树脂、0.001~2 质量份的活性剂、0.1~3 质量份的有机过氧化物、0.02~5 质量份的助交联剂、0.02~2 质量份的硅烷偶联剂、0.005~2 质量份的光稳定剂、0~20 质量份的阻水填料。通过加入带有活性基团的改性树脂和活化剂,提高了胶膜的交联度和交联密度,降低了水汽透过率;加入阻水填料进一步提高胶膜阻水性能,保证组件可靠性,延长组件寿命。
Description
本发明属于光伏封装材料领域,涉及一种用于电子器件封装的具有低水汽透过率的聚烯烃弹性体胶膜及制备方法。
能源紧缺和环境问题日益凸显的今天,寻找可再生、环境友好的绿色能源已成为必然趋势。光伏发电是将太阳能转化成电能的过程,具有永久性、清洁性和灵活性三大优点,而且与传统的火力发电、水力发电和核能发电相比,它的制备过程简单,复制性强,因此具有很好的发展前景。
目前光伏组件的封装材料主要采用乙烯醋酸乙烯酯共聚物(EVA)。但是EVA材料自身分子结构决定了EVA胶膜存在水汽透过率偏高、耐候性较差等不足。随着电池技术的发展,各种新型高效电池片如N型电池、PERC电池、双面电池等相继面世,对封装材料的性能提出了更高的要求。此外,在渔光互补等项目中,组件的工作环境湿度很高,也需要有更低水汽透过率的封装材料来为组件长期高效工作保驾护航。这些新型高效电池片或特殊水汽环境对封装材料的水汽阻隔性能提出了更高要求。如何降低封装材料的水汽阻隔性能提升光伏组件的寿命是行业需要解决的问题。
如果降低基体树脂EVA中的醋酸乙烯酯(VA)含量,随着极性官能团比例的下降,可相应增加封装材料的阻隔性,但会带来透光率降低的问题,不利于光伏电池发电量的提升。极端的情形是不采用极性单体共聚物作为基体树脂,如专利CN106752997A(公开号)、专利CN102863916B(公开号)等,采用茂金属催化的乙烯和α-烯烃单体比如丁烯、戊烯、辛烯等进行共聚得到的聚合物作为基体树脂进行封装,由于分子链中没有不饱和键,所有耐候性和阻水性均明显好于EVA,但这种改进方式只能在聚合过程中进行实现,而在封装胶膜制作过程无法进行二次改良
为了提高封装胶膜的阻水性能,常见的方法是在胶膜中添加吸水剂,通过物理吸附或者化学反应的方式,减缓水汽在胶膜中的扩散。如专利CN103756579A添加了离子聚合物、专利CN104962216A(公开号)添加了二环己基碳二亚胺、1-乙基-(3-二甲基氨基丙基)碳酰二亚胺。这种方法对胶膜阻水性能的提升效果比较有限,且当吸水剂吸附饱和或者全部和水反应后就失去阻水效果,并不能完全保证组件长期使用的可靠性。
基于上述情况,目前开发一种具有低水汽透过率的新胶膜,保证光伏组件长期高效工作是很有必要的。
发明内容
本发明的目的是弥补现有技术的不足,提供一种交联型低水汽透过率的聚烯烃弹性体封装胶膜。过氧化物和助交联剂可以引发聚烯烃弹性体交联,通过添加含有活性基团的聚烯烃弹性体和活化剂,进一步提高胶膜的交联密度和交联度,再配合阻水填料,保证胶膜的高效阻水特性。本发明不仅适用于透明烯烃胶膜,也适用于有色胶膜。对于有色胶膜,除了过氧化物交联体系,还可以用紫外辐射、电子辐射交联等方式对胶膜进行预处理,提高胶膜的交联度和交联密度,进一步改善胶膜的阻水性能。通过本发明制备的聚烯烃弹性体封装胶膜,具有超低的水汽透过率和优异的耐候性,能为组件在户外长期高效工作提供可靠保证。
本发明的目的是通过以下技术方案实现的:一种用于电子器件封装的低水汽透过率聚烯烃弹性体胶膜,它包括:50~100质量份的基体树脂、0~40质量份的改性树脂、0.001~2质量份的活性剂、0.1~3质量份的有机过氧化物、0.02~5质量份的助交联剂、0.02~2质量份的硅烷偶联剂、0.005~2质量份的光稳定剂、0~20质量份的阻水填料。
进一步地,所述胶膜的厚度为0.01~1mm。
进一步地,所述基体树脂由乙烯分别与丙烯、丁烯、戊烯、己烯、辛烯发生共聚反应而形成的聚合物的一种或多种按任意配比混合组成,基体树脂的熔融指数为0.5~45g/10min。
进一步地,所述改性树脂由具有以下结构式(1)的改性树脂~具有结构式(14)的改性树脂的一种或多种按任意配比混合组成:
其中,a、b、c、d为自然数,X
1选自甲基、乙基、丙基、丁基、己基;R
1、R
2和R
3分别独立地为碳原子个数为1~10的烷基;X
2和X
3为可以参与交联反应的活性基团,通过含有X
2和X
3基团的单体参与共聚或者通过自由基引发的接枝反应的方式引入聚烯烃弹性体分子链;所述X
2选自卤素、氨基、羧基、羟基、醛基、巯基、酸酐基、丙烯酰胺基、磺酸基、环氧基、氰基、异氰酸酯基、碳碳双键、碳碳三键、酰氯基,其含量为0.05%~15wt%。所述X
3选自亚氨基,磷酸二酯基、碳碳双键、碳碳三键,其含量为0.05%~15wt%。
进一步地,所述活性剂含有两个或者两个以上活性基团,所述活性基团选自卤素、羧基、 氨基、羟基、巯基、酸酐基、丙烯酰胺基、异氰酸酯基、醛基、磺酸基、硅烷偶联基、酰氯基。
进一步地,所述有机过氧化物由叔丁基过氧化碳酸异丙酯、2,5-二甲基-2,5-(双叔丁过氧基)己烷、叔丁基过氧化碳酸-2-乙基己酯、1,1-双(叔丁基过氧)-3,3,5-三甲基环己烷、1,1-双(叔戊基过氧)-3,3,5-三甲基环己烷、1,1-双(叔戊基过氧)环己烷、1,1-双(叔丁基过氧)环己烷、2,2-双(叔丁基过氧)丁烷、过氧化2-乙基己基碳酸叔戊酯、2,5-二甲基2,5-二甲基2,5-二甲基2,5-双(苯甲酰过氧)-己烷、过氧化碳酸叔戊酯、过氧化3,3,5三甲基己酸叔丁酯的一种或多种按任意配比混合组成;所述助交联剂由三烯丙基异氰尿酸酯、三聚氰酸三烯丙酯、三羟甲基丙烷三丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯、季戊四醇三丙烯酸酯、三(2-羟乙基)异氰脲酸三丙烯酸酯、乙氧化三羟甲基丙烷三丙烯酸酯、丙氧化三羟甲基丙烷三丙烯酸酯、乙氧化甘油三丙烯酸酯、丙氧化甘油三丙烯酸酯、季戊四醇四丙烯酸酯、乙氧化季戊四醇四丙烯酸酯、三羟甲基丙烷四丙烯酸酯、双三羟甲基丙烷四丙烯酸酯、双三羟甲基丙烷四甲基丙烯酸酯、丙氧化季戊四醇四丙烯酸酯、2,4,6-三(2-丙烯基氧基)-1,3,5-三嗪、三环葵烷二甲醇二丙烯酸酯、丙氧化新戊二醇二丙烯酸酯、乙氧化双酚A二丙烯酸酯、乙氧化双酚A二甲基丙烯酸酯、2-丁基-2-乙基-1,3-丙二醇二丙烯酸酯、二乙二醇二甲基丙烯酸酯、三乙二醇二甲基丙烯酸酯、聚乙二醇二甲基丙烯酸酯的一种或多种按任意配比混合组成;所述硅烷偶联剂由乙烯基三乙氧基硅烷、乙烯基三甲氧基硅烷、乙烯基三过氧化叔丁基硅烷、乙烯基三乙酰氧基硅烷、乙烯基三(β-甲氧基乙氧基)硅烷、γ-氨丙基三乙氧基硅烷、γ-甲基丙烯酸酰氧基丙基三甲氧基硅烷、γ-缩水甘油醚氧丙基三甲基硅烷、3-氨丙基三甲基硅烷的一种或多种按任意配比混合组成;所述光稳定剂由双(2,2,6,6-四甲基-4-哌啶基)葵二酸酯、双(1-辛氧基-2,2,6,6-四甲基-4-哌啶基)葵二酸酯、4-(甲基)丙烯酰氧基-2,2,6,6-四甲基哌啶与α-烯类单体聚合得到的接枝共聚物、4-羟基-2,2,6,6-四甲基-1-哌啶醇、3,5-二叔丁基-4-羟基-苯甲酸十六烷基酯、葵二酸双-2,2,6,6-四甲基哌啶醇和三(1,2,2,6,6-五甲基-4-哌啶基)亚磷酸酯的一种或多种按任意配比混合组成。
进一步地,所述吸水填料为多孔吸附型材料或能吸附水汽形成结晶水的化合物。
进一步地,所述吸水填料由分子筛、沸石、硅藻土、活性炭、多孔二氧化硅、多孔三氧化二铝、炭黑、氧化钙、碳酸钙、氯化钙、硫酸镁、氯化镁、硫酸铜、硫酸钠、硫酸钙、硫酸锌、氢氧化钙的一种或多种按任意配比混合组成。
一种上述低水汽透过率聚烯烃弹性体胶膜的制备方法,该方法具体为:按照50~100质量份的基体树脂、0~40质量份的改性树脂、0.001~2质量份的活性剂、0.1~3质量份的有机过氧化物、0.02~5质量份的助交联剂、0.02~2质量份的硅烷偶联剂、0.005~2质量份的光稳定剂、 0~20质量份的阻水填料取材,将所有组分混合后加入挤出机,经过T型模头流延成膜,得到超低水汽透过率聚烯烃弹性体胶膜。
进一步地,经过T型模头流延成膜后,再通过辐照剂量为0.01~0.1kWh/m
2的紫外光或者辐照剂量为0.2~100KGY电子束等方式进行处理,使基体树脂、改性树脂与活性剂、有机过氧化物、助交联剂发生交联、接枝等反应。
本发明的有益效果是,本发明内容不限于聚烯烃弹性体体系,同样适用于EVA胶膜、PE胶膜、EMMA胶膜中。通过加入改性的树脂和活性剂的方式,提高胶膜的交联密度和交联度,再配合适当的阻水填料,可以大大提高高分子材料的阻水性能。其中基体树脂、活化剂、交联剂、有机过氧化物中的两种或多种可以发生增加阻隔性的化学反应。
下面结合具体实施例对本发明做进一步描述,但本发明的保护范围不仅局限于实施例。
实施例1
包括以下质量份的组分:80份熔融指数为5g/10min的聚烯烃弹性体,牌号C5070D(SABIC Innovative Plastics),20份含有2.5%氨基的乙烯辛烯共聚物改性树脂,0.26份乙二酸,0.65份叔丁基过氧化碳酸异丙酯,0.6份三烯丙基异氰尿酸酯,0.5份乙烯基三乙氧基硅烷,0.04份3,5-二叔丁基-4-羟基-苯甲酸十六烷基酯,0.2份分子筛,记为S-1。
实施例2
包括以下质量份的组分:65份熔融指数为15g/10min的聚烯烃弹性体,牌号C13060D(SABIC Innovative Plastics),35份含有1.0%羧基的乙烯和戊烯共聚物改性树脂,0.20份1,4-丁二胺,0.40过氧化3,3,5三甲基己酸叔丁酯,0.35三烯丙基异氰尿酸酯B,0.5份乙烯基三甲氧基硅烷,0.08份4-羟基-2,2,6,6-四甲基-1-哌啶醇,0.25份二氧化硅,记为S-2。
实施例3
包括以下质量份的组分:80份熔融指数为30g/10min的聚烯烃弹性体,牌号C30070D(SABIC Innovative Plastics),20份含有2.0%异氰酸酯基的乙烯丁烯共聚物改性树脂,0.22份1,3-丙二醇,0.65份1,1-双(过氧化叔丁基)-3,3,5-三甲基环己烷,0.6份三烯丙基异氰尿酸酯,0.5份乙烯基三乙氧基硅烷,0.02份4-羟基-2,2,6,6-四甲基-1-哌啶醇,0.2份硫酸镁,记为S-3。
实施例4
包括以下质量份的组分:60份熔融指数为0.5g/10min的聚烯烃弹性体,牌号8150(Dow),40份含有0.2%异氰酸酯基的乙烯和己烯共聚物改性树脂,0.30份1,4-丁二酸,0.35份1,1-双(过氧化叔丁基)-3,3,5-三甲基环己烷,0.3三羟甲基丙烷三丙烯酸酯,0.5份乙烯基三甲氧 基硅烷,0.005份3,5-二叔丁基-4-羟基-苯甲酸十六烷基酯,0.2份氯化钙,记为S-4。
实施例5
包括以下质量份的组分:60份熔融指数为5g/10min的聚烯烃弹性体,牌号8200(Dow),40份含有1.0%羟基的乙烯戊烯共聚物改性树脂,2.0份1,5-戊二磺酸,0.1份叔丁基过氧化碳酸-2-乙基己酯,0.02份季戊四醇四丙烯酸酯,0.8份乙烯基三乙酰氧基硅烷,0.5份分子筛,0.02份3,5-二叔丁基-4-羟基-苯甲酸十六烷基酯,记为S-5。
实施例6
包括以下质量份的组分:60份熔融指数为5g/10min的聚烯烃弹性体,牌号8200(Dow),40份含有1.0%羟基的乙烯戊烯共聚物改性树脂,0.22份甲苯二异氰酸酯,0.55份3,3,5三甲基己酸叔丁酯,0.5份三羟甲基丙烷三丙烯酸酯,1.0份乙烯基三甲氧基硅烷,0.07份4-羟基-2,2,6,6-四甲基-1-哌啶醇,0.5份硫酸钙,记为S-6。
实施例7
包括以下质量份的组分:70份熔融指数为20g/10min的聚烯烃弹性体8200(Dow)和C30070D(SABIC Innovative Plastics)的混合物,30份含有1.5%羟基的乙烯丁烯共聚物改性树脂,0.24份1,6-己二酸,0.55份份叔丁基过氧化碳酸-2-乙基己酯,0.5份季戊四醇四丙烯酸酯,0.5份乙烯基三甲氧基硅烷,0.05份3,5-二叔丁基-4-羟基-苯甲酸十六烷基酯,0.5份氯化镁记为S-7。
实施例8
包括以下质量份的组分:60份熔融指数为15g/10min的聚烯烃弹性体8402(Dow)和8200(Dow)的混合物,40份含有1.5%磺酸基的乙烯辛烯共聚物改性树脂,0.30份3-氨基-1-丁醇,0.5份叔丁基过氧化碳酸-2-乙基己酯,0.5三羟甲基丙烷三丙烯酸酯,0.4份乙烯基三乙氧基硅烷,0.05份4-羟基-2,2,6,6-四甲基-1-哌啶醇,0.15份硫酸钠,记为S-8。
实施例9
包括以下质量份的组分:70份熔融指数为10g/10min的聚烯烃弹性体8402(Dow)和8200(Dow)的混合物,30份含有1.5%磺酸基的乙烯辛烯共聚物改性树脂,0.30份1,3-二烯丙基脲,0.5份叔丁基过氧化碳酸-2-乙基己酯,0.5乙氧化三羟甲基丙烷三丙烯酸酯,0.3份乙烯基三乙酰氧基硅烷,2份3,5-二叔丁基-4-羟基-苯甲酸十六烷基酯,0.2份硫酸镁,记为S-9。
实施例10
包括以下质量份的组分:95份熔融指数为10g/10min的聚烯烃弹性体8402(Dow)和8200(Dow)的混合物,5份含有2.0%磺酸基的乙烯辛烯共聚物改性树脂,0.001份1,4-己二硫醇,0.5份1,1-双(叔丁基过氧)环己烷,0.5乙氧化三烯丙基异氰尿酸酯,0.3份乙烯基三甲氧基 硅烷,0.09份4-羟基-2,2,6,6-四甲基-1-哌啶醇,0.2份氯化钙,记为S-10。
实施例11
包括以下质量份的组分:90份熔融指数为20g/10min的聚烯烃弹性体8200(Dow)和C30070D(SABIC Innovative Plastics)的混合物,10份含有0.1%酰氯基团的乙烯辛烯共聚物改性树脂,0.08份4-氨基-1-丁酸,0.5份叔丁基过氧化碳酸-2-乙基己酯,0.5份三羟甲基丙烷三甲基丙烯酸酯,0.2份乙烯基三乙氧基硅烷,0.08份3,5-二叔丁基-4-羟基-苯甲酸十六烷基酯,0.1份氯化钙,0.1份硫酸镁,记为S-11。
实施例12
包括以下质量份的组分:60份熔融指数为10g/10min的聚烯烃弹性体8200(Dow)和8402(Dow)的混合物,40份含有0.1%酰氯基团的乙烯辛烯共聚物改性树脂,0.95份乙二酸,0.5份叔丁基过氧化碳酸-2-乙基己酯,0.5份三羟甲基丙烷三甲基丙烯酸酯,2.0份乙烯基三甲氧基硅烷,1.2份3,5-二叔丁基-4-羟基-苯甲酸十六烷基酯,记为S-12。
实施例13
包括以下质量份的组分:70份熔融指数为5g/10min的聚烯烃弹性体,牌号8200(Dow),30份含有3.0%酸酐基团的乙烯辛烯共聚物改性树脂,0.65份1,4-丁二醇,0.5份叔丁基过氧化碳酸-2-乙基己酯,0.5份三羟甲基丙烷三甲基丙烯酸酯,0.6份乙烯基三乙酰氧基硅烷,1.0份4-羟基-2,2,6,6-四甲基-1-哌啶醇,0.1份碳酸钙,0.1份硫酸镁、记为S-13。
实施例14
包括以下质量份的组分:70份熔融指数为5g/10min的聚烯烃弹性体,牌号8200(Dow),30份含有3.0%酸酐基团的乙烯辛烯共聚物改性树脂,0.65份4-氨基-1-丁醇,0.5份叔丁基过氧化碳酸-2-乙基己酯,0.5份三羟甲基丙烷三甲基丙烯酸酯,0.3份乙烯基三乙酰氧基硅烷,0.02份4-羟基-2,2,6,6-四甲基-1-哌啶醇,0.2份分子筛记为S-14。
实施例15
包括以下质量份的组分:70份熔融指数为15g/10min的聚烯烃弹性体8200(Dow)和8402(Dow)的混合物,30份含有3.0%磺酸基团的乙烯辛烯共聚物改性树脂,0.65份对苯二酰胺,0.5份叔丁基过氧化碳酸-2-乙基己酯,0.5份三羟甲基丙烷三甲基丙烯酸酯,0.3份乙烯基三乙酰氧基硅烷,0.02份4-羟基-2,2,6,6-四甲基-1-哌啶醇,0.2份分子筛记为S-15。
实施例16
包括以下质量份的组分:60份熔融指数为20g/10min的聚烯烃弹性体8200(Dow)和C30070D(SABIC Innovative Plastics)的混合物,30份含有3.0%酸酐基团的乙烯辛烯共聚物改性树脂,0.65份1,4-丁二醇,0.5份叔丁基过氧化碳酸-2-乙基己酯,0.5份三羟甲基丙烷三 甲基丙烯酸酯,0.2份乙烯基三乙氧基硅烷,0.06份3,5-二叔丁基-4-羟基-苯甲酸十六烷基酯,4份三氧化二铝,6份碳酸钙,记为S-16。
实施例17
包括以下质量份的组分:50份熔融指数为5g/10min的聚烯烃弹性体,牌号8200(Dow),40份含有1.5%异氰酸酯基团的乙烯辛烯共聚物改性树脂,0.25份1,6-己二硫醇,0.5份叔丁基过氧化碳酸-2-乙基己酯,0.5份三羟甲基丙烷三甲基丙烯酸酯,0.2份乙烯基三甲氧基硅烷,0.08份3,5-二叔丁基-4-羟基-苯甲酸十六烷基酯,10份二氧化硅,5份氯化钙,5份碳酸钙,记为S-17。
实施例18
包括以下质量份的组分:70份熔融指数为20g/10min的聚烯烃弹性体8200(Dow)和C30070D(SABIC Innovative Plastics)的混合物,30份含有3.0%磺酸基团的乙烯辛烯共聚物改性树脂,0.50份1,4-丁二胺,0.3份叔丁基过氧化碳酸-2-乙基己酯,0.3份三羟甲基丙烷三甲基丙烯酸酯,0.2份乙烯基三甲氧基硅烷,0.09份3,5-二叔丁基-4-羟基-苯甲酸十六烷基酯,0.5份炭黑,记为S-18。
实施例19
包括以下质量份的组分:100份熔融指数为5g/10min的聚烯烃弹性体,牌号8200(Dow),0.26份乙二酸,0.65份叔丁基过氧化碳酸异丙酯,0.6份三烯丙基异氰尿酸酯,0.5份乙烯基三乙氧基硅烷,0.06份4-羟基-2,2,6,6-四甲基-1-哌啶醇,0.2份分子筛,记为S-19。
实施例20
包括以下质量份的组分:100份熔融指数为5g/10min的聚烯烃弹性体,牌号8200(Dow),0.26份1,3-丙二醇,0.65份叔丁基过氧化碳酸异丙酯,0.6份三烯丙基异氰尿酸酯,0.5份乙烯基三乙酰氧基硅烷,0.05份4-羟基-2,2,6,6-四甲基-1-哌啶醇,0.2份分子筛,记为S-20。
对比例1
包括以下质量份的组分:100份熔融指数为5g/10min的聚烯烃弹性体,牌号C5070D(SABIC Innovative Plastics)0.65份叔丁基过氧化碳酸异丙酯,0.6份三烯丙基异氰尿酸酯,0.5份乙烯基三甲氧基硅烷,0.08份3,5-二叔丁基-4-羟基-苯甲酸十六烷基酯,0.2份分子筛,记为C-1。
对比例2
包括以下质量份的组分:80份熔融指数为5g/10min的聚烯烃弹性体,牌号8200(Dow),20份含有2.5%氨基的乙烯丁烯共聚物改性树脂,0.65份叔丁基过氧化碳酸异丙酯,0.6份三烯丙基异氰尿酸酯,0.5份乙烯基三乙氧基硅烷,0.05份3,5-二叔丁基-4-羟基-苯甲酸十六烷 基酯,0.2份分子筛,记为C-2。
对比例3
包括以下质量份的组分:100份熔融指数为25g/10min的乙烯醋酸乙烯酯,0.65份叔丁基过氧化碳酸异丙酯,0.6份三烯丙基异氰尿酸酯,0.5份乙烯基三乙氧基硅烷,0.06份4-羟基-2,2,6,6-四甲基-1-哌啶醇,0.2份分子筛记为C-5。
对比例4
包括以下质量份的组分:90份熔融指数为25g/10min的乙烯醋酸乙烯酯,0.65份叔丁基过氧化碳酸异丙酯,0.6份三烯丙基异氰尿酸酯,0.5份乙烯基三乙氧基硅烷,0.07份4-羟基-2,2,6,6-四甲基-1-哌啶醇,4份钛白粉,6份氯化钙,记为C-6。
将上述实施例和对比例中组分按比例混合后加入挤出机,通过螺杆精密挤出,经过T型模头流延成膜,以上例中为便于比较,流延成膜厚度统一为0.5mm。
通过上述实施例得到的封装胶膜应用于太阳能电池组件的封装,经下述测试方法进行评价,评价结果列于表1:
1.封装胶膜的交联度
测试方法参照标准GB/T 29848《光伏组件封装用乙烯-醋酸乙烯酯共聚物(EVA)胶膜》。
2.水汽透过率
测试方法参照标准GB/T 29848《光伏组件封装用乙烯-醋酸乙烯酯共聚物(EVA)胶膜》
3.恒定耐湿热老化性能
测试方法参照标准GB/T 29848《光伏组件封装用乙烯-醋酸乙烯酯共聚物(EVA)胶膜》,试验温度为85℃,试验相对湿度为85%,老化时间为1000h。试验前后按照国标GB 2409《塑料黄色指数试验方法》测定黄变指数(ΔYI)。
表1.实施例和对比例样品测试汇总
测试结果表明,根据本发明方案制备的聚烯烃弹性体胶膜,具有很低的水汽透过率和优异的耐候性,是一种理想的高分子封装材料,可以用于光伏组件、电子设备、显示器件等封装。该结果证明通过引入带有活性基团的活性树脂和活性剂,引发活性基团反应,提高胶膜的交联密度和交联度,是一种提高材料阻水性能的好方法。再配合适当的阻水填料,就能得 到阻水性能优异的封装材料。这种方法不仅适用于聚烯烃弹性体胶膜,还可以推广到EVA、EMMA等材料。它提高了材料阻水性能的同时,还改善了材料的耐候性。可用于制备透明胶膜,也可以用不制备有色胶膜,例如黑色、白色等。
Claims (10)
- 一种用于电子器件封装的低水汽透过率聚烯烃弹性体胶膜,其特征在于,它包括:50~100质量份的基体树脂、0~40质量份的改性树脂、0.001~2质量份的活性剂、0.1~3质量份的有机过氧化物、0.02~5质量份的助交联剂、0.02~2质量份的硅烷偶联剂、0.005~2质量份的光稳定剂、0~20质量份的阻水填料。
- 根据权利要求1所述的低水汽透过率聚烯烃弹性体胶膜,其特征在于,所述胶膜的厚度为0.01~1mm。
- 根据权利要求1所述的低水汽透过率聚烯烃弹性体胶膜,其特征在于,所述基体树脂由乙烯分别与丙烯、丁烯、戊烯、己烯、辛烯发生共聚反应而形成的聚合物的一种或多种按任意配比混合组成,基体树脂的熔融指数为0.5~45g/10min。
- 根据权利要求1所述的低水汽透过率聚烯烃弹性体胶膜,其特征在于,所述改性树脂由具有以下结构式(1)的改性树脂~具有结构式(14)的改性树脂的一种或多种按任意配比混合组成:其中,a、b、c、d为自然数,X 1选自甲基、乙基、丙基、丁基、己基;R 1、R 2和R 3分别独立地为碳原子个数为1~10的烷基;X 2和X 3为可以参与交联反应的活性基团,通过含有X 2和X 3基团的单体参与共聚或者通过自由基引发的接枝反应的方式引入聚烯烃弹性体分子链;所述X 2选自卤素、氨基、羧基、羟基、醛基、巯基、酸酐基、丙烯酰胺基、磺酸基、环氧基、氰基、异氰酸酯基、碳碳双键、碳碳三键、酰氯基,其含量为0.05%~15wt%。所述X 3选自亚氨基,磷酸二酯基、碳碳双键、碳碳三键,其含量为0.05%~15wt%。
- 根据权利要求1所述的低水汽透过率聚烯烃弹性体胶膜,其特征在于,所述活性剂含有两 个或者两个以上活性基团,所述活性基团选自卤素、羧基、氨基、羟基、巯基、酸酐基、丙烯酰胺基、异氰酸酯基、醛基、磺酸基、硅烷偶联基、酰氯基。
- 根据权利要求1所述的低水汽透过率聚烯烃弹性体胶膜,其特征在于,所述有机过氧化物由叔丁基过氧化碳酸异丙酯、2,5-二甲基-2,5-(双叔丁过氧基)己烷、叔丁基过氧化碳酸-2-乙基己酯、1,1-双(叔丁基过氧)-3,3,5-三甲基环己烷、1,1-双(叔戊基过氧)-3,3,5-三甲基环己烷、1,1-双(叔戊基过氧)环己烷、1,1-双(叔丁基过氧)环己烷、2,2-双(叔丁基过氧)丁烷、过氧化2-乙基己基碳酸叔戊酯、2,5-二甲基2,5-二甲基2,5-二甲基2,5-双(苯甲酰过氧)-己烷、过氧化碳酸叔戊酯、过氧化3,3,5三甲基己酸叔丁酯的一种或多种按任意配比混合组成;所述助交联剂由三烯丙基异氰尿酸酯、三聚氰酸三烯丙酯、三羟甲基丙烷三丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯、季戊四醇三丙烯酸酯、三(2-羟乙基)异氰脲酸三丙烯酸酯、乙氧化三羟甲基丙烷三丙烯酸酯、丙氧化三羟甲基丙烷三丙烯酸酯、乙氧化甘油三丙烯酸酯、丙氧化甘油三丙烯酸酯、季戊四醇四丙烯酸酯、乙氧化季戊四醇四丙烯酸酯、三羟甲基丙烷四丙烯酸酯、双三羟甲基丙烷四丙烯酸酯、双三羟甲基丙烷四甲基丙烯酸酯、丙氧化季戊四醇四丙烯酸酯、2,4,6-三(2-丙烯基氧基)-1,3,5-三嗪、三环葵烷二甲醇二丙烯酸酯、丙氧化新戊二醇二丙烯酸酯、乙氧化双酚A二丙烯酸酯、乙氧化双酚A二甲基丙烯酸酯、2-丁基-2-乙基-1,3-丙二醇二丙烯酸酯、二乙二醇二甲基丙烯酸酯、三乙二醇二甲基丙烯酸酯、聚乙二醇二甲基丙烯酸酯的一种或多种按任意配比混合组成;所述硅烷偶联剂由乙烯基三乙氧基硅烷、乙烯基三甲氧基硅烷、乙烯基三过氧化叔丁基硅烷、乙烯基三乙酰氧基硅烷、乙烯基三(β-甲氧基乙氧基)硅烷、γ-氨丙基三乙氧基硅烷、γ-甲基丙烯酸酰氧基丙基三甲氧基硅烷、γ-缩水甘油醚氧丙基三甲基硅烷、3-氨丙基三甲基硅烷的一种或多种按任意配比混合组成;所述光稳定剂由双(2,2,6,6-四甲基-4-哌啶基)葵二酸酯、双(1-辛氧基-2,2,6,6-四甲基-4-哌啶基)葵二酸酯、4-(甲基)丙烯酰氧基-2,2,6,6-四甲基哌啶与α-烯类单体聚合得到的接枝共聚物、4-羟基-2,2,6,6-四甲基-1-哌啶醇、3,5-二叔丁基-4-羟基-苯甲酸十六烷基酯、葵二酸双-2,2,6,6-四甲基哌啶醇和三(1,2,2,6,6-五甲基-4-哌啶基)亚磷酸酯的一种或多种按任意配比混合组成。
- 根据权利要求1所述的低水汽透过率聚烯烃弹性体胶膜,其特征在于,所述吸水填料为多孔吸附型材料或能吸附水汽形成结晶水的化合物。
- 根据权利要求7所述的低水汽透过率聚烯烃弹性体胶膜,其特征在于,所述吸水填料由分子筛、沸石、硅藻土、活性炭、多孔二氧化硅、多孔三氧化二铝、炭黑、氧化钙、碳酸钙、氯化钙、硫酸镁、氯化镁、硫酸铜、硫酸钠、硫酸钙、硫酸锌、氢氧化钙的一种或多种按任意配比混合组成。
- 一种权利要求1所述低水汽透过率聚烯烃弹性体胶膜的制备方法,其特征在于,该方法具体为:按照50~100质量份的基体树脂、0~40质量份的改性树脂、0.001~2质量份的活性剂、0.1~3质量份的有机过氧化物、0.02~5质量份的助交联剂、0.02~2质量份的硅烷偶联剂、0.005~2质量份的光稳定剂、0~20质量份的阻水填料取材,将所有组分混合后加入挤出机,经过T型模头流延成膜,得到超低水汽透过率聚烯烃弹性体胶膜。
- 根据权利要求9所述的方法,其特征在于,经过T型模头流延成膜后,再通过辐照剂量为0.01~0.1kWh/m 2的紫外光或者辐照剂量为0.2~100KGY电子束等方式进行处理,使基体树脂、改性树脂与活性剂、有机过氧化物、助交联剂发生交联、接枝等反应。
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EP4021968A4 (en) * | 2019-08-30 | 2023-04-12 | Dow Global Technologies Llc | PHOTOVOLTAIC ENCAPSULATION FILMS MADE OF PYROGENIC ALUMINUM OXIDE |
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JP6900519B2 (ja) | 2021-07-07 |
EP3739638A1 (en) | 2020-11-18 |
CN110016170B (zh) | 2020-12-01 |
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CN110016170A (zh) | 2019-07-16 |
EP3739638A4 (en) | 2021-12-22 |
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US11578196B2 (en) | 2023-02-14 |
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