CN117801691B - Anti-precipitation EPE co-extrusion packaging adhesive film - Google Patents
Anti-precipitation EPE co-extrusion packaging adhesive film Download PDFInfo
- Publication number
- CN117801691B CN117801691B CN202311853479.9A CN202311853479A CN117801691B CN 117801691 B CN117801691 B CN 117801691B CN 202311853479 A CN202311853479 A CN 202311853479A CN 117801691 B CN117801691 B CN 117801691B
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- CN
- China
- Prior art keywords
- parts
- adhesive film
- coupling agent
- resin layer
- silane coupling
- Prior art date
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- 239000002313 adhesive film Substances 0.000 title claims abstract description 90
- 238000004806 packaging method and process Methods 0.000 title claims abstract description 64
- 238000001125 extrusion Methods 0.000 title claims abstract description 59
- 238000001556 precipitation Methods 0.000 title claims abstract description 44
- 229920005989 resin Polymers 0.000 claims abstract description 139
- 239000011347 resin Substances 0.000 claims abstract description 139
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 70
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 61
- 150000004756 silanes Chemical class 0.000 claims abstract description 49
- 239000002994 raw material Substances 0.000 claims abstract description 31
- 230000009471 action Effects 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 100
- 239000003963 antioxidant agent Substances 0.000 claims description 95
- 230000003078 antioxidant effect Effects 0.000 claims description 94
- 239000004611 light stabiliser Substances 0.000 claims description 69
- 238000002360 preparation method Methods 0.000 claims description 56
- 238000006243 chemical reaction Methods 0.000 claims description 53
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 47
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 45
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 42
- 239000013067 intermediate product Substances 0.000 claims description 40
- 238000003756 stirring Methods 0.000 claims description 38
- 238000002156 mixing Methods 0.000 claims description 32
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 29
- 150000001412 amines Chemical class 0.000 claims description 29
- 229940114081 cinnamate Drugs 0.000 claims description 29
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 29
- WBYWAXJHAXSJNI-VOTSOKGWSA-M trans-cinnamate Chemical compound [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 claims description 29
- 125000005442 diisocyanate group Chemical group 0.000 claims description 28
- 150000002989 phenols Chemical class 0.000 claims description 28
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical class ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 24
- 150000002085 enols Chemical class 0.000 claims description 22
- 125000003396 thiol group Chemical class [H]S* 0.000 claims description 22
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical group C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 claims description 20
- 238000013329 compounding Methods 0.000 claims description 20
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 17
- 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 17
- 239000000203 mixture Substances 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 15
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 13
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 13
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 12
- BVOJCPQWSXCCKU-UHFFFAOYSA-N bis(1-adamantyl)-chlorophosphane Chemical group C1C(C2)CC(C3)CC2CC13P(Cl)C1(C2)CC(C3)CC2CC3C1 BVOJCPQWSXCCKU-UHFFFAOYSA-N 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- KZMYFIUFUAOZHP-UHFFFAOYSA-N 4-(1-adamantyl)phenol Chemical group C1=CC(O)=CC=C1C1(C2)CC(C3)CC2CC3C1 KZMYFIUFUAOZHP-UHFFFAOYSA-N 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 7
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 7
- 239000012948 isocyanate Substances 0.000 claims description 7
- -1 vinyl siloxane Chemical class 0.000 claims description 7
- TYZFMFVWHZKYSE-UHFFFAOYSA-N 3-mercaptohexanol Chemical compound CCCC(S)CCO TYZFMFVWHZKYSE-UHFFFAOYSA-N 0.000 claims description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 6
- 238000005266 casting Methods 0.000 claims description 6
- RGIBXDHONMXTLI-UHFFFAOYSA-N chavicol Chemical compound OC1=CC=C(CC=C)C=C1 RGIBXDHONMXTLI-UHFFFAOYSA-N 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- UIZVMOZAXAMASY-UHFFFAOYSA-N hex-5-en-1-ol Chemical compound OCCCCC=C UIZVMOZAXAMASY-UHFFFAOYSA-N 0.000 claims description 6
- 150000002513 isocyanates Chemical class 0.000 claims description 6
- 238000005259 measurement Methods 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 6
- 238000005096 rolling process Methods 0.000 claims description 6
- 238000007493 shaping process Methods 0.000 claims description 6
- 238000009966 trimming Methods 0.000 claims description 6
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- 239000007822 coupling agent Substances 0.000 claims description 4
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 claims description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- LEAQUNCACNBDEV-ZHACJKMWSA-N (e)-undec-1-en-1-ol Chemical compound CCCCCCCCC\C=C\O LEAQUNCACNBDEV-ZHACJKMWSA-N 0.000 claims description 3
- FIYMNUNPPYABMU-UHFFFAOYSA-N 2-benzyl-5-chloro-1h-indole Chemical compound C=1C2=CC(Cl)=CC=C2NC=1CC1=CC=CC=C1 FIYMNUNPPYABMU-UHFFFAOYSA-N 0.000 claims description 3
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 claims description 3
- WQABCVAJNWAXTE-UHFFFAOYSA-N dimercaprol Chemical compound OCC(S)CS WQABCVAJNWAXTE-UHFFFAOYSA-N 0.000 claims description 3
- LQAVWYMTUMSFBE-UHFFFAOYSA-N pent-4-en-1-ol Chemical compound OCCCC=C LQAVWYMTUMSFBE-UHFFFAOYSA-N 0.000 claims description 3
- RVEZZJVBDQCTEF-UHFFFAOYSA-N sulfenic acid Chemical compound SO RVEZZJVBDQCTEF-UHFFFAOYSA-N 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 238000005859 coupling reaction Methods 0.000 claims description 2
- 150000003254 radicals Chemical group 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims 1
- 239000012752 auxiliary agent Substances 0.000 abstract description 11
- 230000032683 aging Effects 0.000 abstract description 8
- 238000013508 migration Methods 0.000 abstract description 8
- 230000005012 migration Effects 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 4
- 230000032798 delamination Effects 0.000 abstract description 3
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000004814 polyurethane Substances 0.000 abstract description 2
- 229920002635 polyurethane Polymers 0.000 abstract description 2
- 125000000217 alkyl group Chemical group 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 140
- 239000005038 ethylene vinyl acetate Substances 0.000 description 78
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 78
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 33
- 230000000052 comparative effect Effects 0.000 description 28
- 239000002356 single layer Substances 0.000 description 24
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 24
- 238000012360 testing method Methods 0.000 description 18
- 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 description 13
- 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 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 11
- 239000000706 filtrate Substances 0.000 description 11
- 238000004821 distillation Methods 0.000 description 10
- 238000001914 filtration Methods 0.000 description 10
- 239000011521 glass Substances 0.000 description 9
- 238000001291 vacuum drying Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000004224 protection Effects 0.000 description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 230000001678 irradiating effect Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000012544 monitoring process Methods 0.000 description 4
- 238000005292 vacuum distillation Methods 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical group 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 2
- 230000000903 blocking effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 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 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 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 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical group 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/10—Adhesives in the form of films or foils without carriers
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- 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
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/04—Homopolymers or copolymers of ethene
- C09J123/08—Copolymers of ethene
- C09J123/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C09J123/0815—Copolymers of ethene with aliphatic 1-olefins
-
- 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
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/04—Homopolymers or copolymers of ethene
- C09J123/08—Copolymers of ethene
- C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C09J123/0853—Vinylacetate
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/048—Encapsulation of modules
-
- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/20—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself
- C09J2301/208—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself the adhesive layer being constituted by at least two or more adjacent or superposed adhesive layers, e.g. multilayer adhesive
-
- 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
- C09J2423/04—Presence of homo or copolymers of ethene
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
Abstract
The invention belongs to the technical field of photovoltaic materials, and particularly relates to an anti-precipitation EPE co-extrusion packaging adhesive film. The polarity difference between the POE layer and the EVA layer in the EPE adhesive film is large, delamination is easy, and the aging speed of the packaging adhesive film is too high. Aiming at the problems, the invention provides an anti-precipitation EPE co-extrusion packaging adhesive film which is of a layered structure, wherein the outermost layer is an EVA resin layer, the middle layer is a POE resin layer, the raw materials of the POE resin layer comprise a modified cross-linking agent and a modified silane coupling agent, the modified cross-linking agent contains a polyurethane structure, the polarity of the modified cross-linking agent is improved, other polar auxiliary agents in a system can be adsorbed, and the overall mobility of the auxiliary agents is reduced; the adamantyl structure in the modified cross-linking agent and the modified silane coupling agent belongs to a large-steric-hindrance alkyl structure, can block the action of electron migration, and is beneficial to improving the PID resistance.
Description
Technical Field
The invention belongs to the technical field of photovoltaic materials, and particularly relates to an anti-precipitation EPE co-extrusion packaging adhesive film.
Background
The photovoltaic packaging adhesive film is one of important materials in the photovoltaic industry, plays a role in bonding a solar cell with glass and a back plate, and has multiple functions of mechanical buffering, packaging protection and ultraviolet resistance protection of the back plate of a photovoltaic module. The photovoltaic packaging adhesive film is one of key materials affecting the service life and the generated power of the photovoltaic module. The development and the upgrading of the technology of the photovoltaic packaging adhesive film have pushing significance to the development of the photovoltaic industry.
At present, two main body packaging adhesive films of EVA and POE are mainly used in the market. The EVA adhesive film has the advantages of low processing temperature, strong impact resistance, high transmittance, good fusion fluidity, excellent cohesiveness and the like, but has the problems of photo-thermal oxidation aging, high water vapor transmittance, metal cation migration induced by hydrolysis of acetate ions in EVA, positive charge aggregation on the surface of a battery chip, potential Induced Degradation (PID) caused, and serious influence on the output power of the battery. The POE film has obvious advantages in the aspects of photo-thermal oxidation aging, PID resistance and the like, but the POE film has low polarity, weak adhesion with glass or backboard, easy occurrence of string deviation during lamination, poor compatibility of POE resin and polar auxiliary agent, and easy precipitation during subsequent processing and use.
To address the above problems, a new type of composite adhesive film (EPE) has been developed in the industry. Namely, EVA and POE are obtained by coextrusion, POE is used as an intermediate layer, EVA is used as outer layers on two sides, and a glue film product is obtained by compounding. The adhesive film well solves the problem of adhesiveness of POE adhesive films and the problem of PID effect of EVA adhesive films, and can reduce cost and increase efficiency to a certain extent. However, the EVA layer and the POE layer in the EPE adhesive film are easy to delaminate, and the POE layer auxiliary agent is easy to migrate (mainly migrate the cross-linking agent and the silane coupling agent), so that the service life of the EPE adhesive film is seriously affected, and the wide application of the EPE adhesive film is seriously hindered.
Disclosure of Invention
The problems in the prior art are: the polarity difference between the POE layer and the EVA layer in the EPE adhesive film is large, delamination is easy, and the aging speed of the packaging adhesive film is too high. Aiming at the problems, the invention provides an anti-precipitation EPE co-extrusion packaging adhesive film which is of a layered structure, wherein the outermost layer is an EVA resin layer, and the middle layer is a POE resin layer;
the POE resin layer comprises a modified cross-linking agent and a modified silane coupling agent as raw materials; wherein the method comprises the steps of
The modified cross-linking agent is obtained by reacting diisocyanate with a phenol derivative to form a carbamate chemical bond;
The modified silane coupling agent is obtained by sequentially reacting a phosphorus chloride derivative with enol, mercaptoalcohol, vinyl siloxane or mercaptopropyl siloxane; and
The modified silane coupling agent contains a-Si-O-Si-structure, an adamantane structure and a-C=C-structure in the molecular structure.
Further, the EVA resin layer comprises the following components in parts by weight:
100 parts of EVA resin;
0.5-1.5 parts of initiator;
0.5-1 part of cross-linking agent;
0.1-0.5 part of antioxidant;
0.1-0.5 part of light stabilizer;
0.2-0.6 part of coupling agent.
Further, the POE resin layer comprises the following components in parts by weight:
100 parts of POE resin;
0.5-1.5 parts of initiator;
1.5-2.5 parts of modified cross-linking agent;
0.05-0.3 part of antioxidant;
0.05-0.3 part of light stabilizer;
0.6-1.8 parts of modified silane coupling agent.
Further, the content of octene in the POE resin is 20-35wt%.
Further, the phosphorus chloride derivative is bis (1-adamantyl) phosphorus chloride.
Further, the antioxidant is a mixture of hindered phenol antioxidant and phosphite antioxidant according to the mass ratio of 1:1-3.
Further, the light stabilizer is a mixture of hindered amine light stabilizer and cinnamate according to the mass ratio of 1:1-3.
The preparation method of the modified cross-linking agent comprises the following steps:
step S11, evenly mixing diisocyanate, dibutyl tin dilaurate and N, N-dimethylformamide;
Step S12, mixing a phenol derivative and N, N-dimethylformamide, and dripping the mixture into the reaction system in the step S11, so as to react until the hydroxyl in the reaction system disappears; then pentaerythritol triacrylate is added into the reaction system, and the reaction is carried out until isocyanate in the reaction system disappears, thus obtaining the modified crosslinking agent.
The preparation method of the modified silane coupling agent comprises the following steps:
step S21, adding a phosphorus chloride derivative, enol and triethylamine into N, N-dimethylformamide, and stirring for reaction to obtain an intermediate product I; wherein the method comprises the steps of
Step S22, reacting the intermediate product I with mercapto alcohol under the action of a photoinitiator to obtain an intermediate product II;
And S23, performing a coupling reaction on the intermediate product II, acetic acid and the silane coupling agent to obtain the modified silane coupling agent.
A preparation method of an anti-precipitation EPE co-extrusion packaging adhesive film comprises the following steps:
S1: mixing, namely adding and mixing the raw materials of each layer of the anti-precipitation EPE co-extrusion packaging adhesive film in any one of claims 1-7 into a mixer according to the formula amount to obtain mixed raw materials for later use;
S2: co-extrusion is carried out to obtain the product,
Placing POE layer raw materials into a double-screw extruder, and carrying out melt blending;
placing EVA layer raw materials into a double-screw extruder, and melt blending;
Packaging the layered structure of the adhesive film, and simultaneously discharging, traction compounding and stretching to form a film through co-extrusion casting film dies of a plurality of double-screw extruders;
s3: the composite film is subjected to thickness measurement, edge pressing, shaping, trimming and rolling to obtain the anti-precipitation EPE co-extrusion packaging adhesive film.
The invention has the following beneficial effects:
(1) The invention provides an anti-precipitation EPE co-extrusion packaging adhesive film, wherein a POE formula system comprises a self-made modified cross-linking agent and a self-made modified silane coupling agent, and the self-made modified adhesive film is modified by adamantane which contains a large steric hindrance group structure, and firstly, the large steric hindrance structure of adamantane is an alkane structure, so that the adhesive film is not easy to hydrolyze and has a stable chemical structure; secondly, the large steric hindrance structure of adamantane can anchor the structures of the cross-linking agent and the silane coupling agent which are easy to migrate, so that migration and precipitation properties of the adamantane are reduced; thirdly, the self-made modified cross-linking agent contains a polyurethane structure, so that the polarity of the self-made modified cross-linking agent is improved, other polar auxiliary agents in the system can be adsorbed, and the mobility of the whole auxiliary agent is reduced; fourth, the large steric hindrance structure of adamantyl plays a role in blocking electron migration, so that PID resistance can be improved;
(2) The invention provides an anti-precipitation EPE co-extrusion packaging adhesive film, which adopts a higher-density POE resin as a main body through formulation design, so that on one hand, the auxiliary agent migration of a fixed POE layer is facilitated; on the other hand, the barrier property to small molecules, ions and water vapor is further improved, and the anti-PID performance is excellent.
Detailed Description
The present invention will be described in detail with reference to examples. It is to be understood that the following examples are illustrative of embodiments of the present invention and are not intended to limit the scope of the invention.
An anti-precipitation EPE co-extrusion packaging adhesive film is of a layered structure, wherein the outermost layer is an EVA resin layer, and the middle layer is a POE resin layer;
the POE resin layer comprises a modified cross-linking agent and a modified silane coupling agent as raw materials; wherein the modified cross-linking agent is obtained by reacting diisocyanate with a phenol derivative to form a carbamate chemical bond;
The modified silane coupling agent is obtained by sequentially reacting a phosphorus chloride derivative with enol, mercaptoalcohol, vinyl siloxane or mercaptopropyl siloxane; the modified silane coupling agent contains a-Si-O-Si-structure, an adamantane structure and a-C=C-structure in the molecular structure.
In the packaging adhesive film, the EVA resin layer comprises the following components in parts by weight:
100 parts of EVA resin;
0.5-1.5 parts of initiator;
0.5-1 part of cross-linking agent;
0.1-0.5 part of antioxidant;
0.1-0.5 part of light stabilizer;
0.2-0.6 part of coupling agent.
In the packaging adhesive film, the crosslinking agent comprises at least one of triallyl isocyanurate and trimethylolpropane trimethacrylate.
In the packaging adhesive film, the coupling agent comprises at least one of vinyl tri (beta-methoxyethoxy) silane and vinyl triethoxysilane.
In the packaging adhesive film, the POE resin layer comprises the following components in parts by weight:
100 parts of POE resin;
0.5-1.5 parts of initiator;
1.5-2.5 parts of modified cross-linking agent;
0.05-0.3 part of antioxidant;
0.05-0.3 part of light stabilizer;
0.6-1.8 parts of modified silane coupling agent.
Specifically, the content of octene in the POE resin is 20-35wt%.
Specifically, the phosphorus chloride derivative is bis (1-adamantyl) phosphorus chloride.
Specifically, the antioxidant is a mixture of hindered phenol antioxidant and phosphite antioxidant according to the mass ratio of 1:1-3.
Specifically, the light stabilizer is a mixture of hindered amine light stabilizer and cinnamate according to the mass ratio of 1:1-3.
The preparation method of the modified cross-linking agent comprises the following steps:
step S11, under the protection of N2, diisocyanate, dibutyltin dilaurate and N, N-dimethylformamide are added into a container, stirred uniformly and heated to 30-40 ℃;
Step S12, phenol derivative and N, N-dimethylformamide are mixed according to the dosage ratio of 1mol:500-800mL is placed in a constant pressure dropping funnel, and is added into the reaction system in the step S11 in a dropwise manner while stirring, the reaction is monitored by FTIR, the reaction is stirred until the hydroxyl absorption peak in the reaction system disappears in an infrared spectrogram, and the dropwise addition is stopped; then, under the condition of avoiding light, pentaerythritol triacrylate is added into a reaction system, the temperature is kept at 35-40 ℃ for reaction until isocyanate radical in the reaction system disappears in an infrared spectrogram, the reaction is stopped, the temperature is reduced to room temperature, the reaction product is filtered, filtrate is taken, reduced pressure distillation is carried out, and vacuum drying is carried out for 12-24 hours at 3-4 ℃ to obtain the modified cross-linking agent; wherein the dosage ratio of the diisocyanate, the phenol derivative, the pentaerythritol triacrylate and the N, N-dimethylformamide in the step S11 is as follows: 1mol:1mol:1.1 to 1.2mol:500-800mL; and
The dosage of the dibutyl tin dilaurate is 0.3-0.5wt% of the total mass of the diisocyanate and the phenol derivative.
In the preparation method, the diisocyanate comprises at least one of isophorone diisocyanate and dicyclohexylmethane-4, 4' -diisocyanate.
In the above preparation method, the phenol derivative includes 4- (1-adamantyl) phenol.
The preparation method of the modified silane coupling agent comprises the following steps:
Step S21, adding the phosphorus chloride derivative, enol and triethylamine into N, N-dimethylformamide, stirring for 2-3h at 0 ℃, slowly heating to room temperature, and stirring overnight; after the reaction is finished, carrying out reduced pressure distillation, dissolving the concentrate in dichloromethane, adding deionized water, oscillating, separating liquid, taking an organic phase, adding anhydrous sodium sulfate for drying, filtering, taking filtrate, carrying out reduced pressure distillation, and carrying out vacuum drying at 2-4 ℃ for 12-24 hours to obtain an intermediate product I;
In the preparation method, the dosage ratio of the phosphorus chloride derivative, the enol, the triethylamine and the N, N-dimethylformamide is 1mol:1.1 to 1.2mol:1.1 to 1.2mol:500-800mL;
S22, adding the intermediate product I, mercapto alcohol and a photoinitiator into 600-800mL of dichloromethane, stirring, placing under a UV lamp, irradiating for 10-20min, standing, and distilling under reduced pressure to obtain an intermediate product II; and
Step S23, adding the intermediate product II, acetic acid and a silane coupling agent into 600-800mL of ethanol water solution, adding acetic acid to adjust pH=4.5-5.5, stirring at room temperature for 2-3h, and then performing reduced pressure distillation at 80-100 ℃ to obtain a target product III.
In the preparation method, the dosage ratio of the intermediate product II to the silane coupling agent is 1mol:1mol;
in the preparation method, the ethanol aqueous solution has an ethanol content of 95wt%.
In the above preparation method, the phosphorus chloride derivative includes bis (1-adamantyl) phosphorus chloride.
In the preparation method, the enol comprises at least one of 5-hexen-1-ol, 4-penten-1-ol, undecenol and 4-allylphenol.
In the above preparation method, the mercapto alcohol comprises at least one of 6-mercapto hex-1-ol, 3-mercapto-1-hexanol and dimercaptopropanol.
In the preparation method, the silane coupling agent comprises at least one of vinyl triethoxysilane and gamma-mercaptopropyl triethoxysilane.
In the preparation method, the photoinitiator is a free radical type I photoinitiator.
In the preparation method, the initiator comprises at least one of tert-butyl peroxy-2-ethylhexyl carbonate, dibenzoyl peroxide, 2, 5-dimethyl-2, 5-bis (benzoyl peroxide) hexane and 1,1- (tert-butyl diperoxide) -3, 5-trimethylcyclohexane.
The EVA resin of the following examples of the present invention had a VA content of 33% and a Melt Index (MI) of 31, and was purchased from DuPont, U.S.A.
The hindered phenol antioxidant in the following examples of the present invention is antioxidant 1076; the phosphite antioxidant is antioxidant 168.
The hindered amine light stabilizer in the following examples in the present invention is UV-292; the cinnamate light stabilizer was UV-41.
Example 1
The anti-precipitation EPE co-extrusion packaging adhesive film is of a three-layer laminated structure and is formed by compounding an EVA resin layer, a POE resin layer and an EVA resin layer in sequence from top to bottom, wherein the single-layer thickness of the EVA resin layer is 100 mu m, and the single-layer thickness of the POE resin layer is 250 mu m;
the EVA resin layer comprises the following components in parts by weight:
100 parts of EVA resin;
1.1 parts of 1,1- (tert-butyl diperoxide) -3, 5-trimethylcyclohexane;
0.4 parts of triallyl isocyanurate;
0.4 parts of trimethylolpropane trimethacrylate;
0.36 parts of antioxidant (mass ratio of hindered phenol antioxidant to phosphite antioxidant is 1:2);
0.3 part of light stabilizer (mass ratio of hindered amine light stabilizer to cinnamate is 1:2);
0.3 part of vinyltris (. Beta. -methoxyethoxy) silane.
The POE resin layer comprises the following components in parts by weight:
100 parts of POE resin (with the octene content of 25 weight percent);
1.2 parts of 1,1- (tert-butyl diperoxide) -3, 5-trimethylcyclohexane;
2.2 parts of modified cross-linking agent;
0.1 part of antioxidant (mass ratio of hindered phenol antioxidant to phosphite antioxidant is 1:2);
0.15 parts of light stabilizer (mass ratio of hindered amine light stabilizer to cinnamate is 1:2);
1.3 parts of modified silane coupling agent;
the preparation method of the modified cross-linking agent comprises the following steps:
(1) Under the protection of N 2, diisocyanate, dibutyltin dilaurate and N, N-dimethylformamide are added into a three-neck flask, stirred uniformly and heated to 35 ℃;
(2) Then placing phenol derivative and N, N-dimethylformamide in a constant pressure dropping funnel according to the dosage ratio of 1.1mol:800mL, dropwise adding the mixture into a reaction system in the step (1) while stirring, monitoring the reaction by adopting FTIR, stirring until the absorption peak of hydroxyl in the reaction system disappears in an infrared spectrogram, stopping dropwise adding, adding pentaerythritol triacrylate into the reaction system under the condition of avoiding light, carrying out heat preservation reaction at 40 ℃ until the isocyanate in the reaction system disappears in the infrared spectrogram, stopping the reaction, cooling to room temperature, filtering a reaction product, taking filtrate, carrying out vacuum drying at 4 ℃ for 12 hours after vacuum distillation, and obtaining a modified crosslinking agent, wherein the infrared data are as follows:
3300-3500cm -1: -OH is absent; 2275cm -1: -NCO is not present; 3014cm -1: benzene ring-C-H is present; 1722cm -1、1735cm-1: -c=o present; 1608cm -1、811cm-1: -c=c-present;
the dosage ratio of the diisocyanate, the phenol derivative and the pentaerythritol triacrylate to the N, N-dimethylformamide in the step (1) is as follows: 1mol:1mol:1.2mol:500mL;
The dosage of the dibutyl tin dilaurate is 0.5 weight percent of the total weight of the diisocyanate and the phenol derivative.
The diisocyanate is dicyclohexylmethane-4, 4' -diisocyanate.
The phenol derivative is 4- (1-adamantyl) phenol.
The preparation method of the modified silane coupling agent comprises the following steps:
(1) Adding the phosphorus chloride derivative, enol and triethylamine into N, N-dimethylformamide, stirring for 2 hours at 0 ℃, slowly heating to room temperature, and stirring overnight; after the reaction, distilling under reduced pressure, dissolving the concentrate in dichloromethane, adding deionized water, oscillating, separating liquid, taking an organic phase, adding anhydrous sodium sulfate for drying, filtering, taking filtrate, distilling under reduced pressure, and vacuum drying at 4 ℃ for 12 hours to obtain an intermediate product I, wherein the infrared data are as follows:
3516cm -1: -OH is absent; 1126cm -1: -P-O-present; 1619cm -1: -c=c-present;
the dosage ratio of the phosphorus chloride derivative, the enol, the triethylamine and the N, N-dimethylformamide is 1mol:1.1mol:1.1mol:800mL;
(2) Adding the intermediate product I, mercapto alcohol and photoinitiator into 600mL of dichloromethane, stirring, placing under a UV lamp, irradiating for 15min at the light intensity of 400mJ/cm 2, standing, and distilling under reduced pressure to obtain an intermediate product II, wherein the infrared data are as follows:
3522cm -1: -OH is present; 1126cm -1: -P-O-present; 1619cm -1: -c=c-vanishes; 2550cm -1: SH is absent;
the dosage ratio of the intermediate product I to the mercapto alcohol is added according to the molar ratio of the carbon-carbon double bond to the mercapto group of 1:1;
the photoinitiator is used in an amount of 2wt% of the total mass of the reactants;
(3) Adding the intermediate product II, acetic acid and a silane coupling agent into 800mL of ethanol water solution (ethanol concentration is 95 wt%) and adding acetic acid to adjust the pH=5, stirring for 2 hours at room temperature, and then carrying out reduced pressure distillation at 90 ℃ to obtain a target product III, wherein the infrared data are as follows:
3522cm -1: -OH vanishes; 1091cm -1: -Si-O-Si-presence; 1126cm -1: -P-O-present; 1620cm -1: -c=c-present;
the dosage ratio of the intermediate product II to the silane coupling agent is 1mol:1mol;
the ethanol aqueous solution has an ethanol content of 95wt%.
The phosphorus chloride derivative is bis (1-adamantyl) phosphorus chloride.
The enol is 5-hexen-1-ol.
The mercapto alcohol is 6-mercapto hex-1-ol.
The silane coupling agent is vinyl triethoxysilane.
The photoinitiator is photoinitiator 1173.
The initiator is 1,1- (tert-butyl diperoxide) -3, 5-trimethylcyclohexane.
The preparation method of the precipitation-preventing EPE co-extrusion packaging adhesive film comprises the following steps:
S1: mixing, namely mixing the raw materials of all layers into a mixer according to a formula, and mixing and stirring for 2 hours at the temperature of 40 ℃ and the rotating speed of 80rpm to obtain mixed raw materials for later use;
S2: co-extrusion is carried out to obtain the product,
Placing POE layer raw materials into a double-screw extruder, and carrying out melt blending at the temperature of 90 ℃, 95 ℃ and 100 ℃ and the rotating speed of 50rpm in each region;
placing EVA layer raw material into a double screw extruder, melting and blending at 80 deg.C, 90 deg.C, 95 deg.C and rotating speed of 50rpm respectively,
The three-layer laminated structure of the packaging adhesive film is formed by simultaneously discharging, traction compounding and stretching through co-extrusion casting film dies of three double-screw extruders;
s3: the composite film is subjected to thickness measurement, edge pressing, shaping, trimming and rolling to obtain the anti-precipitation EPE co-extrusion packaging adhesive film.
Example 2
The anti-precipitation EPE co-extrusion packaging adhesive film is of a three-layer laminated structure and is formed by compounding an EVA resin layer, a POE resin layer and an EVA resin layer in sequence from top to bottom, wherein the single-layer thickness of the EVA resin layer is 100 mu m, and the single-layer thickness of the POE resin layer is 250 mu m;
the EVA resin layer comprises the following components in parts by weight:
100 parts of EVA resin;
1.5 parts of dibenzoyl peroxide;
0.3 parts of triallyl isocyanurate;
0.2 parts of trimethylolpropane trimethacrylate;
0.5 part of antioxidant (the mass ratio of hindered phenol antioxidant to phosphite antioxidant is 1:1-3);
0.35 parts of light stabilizer (mass ratio of hindered amine light stabilizer to cinnamate is 1:2);
0.2 part of vinyl triethoxysilane.
The POE resin layer comprises the following components in parts by weight:
100 parts of POE resin (with the octene content of 25 weight percent);
1.2 parts of 1,1- (tert-butyl diperoxide) -3, 5-trimethylcyclohexane;
2.5 parts of modified cross-linking agent;
0.05 part of antioxidant (mass ratio of hindered phenol antioxidant to phosphite antioxidant is 1:2);
0.075 parts of light stabilizer (hindered amine light stabilizer to cinnamate in a mass ratio of 1:2);
1.3 parts of modified silane coupling agent;
the preparation method of the modified cross-linking agent comprises the following steps:
(1) Under the protection of N 2, diisocyanate, dibutyltin dilaurate and N, N-dimethylformamide are added into a three-neck flask, stirred uniformly and heated to 30 ℃;
(2) Then placing phenol derivative and N, N-dimethylformamide in a constant pressure dropping funnel according to the dosage ratio of 1mol:800mL, dropwise adding the mixture into a reaction system while stirring, monitoring the reaction by adopting FTIR, stirring until the hydroxyl absorption peak in the reaction system disappears in an infrared spectrogram, stopping dropwise adding, adding pentaerythritol triacrylate into the reaction system under the condition of avoiding light, keeping the temperature at 40 ℃ until the isocyanate in the reaction system disappears in the infrared spectrogram, stopping the reaction, cooling to room temperature, filtering a reaction product, taking filtrate, carrying out vacuum distillation at 4 ℃ and then carrying out vacuum drying for 12 hours to obtain the modified crosslinking agent, wherein the infrared data are as follows:
3300-3500cm -1: -OH is absent; 2275cm -1: -NCO is not present; 3014cm -1: benzene ring-C-H is present; 1722cm -1、1735cm-1: -c=o present; 1608cm -1、811cm-1: -c=c-present;
the dosage ratio of the diisocyanate, the phenol derivative and the pentaerythritol triacrylate to the N, N-dimethylformamide in the step (1) is as follows: 1mol:1mol:1.2mol:800mL;
The dosage of the dibutyl tin dilaurate is 0.5 weight percent of the total weight of the diisocyanate and the phenol derivative.
The diisocyanate is isophorone diisocyanate.
The phenol derivative is 4- (1-adamantyl) phenol.
The preparation method of the modified silane coupling agent comprises the following steps:
(1) Adding the phosphorus chloride derivative, enol and triethylamine into N, N-dimethylformamide, stirring for 2 hours at 0 ℃, slowly heating to room temperature, and stirring overnight; after the reaction is finished, distilling under reduced pressure, dissolving the concentrate in dichloromethane, adding deionized water, oscillating, separating liquid, taking an organic phase, adding anhydrous sodium sulfate for drying, filtering, taking filtrate, distilling under reduced pressure, and drying in vacuum at 4 ℃ for 12 hours to obtain an intermediate product I;
the dosage ratio of the phosphorus chloride derivative, the enol and the triethylamine is 1mol:1.1mol:1.1mol:800mL;
(2) Adding the intermediate product I and mercaptoethanol into 600mL of dichloromethane, stirring, placing under a UV lamp, irradiating for 20min at a light intensity of 400mJ/cm 2, standing, and distilling under reduced pressure to obtain an intermediate product II, wherein the infrared data are as follows:
3522cm -1: -OH is present; 1126cm -1: -P-O-present; 1619cm -1: -c=c-vanishes; 2550cm -1: SH is absent;
the dosage ratio of the intermediate product I to the mercapto alcohol is added according to the molar ratio of the carbon-carbon double bond to the mercapto group of 1:1;
(3) Adding the intermediate product II, acetic acid and a silane coupling agent into 800mL of ethanol water solution, adding acetic acid to adjust the pH=5.5, stirring for 2 hours at room temperature, and performing reduced pressure distillation at 100 ℃ to obtain a target product III, wherein the infrared data are as follows:
3522cm -1: -OH vanishes; 1091cm -1: -Si-O-Si-presence; 1126cm -1: -P-O-present; 2550cm -1: SH is present.
The dosage ratio of the intermediate product II to the silane coupling agent is 1mol:1mol;
the ethanol aqueous solution has an ethanol content of 95wt%.
The phosphorus chloride derivative is bis (1-adamantyl) phosphorus chloride.
The enol is 4-penten-1-ol.
The mercapto alcohol is 3-mercapto-1-hexanol.
The silane coupling agent is gamma-mercaptopropyl triethoxysilane.
The preparation method of the anti-precipitation EPE co-extrusion packaging adhesive film of the embodiment 2 is the same as that of the embodiment 1.
Example 3
The anti-precipitation EPE co-extrusion packaging adhesive film is of a three-layer laminated structure and is formed by compounding an EVA resin layer, a POE resin layer and an EVA resin layer in sequence from top to bottom, wherein the single-layer thickness of the EVA resin layer is 100 mu m, and the single-layer thickness of the POE resin layer is 250 mu m;
the EVA resin layer comprises the following components in parts by weight:
100 parts of EVA resin;
0.5 part of 2, 5-dimethyl-2, 5-bis (benzoyl peroxide) hexane;
0.4 parts of triallyl isocyanurate;
0.4 parts of trimethylolpropane trimethacrylate;
0.2 parts of ethoxylated trimethylolpropane triacrylate;
0.1 part of antioxidant (mass ratio of hindered phenol antioxidant to phosphite antioxidant is 1:2);
0.1 part of light stabilizer (mass ratio of hindered amine light stabilizer to cinnamate is 1:2);
0.3 parts of vinyltriethoxysilane.
The POE resin layer comprises the following components in parts by weight:
100 parts of POE resin (with the octene content of 25 weight percent);
1.2 parts of 1,1- (tert-butyl diperoxide) -3, 5-trimethylcyclohexane;
1.5 parts of modified cross-linking agent;
0.20 part of antioxidant (mass ratio of hindered phenol antioxidant to phosphite antioxidant is 1:2);
0.30 parts of light stabilizer (mass ratio of hindered amine light stabilizer to cinnamate is 1:2);
1.3 parts of modified silane coupling agent;
the preparation method of the modified cross-linking agent comprises the following steps:
(1) Under the protection of N 2, diisocyanate, dibutyltin dilaurate and N, N-dimethylformamide are added into a three-neck flask, stirred uniformly and heated to 40 ℃;
(2) Then placing phenol derivative and N, N-dimethylformamide in a constant pressure dropping funnel according to the dosage ratio of 1mol:800mL, dropwise adding the mixture into a reaction system while stirring, monitoring the reaction by adopting FTIR, stirring until the hydroxyl absorption peak in the reaction system disappears in an infrared spectrogram, stopping dropwise adding, adding pentaerythritol triacrylate into the reaction system under the condition of avoiding light, keeping the temperature at 40 ℃ until the isocyanate in the reaction system disappears in the infrared spectrogram, stopping the reaction, cooling to room temperature, filtering a reaction product, taking filtrate, carrying out vacuum distillation at 4 ℃ and then carrying out vacuum drying for 12 hours to obtain the modified crosslinking agent, wherein the infrared data are as follows:
3300-3500cm -1: -OH is absent; 2275cm -1: -NCO is not present; 3014cm -1: benzene ring-C-H is present; 1722cm -1、1735cm-1: -c=o present; 1608cm -1、811cm-1: -c=c-present;
the dosage ratio of the diisocyanate, the phenol derivative and the pentaerythritol triacrylate to the N, N-dimethylformamide in the step (1) is as follows: 1mol:1mol:1.2mol:800mL;
The dosage of the dibutyl tin dilaurate is 0.5 weight percent of the total weight of the diisocyanate and the phenol derivative.
The diisocyanate is isophorone diisocyanate.
The phenol derivative is 4- (1-adamantyl) phenol.
The preparation method of the modified silane coupling agent comprises the following steps:
(1) Adding the phosphorus chloride derivative, enol and triethylamine into N, N-dimethylformamide, stirring for 2 hours at 0 ℃, slowly heating to room temperature, and stirring overnight; after the reaction is finished, distilling under reduced pressure, dissolving the concentrate in dichloromethane, adding deionized water, oscillating, separating liquid, taking an organic phase, adding anhydrous sodium sulfate for drying, filtering, taking filtrate, distilling under reduced pressure, and drying in vacuum at 4 ℃ for 12 hours to obtain an intermediate product I;
the dosage ratio of the phosphorus chloride derivative, the enol, the triethylamine and the N, N-dimethylformamide is 1mol:1.1mol:1.1mol:500mL;
(2) Adding the intermediate product I, mercapto alcohol and photoinitiator into 600mL of dichloromethane, stirring, placing under a UV lamp, irradiating for 10min at the light intensity of 400mJ/cm 2, standing, and distilling under reduced pressure to obtain an intermediate product II, wherein the infrared data are as follows: 3522cm -1: -OH is present; 1126cm -1: -P-O-present; 1619cm -1: -c=c-vanishes; 2550cm -1: SH is absent;
the dosage ratio of the intermediate product I to the mercapto alcohol is added according to the molar ratio of the carbon-carbon double bond to the mercapto group of 1:1;
The photoinitiator is used in an amount of 0.5wt% of the total mass of the reactants;
(3) Adding the intermediate product II, acetic acid and a silane coupling agent into 800mL of ethanol water solution (ethanol concentration is 95 wt%) and adding acetic acid to adjust pH=4.5, stirring for 2 hours at room temperature, and then carrying out reduced pressure distillation at 80 ℃ to obtain a target product III, wherein the infrared data are as follows:
3522cm -1: -OH vanishes; 1091cm -1: -Si-O-Si-presence; 1126cm -1: -P-O-present; 1620cm -1: -c=c-present;
the dosage ratio of the intermediate product II to the silane coupling agent is 1mol:1mol;
the ethanol aqueous solution has an ethanol content of 95wt%.
The phosphorus chloride derivative is bis (1-adamantyl) phosphorus chloride.
The enol is undecenol.
The mercapto alcohol is dimercaptopropanol.
The silane coupling agent is vinyl triethoxysilane.
The photoinitiator is a photoinitiator TPO-L.
The preparation method of the anti-precipitation EPE co-extrusion packaging adhesive film of the embodiment 2 is the same as that of the embodiment 1.
Example 4
The anti-precipitation EPE co-extrusion packaging adhesive film is of a three-layer laminated structure and is formed by compounding an EVA resin layer, a POE resin layer and an EVA resin layer in sequence from top to bottom, wherein the single-layer thickness of the EVA resin layer is 50 mu m, and the single-layer thickness of the POE resin layer is 350 mu m;
the EVA resin layer comprises the following components in parts by weight:
100 parts of EVA resin;
1.1 parts of 1,1- (tert-butyl diperoxide) -3, 5-trimethylcyclohexane;
0.4 parts of triallyl isocyanurate;
0.4 parts of trimethylolpropane trimethacrylate;
0.3 part of antioxidant (mass ratio of hindered phenol antioxidant to phosphite antioxidant is 1:2);
0.25 part of light stabilizer (mass ratio of hindered amine light stabilizer to cinnamate is 1:2);
0.3 part of vinyltris (. Beta. -methoxyethoxy) silane.
The POE resin layer comprises the following components in parts by weight:
100 parts of POE resin (with 30 weight percent of octene content);
1.2 parts of 1,1- (tert-butyl diperoxide) -3, 5-trimethylcyclohexane;
2.2 parts of modified cross-linking agent;
0.1 part of antioxidant (mass ratio of hindered phenol antioxidant to phosphite antioxidant is 1:2);
0.15 parts of light stabilizer (mass ratio of hindered amine light stabilizer to cinnamate is 1:2);
1.3 parts of modified silane coupling agent;
the preparation method of the modified cross-linking agent comprises the following steps:
(1) Under the protection of N 2, diisocyanate, dibutyltin dilaurate and N, N-dimethylformamide are added into a three-neck flask, stirred uniformly and heated to 40 ℃;
(2) Then placing phenol derivative and N, N-dimethylformamide in a constant pressure dropping funnel according to the dosage ratio of 1mol:800mL, dropwise adding the mixture into a reaction system while stirring, monitoring the reaction by adopting FTIR, stirring until the hydroxyl absorption peak in the reaction system disappears in an infrared spectrogram, stopping dropwise adding, adding pentaerythritol triacrylate into the reaction system under the condition of avoiding light, keeping the temperature at 40 ℃ until the isocyanate in the reaction system disappears in the infrared spectrogram, stopping the reaction, cooling to room temperature, filtering a reaction product, taking filtrate, carrying out vacuum distillation at 4 ℃ and then carrying out vacuum drying for 12 hours to obtain the modified crosslinking agent, wherein the infrared data are as follows:
3300-3500cm -1: -OH is absent; 2275cm -1: -NCO is not present; 3014cm -1: benzene ring-C-H is present; 1722cm -1、1735cm-1: -c=o present; 1608cm -1、811cm-1: -c=c-present;
The dosage ratio of the diisocyanate, the phenol derivative and the pentaerythritol triacrylate to the N, N-dimethylformamide in the step (1) is as follows: 1mol:1mol:1.2mol:800mL;
The dosage of the dibutyl tin dilaurate is 0.5 weight percent of the total weight of the diisocyanate and the phenol derivative.
The diisocyanate is dicyclohexylmethane-4, 4' -diisocyanate.
The phenol derivative is 4- (1-adamantyl) phenol.
The preparation method of the modified silane coupling agent comprises the following steps:
(1) Adding the phosphorus chloride derivative, enol and triethylamine into N, N-dimethylformamide, stirring for 2 hours at 0 ℃, slowly heating to room temperature, and stirring overnight; after the reaction, distilling under reduced pressure, dissolving the concentrate in dichloromethane, adding deionized water, oscillating, separating liquid, taking an organic phase, adding anhydrous sodium sulfate for drying, filtering, taking filtrate, distilling under reduced pressure, and vacuum drying at 4 ℃ for 12 hours to obtain an intermediate product I, wherein the infrared data are as follows:
3516cm -1: -OH is absent; 1126cm -1: -P-O-present; 1619cm -1: -c=c-present;
the dosage ratio of the phosphorus chloride derivative, the enol, the triethylamine and the N, N-dimethylformamide is 1mol:1.1mol:1.1mol:500mL;
(2) Adding the intermediate product I, mercapto alcohol and photoinitiator into 600mL of dichloromethane, stirring, placing under a UV lamp, irradiating for 12min at the light intensity of 400mJ/cm 2, standing, and distilling under reduced pressure to obtain an intermediate product II, wherein the infrared data are as follows:
3522cm -1: -OH is present; 1126cm -1: -P-O-present; 1619cm -1: -c=c-vanishes; 2550cm -1: SH is absent;
the dosage ratio of the intermediate product I to the mercapto alcohol is added according to the molar ratio of the carbon-carbon double bond to the mercapto group of 1:1;
the photoinitiator is used in an amount of 3wt% of the total mass of the reactants;
(3) Adding the intermediate product II, acetic acid and a silane coupling agent into 800mL of ethanol water solution (ethanol concentration is 95 wt%) and adding acetic acid to adjust the pH=5, stirring for 2 hours at room temperature, and then carrying out reduced pressure distillation at 90 ℃ to obtain a target product III, wherein the infrared data are as follows:
3522cm -1: -OH vanishes; 1091cm -1: -Si-O-Si-presence; 1126cm -1: -P-O-present; 2250cm -1: -SH is present;
the dosage ratio of the intermediate product II to the silane coupling agent is 1mol:1mol;
the ethanol aqueous solution has an ethanol content of 95wt%.
The phosphorus chloride derivative is bis (1-adamantyl) phosphorus chloride.
The enol is 4-allylphenol.
The mercapto alcohol is 6-mercapto hex-1-ol.
The silane coupling agent is gamma-mercaptopropyl triethoxysilane.
The photoinitiator is photoinitiator 1173.
The preparation method of the precipitation-preventing EPE co-extrusion packaging adhesive film comprises the following steps:
S1: mixing, namely mixing the raw materials of all layers into a mixer according to a formula, and mixing and stirring for 2 hours at the temperature of 40 ℃ and the rotating speed of 80rpm to obtain mixed raw materials for later use;
S2: co-extrusion is carried out to obtain the product,
Placing POE layer raw materials into a double-screw extruder, and melt blending at the temperature of 80 ℃, 90 ℃ and 100 ℃ and the rotating speed of 50rpm in each region respectively;
placing EVA layer raw material into a double screw extruder, melting and blending at 80 deg.C, 85 deg.C, 90 deg.C and rotating speed of 50rpm,
The three-layer laminated structure of the packaging adhesive film is formed by simultaneously discharging, traction compounding and stretching through co-extrusion casting film dies of three double-screw extruders;
s3: the composite film is subjected to thickness measurement, edge pressing, shaping, trimming and rolling to obtain the anti-precipitation EPE co-extrusion packaging adhesive film.
Example 5
The anti-precipitation EPE co-extrusion packaging adhesive film is of a three-layer laminated structure and is formed by compounding an EVA resin layer, a POE resin layer and an EVA resin layer in sequence from top to bottom, wherein the single-layer thickness of the EVA resin layer is 150 mu m, and the single-layer thickness of the POE resin layer is 150 mu m;
the EVA resin layer comprises the following components in parts by weight:
100 parts of EVA resin;
1.1 parts of 1,1- (tert-butyl diperoxide) -3, 5-trimethylcyclohexane;
0.3 parts of triallyl isocyanurate;
0.2 parts of trimethylolpropane trimethacrylate;
0.3 part of antioxidant (mass ratio of hindered phenol antioxidant to phosphite antioxidant is 1:2);
0.4 part of light stabilizer (mass ratio of hindered amine light stabilizer to cinnamate is 1:2);
0.3 part of vinyltris (. Beta. -methoxyethoxy) silane.
The POE resin layer comprises the following components in parts by weight:
100 parts of POE resin (with 20 weight percent of octene content);
1.2 parts of 1,1- (tert-butyl diperoxide) -3, 5-trimethylcyclohexane;
2.2 parts of modified cross-linking agent;
0.1 part of antioxidant (mass ratio of hindered phenol antioxidant to phosphite antioxidant is 1:2);
0.15 parts of light stabilizer (mass ratio of hindered amine light stabilizer to cinnamate is 1:2);
1.3 parts of modified silane coupling agent;
The preparation method of the modified cross-linking agent is the same as that of the example 1.
The preparation method of the modified silane coupling agent is the same as that of example 1.
The preparation method of the precipitation-preventing EPE co-extrusion packaging adhesive film comprises the following steps:
S1: mixing, namely mixing the raw materials of all layers into a mixer according to a formula, and mixing and stirring for 2 hours at the temperature of 40 ℃ and the rotating speed of 80rpm to obtain mixed raw materials for later use;
S2: co-extrusion is carried out to obtain the product,
Placing POE layer raw materials into a double-screw extruder, and melt blending at the temperature of 90 ℃, 100 ℃, 110 ℃ and the rotating speed of 45rpm in each region;
Placing EVA layer raw material into a double screw extruder, melting and blending at 80 deg.C, 90 deg.C, 100 deg.C and rotating speed of 50rpm respectively,
The three-layer laminated structure of the packaging adhesive film is formed by simultaneously discharging, traction compounding and stretching through co-extrusion casting film dies of three double-screw extruders;
s3: the composite film is subjected to thickness measurement, edge pressing, shaping, trimming and rolling to obtain the anti-precipitation EPE co-extrusion packaging adhesive film.
Example 6
The anti-precipitation EPE co-extrusion packaging adhesive film is of a three-layer laminated structure and is formed by compounding an EVA resin layer, a POE resin layer and an EVA resin layer in sequence from top to bottom, wherein the single-layer thickness of the EVA resin layer is 125 mu m, and the single-layer thickness of the POE resin layer is 200 mu m;
the EVA resin layer comprises the following components in parts by weight:
1.1 parts of 1,1- (tert-butyl diperoxide) -3, 5-trimethylcyclohexane;
0.4 parts of triallyl isocyanurate;
0.4 parts of trimethylolpropane trimethacrylate;
0.25 part of antioxidant (mass ratio of hindered phenol antioxidant to phosphite antioxidant is 1:2);
0.3 part of light stabilizer (mass ratio of hindered amine light stabilizer to cinnamate is 1:2);
0.6 part of vinyltris (. Beta. -methoxyethoxy) silane.
The POE resin layer comprises the following components in parts by weight:
100 parts of POE resin (with the octene content of 25 weight percent);
1.2 parts of 1,1- (tert-butyl diperoxide) -3, 5-trimethylcyclohexane;
2.2 parts of modified cross-linking agent;
0.1 part of antioxidant (mass ratio of hindered phenol antioxidant to phosphite antioxidant is 1:2);
0.15 parts of light stabilizer (mass ratio of hindered amine light stabilizer to cinnamate is 1:2);
0.6 part of modified silane coupling agent;
the preparation method of the modified crosslinking agent is the same as in example 1.
The preparation method of the modified silane coupling agent is the same as that of example 1.
The preparation method of the anti-precipitation EPE co-extrusion packaging adhesive film is the same as that of the embodiment 1.
Example 7
The anti-precipitation EPE co-extrusion packaging adhesive film is of a three-layer laminated structure and is formed by compounding an EVA resin layer, a POE resin layer and an EVA resin layer in sequence from top to bottom, wherein the single-layer thickness of the EVA resin layer is 100 mu m, and the single-layer thickness of the POE resin layer is 250 mu m;
the EVA resin layer comprises the following components in parts by weight:
100 parts of EVA resin;
1.1 parts of 1,1- (tert-butyl diperoxide) -3, 5-trimethylcyclohexane;
0.4 parts of triallyl isocyanurate;
0.4 parts of trimethylolpropane trimethacrylate;
0.4 part of antioxidant (the mass ratio of hindered phenol antioxidant to phosphite antioxidant is 1:2);
0.3 part of light stabilizer (mass ratio of hindered amine light stabilizer to cinnamate is 1:2);
0.3 part of vinyltris (. Beta. -methoxyethoxy) silane.
The POE resin layer comprises the following components in parts by weight:
100 parts of POE resin (with the octene content of 25 weight percent);
1.2 parts of 1,1- (tert-butyl diperoxide) -3, 5-trimethylcyclohexane;
2.2 parts of modified cross-linking agent;
0.1 part of antioxidant (mass ratio of hindered phenol antioxidant to phosphite antioxidant is 1:2);
0.15 parts of light stabilizer (mass ratio of hindered amine light stabilizer to cinnamate is 1:2);
1.8 parts of modified silane coupling agent;
the preparation method of the modified crosslinking agent is the same as in example 1.
The preparation method of the modified silane coupling agent is the same as that of example 1.
The preparation method of the anti-precipitation EPE co-extrusion packaging adhesive film is the same as that of the embodiment 1.
Example 8
The anti-precipitation EPE co-extrusion packaging adhesive film is of a three-layer laminated structure and is formed by compounding an EVA resin layer, a POE resin layer and an EVA resin layer in sequence from top to bottom, wherein the single-layer thickness of the EVA resin layer is 100 mu m, and the single-layer thickness of the POE resin layer is 250 mu m;
the EVA resin layer comprises the following components in parts by weight:
100 parts of EVA resin;
1.1 parts of tert-butyl peroxy-2-ethylhexyl carbonate;
0.4 parts of triallyl isocyanurate;
0.4 parts of trimethylolpropane trimethacrylate;
0.36 parts of antioxidant (mass ratio of hindered phenol antioxidant to phosphite antioxidant is 1:1);
0.3 part of light stabilizer (mass ratio of hindered amine light stabilizer to cinnamate is 1:1);
0.3 part of vinyltris (. Beta. -methoxyethoxy) silane.
The POE resin layer comprises the following components in parts by weight:
100 parts of POE resin (with the octene content of 25 weight percent);
1.2 parts of 1,1- (tert-butyl diperoxide) -3, 5-trimethylcyclohexane;
2.2 parts of modified cross-linking agent;
0.1 part of antioxidant (mass ratio of hindered phenol antioxidant to phosphite antioxidant is 1:1);
0.15 parts of light stabilizer (mass ratio of hindered amine light stabilizer to cinnamate is 1:1);
1.3 parts of modified silane coupling agent;
the preparation method of the modified crosslinking agent is the same as in example 1.
The preparation method of the modified silane coupling agent is the same as that of example 1.
The preparation method of the anti-precipitation EPE co-extrusion packaging adhesive film is the same as that of the embodiment 1.
Example 9
The anti-precipitation EPE co-extrusion packaging adhesive film is of a three-layer laminated structure and is formed by compounding an EVA resin layer, a POE resin layer and an EVA resin layer in sequence from top to bottom, wherein the single-layer thickness of the EVA resin layer is 100 mu m, and the single-layer thickness of the POE resin layer is 250 mu m;
the EVA resin layer comprises the following components in parts by weight:
100 parts of EVA resin;
1.1 parts of 1,1- (tert-butyl diperoxide) -3, 5-trimethylcyclohexane;
0.4 parts of triallyl isocyanurate;
0.4 parts of trimethylolpropane trimethacrylate;
0.36 parts of antioxidant (mass ratio of hindered phenol antioxidant to phosphite antioxidant is 1:4);
0.3 part of light stabilizer (mass ratio of hindered amine light stabilizer to cinnamate is 1:4);
0.3 part of vinyltris (. Beta. -methoxyethoxy) silane.
The POE resin layer comprises the following components in parts by weight:
100 parts of POE resin (with the octene content of 25 weight percent);
1.2 parts of 1,1- (tert-butyl diperoxide) -3, 5-trimethylcyclohexane;
2.2 parts of modified cross-linking agent;
0.1 part of antioxidant (mass ratio of hindered phenol antioxidant to phosphite antioxidant is 1:4);
0.15 parts of light stabilizer (mass ratio of hindered amine light stabilizer to cinnamate is 1:4);
1.3 parts of modified silane coupling agent;
the preparation method of the modified crosslinking agent is the same as in example 1.
The preparation method of the modified silane coupling agent is the same as that of example 1.
The preparation method of the anti-precipitation EPE co-extrusion packaging adhesive film is the same as that of the embodiment 1.
Example 10
The anti-precipitation EPE co-extrusion packaging adhesive film is of a three-layer laminated structure and is formed by compounding an EVA resin layer, a POE resin layer and an EVA resin layer in sequence from top to bottom, wherein the single-layer thickness of the EVA resin layer is 100 mu m, and the single-layer thickness of the POE resin layer is 250 mu m;
the EVA resin layer comprises the following components in parts by weight:
100 parts of EVA resin;
1.1 parts of 1,1- (tert-butyl diperoxide) -3, 5-trimethylcyclohexane;
0.4 parts of triallyl isocyanurate;
0.4 parts of trimethylolpropane trimethacrylate;
0.36 parts of antioxidant (mass ratio of hindered phenol antioxidant to phosphite antioxidant is 1:2);
0.3 part of light stabilizer (mass ratio of hindered amine light stabilizer to cinnamate is 1:2);
0.3 part of vinyltris (. Beta. -methoxyethoxy) silane.
The POE resin layer comprises the following components in parts by weight:
100 parts of POE resin (with the octene content of 25 weight percent);
1.2 parts of 1,1- (tert-butyl diperoxide) -3, 5-trimethylcyclohexane;
2.2 parts of modified cross-linking agent;
0.15 part of antioxidant (mass ratio of hindered phenol antioxidant to phosphite antioxidant is 1:2);
0.15 parts of light stabilizer (mass ratio of hindered amine light stabilizer to cinnamate is 1:2);
1.3 parts of modified silane coupling agent;
the preparation method of the modified crosslinking agent is the same as in example 1.
The preparation method of the modified silane coupling agent is the same as that of example 1.
The preparation method of the anti-precipitation EPE co-extrusion packaging adhesive film is the same as that of the embodiment 1.
Example 11
The anti-precipitation EPE co-extrusion packaging adhesive film is of a three-layer laminated structure and is formed by compounding an EVA resin layer, a POE resin layer and an EVA resin layer in sequence from top to bottom, wherein the single-layer thickness of the EVA resin layer is 100 mu m, and the single-layer thickness of the POE resin layer is 250 mu m;
the EVA resin layer comprises the following components in parts by weight:
100 parts of EVA resin;
1.1 parts of 1,1- (tert-butyl diperoxide) -3, 5-trimethylcyclohexane;
0.4 parts of triallyl isocyanurate;
0.4 parts of trimethylolpropane trimethacrylate;
0.36 parts of antioxidant (mass ratio of hindered phenol antioxidant to phosphite antioxidant is 1:2);
0.3 part of light stabilizer (mass ratio of hindered amine light stabilizer to cinnamate is 1:2);
0.3 part of vinyltris (. Beta. -methoxyethoxy) silane.
The POE resin layer comprises the following components in parts by weight:
100 parts of POE resin (with the octene content of 25 weight percent);
1.2 parts of 1,1- (tert-butyl diperoxide) -3, 5-trimethylcyclohexane;
2.2 parts of modified cross-linking agent;
0.15 part of antioxidant (mass ratio of hindered phenol antioxidant to phosphite antioxidant is 1:2);
0.30 parts of light stabilizer (mass ratio of hindered amine light stabilizer to cinnamate is 1:2);
1.3 parts of modified silane coupling agent;
the preparation method of the modified crosslinking agent is the same as in example 1.
The preparation method of the modified silane coupling agent is the same as that of example 1.
The preparation method of the anti-precipitation EPE co-extrusion packaging adhesive film is the same as that of the embodiment 1.
Example 12
The anti-precipitation EPE co-extrusion packaging adhesive film is of a three-layer laminated structure and is formed by compounding an EVA resin layer, a POE resin layer and an EVA resin layer in sequence from top to bottom, wherein the single-layer thickness of the EVA resin layer is 100 mu m, and the single-layer thickness of the POE resin layer is 250 mu m;
the EVA resin layer comprises the following components in parts by weight:
1.1 parts of 1,1- (tert-butyl diperoxide) -3, 5-trimethylcyclohexane;
0.4 parts of triallyl isocyanurate;
0.4 parts of trimethylolpropane trimethacrylate;
0.36 parts of antioxidant (mass ratio of hindered phenol antioxidant to phosphite antioxidant is 1:2);
0.3 part of light stabilizer (mass ratio of hindered amine light stabilizer to cinnamate is 1:2);
0.3 part of vinyltris (. Beta. -methoxyethoxy) silane.
The POE resin layer comprises the following components in parts by weight:
100 parts of POE resin (with 35 weight percent of octene content);
1.5 parts of 1,1- (tert-butyl diperoxide) -3, 5-trimethylcyclohexane;
2.5 parts of modified cross-linking agent;
0.1 part of antioxidant (mass ratio of hindered phenol antioxidant to phosphite antioxidant is 1:2);
0.15 parts of light stabilizer (mass ratio of hindered amine light stabilizer to cinnamate is 1:2);
1.3 parts of modified silane coupling agent;
the preparation method of the modified crosslinking agent is the same as in example 1.
The preparation method of the modified silane coupling agent is the same as that of example 1.
The preparation method of the precipitation-preventing EPE co-extrusion packaging adhesive film comprises the following steps:
S1: mixing, namely mixing the raw materials of all layers into a mixer according to a formula, and mixing and stirring for 2 hours at the temperature of 40 ℃ and the rotating speed of 80rpm to obtain mixed raw materials for later use;
S2: co-extrusion is carried out to obtain the product,
Placing POE layer raw materials into a double-screw extruder, and melt blending at the temperature of 80 ℃, 90 ℃ and 100 ℃ and the rotating speed of 45rpm in each region respectively;
Placing EVA layer raw material into a double screw extruder, melting and blending at 80 deg.C, 90 deg.C, 100 deg.C and rotating speed of 50rpm respectively,
The three-layer laminated structure of the packaging adhesive film is formed by simultaneously discharging, traction compounding and stretching through co-extrusion casting film dies of three double-screw extruders;
s3: the composite film is subjected to thickness measurement, edge pressing, shaping, trimming and rolling to obtain the anti-precipitation EPE co-extrusion packaging adhesive film.
Comparative example 1 the same as example 1 was carried out, except that comparative example 1 uses the same parts by weight of pentaerythritol instead of the modified crosslinking agent in example 1.
Comparative example 2 the same as example 1 was conducted except that comparative example 2 was conducted using the same weight part of vinyltriethoxysilane as the modified silane coupling agent in example 1.
Comparative example 3 the same as example 1 is different in that the POE resin layer in comparative example 3 is composed of the following raw materials in parts by weight:
100 parts of POE resin (with the octene content of 25 weight percent);
1.2 parts of 1,1- (tert-butyl diperoxide) -3, 5-trimethylcyclohexane;
2.2 parts of pentaerythritol triacrylate;
0.1 part of antioxidant (mass ratio of hindered phenol antioxidant to phosphite antioxidant is 1:2);
0.15 parts of light stabilizer (mass ratio of hindered amine light stabilizer to cinnamate is 1:2);
1.3 parts of vinyl triethoxysilane;
Comparative example 4 the same as example 1 was carried out, except that the modified crosslinking agent of comparative example 4 was prepared as follows:
Adding bis (1-adamantyl) phosphorus chloride, pentaerythritol triacrylate and triethylamine into N, N-dimethylformamide under the condition of avoiding light, stirring for 2 hours at 0 ℃, slowly heating to room temperature, stirring and reacting until the hydroxyl absorption peak in a reaction system disappears on an infrared spectrum, performing reduced pressure distillation after the reaction is finished, dissolving concentrate in dichloromethane, adding deionized water, oscillating, separating liquid, taking an organic phase, adding anhydrous sodium sulfate for drying, filtering, taking filtrate, performing reduced pressure distillation, performing vacuum drying at 4 ℃ for 12 hours to obtain an intermediate product I,
The infrared data are as follows:
3516cm -1: -OH is absent; 1126cm -1: -P-O-present; 1608cm -1、811cm-1: -c=c-present;
the dosage ratio of the bis (1-adamantyl) phosphorus chloride to the pentaerythritol triacrylate to the triethylamine to the N, N-dimethylformamide is 1.1mol:1mol:1.1mol:500mL.
Comparative example 5 the same as example 1 was different in that the modified silane coupling agent in comparative example 5 was prepared as follows:
Adding 4- (1-adamantyl) phenol, acetic acid and vinyltriethoxysilane into 800mL of ethanol water solution (ethanol content 95 wt%) and adding acetic acid to adjust pH=5, stirring at room temperature for 2h, and distilling at 90 ℃ under reduced pressure to obtain a target product, wherein the infrared data are as follows:
3504cm -1: -OH vanishes; 1091cm -1: -Si-O-Si-presence; 1126cm -1: -P-O-present; 1620cm -1: -c=c-present.
The dosage ratio of the 4- (1-adamantyl) phenol to the vinyltriethoxysilane I is 1mol:1mol.
Comparative example 6 the same as example 1 was different in that the POE resin in comparative example 6 had an octene content of 40wt%.
Comparative example 7 the same as in example 1 was different in that the antioxidant in comparative example 7 was a one-component antioxidant 1076.
Comparative example 8 the same as in example 1 was conducted except that the antioxidant in comparative example 8 was a one-component antioxidant 168.
Comparative example 9 the same as example 1, except that the light stabilizer in comparative example 9 was a one-component light stabilizer UV-292.
Comparative example 10 the same as in example 1 was different in that the light stabilizer in comparative example 10 was a one-component light stabilizer UV-41.
Comparative example 11 the same as example 1, except that comparative example 11 was conducted using a mixture of pentaerythritol triacrylate and adamantane (CAS number: 281-23-2) in the same parts by weight at a molar ratio of 1:1.2; meanwhile, a mixture of vinyl triethoxysilane and adamantane (CAS number: 281-23-2) in the same weight part is adopted according to the mol ratio of 1:1.
Performance testing
The EPE co-extruded packaging films obtained in examples 1 to 12 and comparative examples 1 to 11 of the present invention were subjected to the relevant performance test, and the specific test results are shown in Table 1.
The test method comprises the following steps:
(1) Transmittance: the test was performed as described in GB/T29848-2013 ethylene-vinyl acetate copolymer (EVA) film for packaging photovoltaic modules.
(2) Degree of crosslinking: after the crosslinking reaction of the adhesive film, xylene extraction is used to determine the degree of crosslinking. The adhesive film was cut to 1mm size, weighed m 0 and placed in a stainless steel mesh bag, immersed in boiling xylene, extracted for 4 hours, the uncrosslinked adhesive film was extracted into xylene, leaving undissolved, i.e. crosslinked adhesive film m 1.
Crosslinking degree = crosslinked film m 1/film total weight m 0 x 100%
(3) Peel force test:
Sample preparation: 1) Preparing two adhesive film raw materials, a glass block and a flexible backboard block, wherein the adhesive film raw materials, the glass block and the flexible backboard block are 300mm multiplied by 150mm in size; 2) And (3) stacking the glass/adhesive films (two pieces)/flexible back plates in sequence, putting the glass/adhesive films into a vacuum laminating machine, laminating the glass/adhesive films according to the temperature and time required by a product, and ensuring that the adhesive films in the laminated sample have no bubbles. 3 samples were prepared; 3) The flexible back sheet/film layer was cut into test pieces with a width of 10 mm.+ -. 0.5mm every 5mm in the width direction for peel force test between the film and glass.
The test process comprises the following steps: the peel force F between the glass and the film was measured on a tensile tester at a tensile speed of 100 mm/min.+ -. 10mm/min according to the test method of GB/T2790-1995.
Test results: the peel strength was calculated as follows, taking an arithmetic average of 3 samples to the nearest 0.1N/cm.
σ＝F/B
Wherein, the peeling strength is sigma-180 degrees and N/cm; f-peel force, N; b-sample width, cm.
(4) Humid heat aging: and carrying out a wet heat aging test on the EPE adhesive film. Conditions are as follows: test conditions: +85 ℃, 85% relative humidity, test time 1000hr.
(5) Ultraviolet aging: the obtained EPE adhesive film is subjected to ultraviolet irradiation aging test according to the requirements specified by International electrotechnical Commission standard IEC 61345. Test conditions: the surface temperature of the test piece is 60+/-5 ℃, the ultraviolet wavelength range is 280-400nm, the irradiation intensity is 15 kW.h/m 2, and the ultraviolet irradiation test time is 2000hr.
The yellowing index (. DELTA.YI) before and after the test was measured according to HG/T3862-2006.
(6) PID power decay: and (3) testing the PID of the photovoltaic module according to the line standard IEC-62804, and testing the conditions: 1500V voltage, 85 ℃, 85% relative humidity, 192h.
TABLE 1
As can be seen from examples 1 to 12 in Table 1, the anti-precipitation EPE co-extrusion packaging adhesive film of the present invention has excellent low auxiliary agent precipitation property and PID resistance. Wherein, the higher the POE glue line thickness, the better the PID resistance.
As can be seen from example 1 and comparative examples 1, 3-4, the EPE film of the present invention uses an adamantane structure anchoring assistant in the self-made modified crosslinking agent to reduce the migration; the polar group of the carbamate structure plays a role of adsorbing other polar auxiliary agents at the same time. Meanwhile, the large steric hindrance structural group has a larger blocking effect on free molecules and electrons, and is reflected in better PID resistance.
As can be seen from examples 1 and comparative examples 2 to 3 and 5, the EPE adhesive film of the present invention has more adamantane structure content, better migration resistance and good PID resistance by using the self-made modified silane coupling agent.
From example 1 and comparative example 6, it can be observed that the use of lower-octene-content POE particles for the POE gum layer in the EPE adhesive film in the invention can effectively improve the performance of resisting migration of auxiliary agents and the like, and the adhesive film is not delaminated and has excellent PID resistance.
From example 1 and comparative examples 7-10, it can be observed that EPE in the present invention has a positive effect on the selection of antioxidants and light stabilizers and the effect of compounding the adhesive film.
As can be seen from example 1 and comparative example 11, the EPE film of the present invention using the self-made modified silane coupling agent and the modified crosslinking agent has more excellent adamantane structure dispersibility, and adsorptivity of urethane structure to other polar groups, which is manifested in no delamination and more excellent PID resistance.
In conclusion, the precipitation-preventing EPE co-extrusion packaging adhesive film disclosed by the invention is prepared by co-extrusion through the formula design of a self-made modified cross-linking agent and a modified silane coupling agent, has excellent auxiliary agent precipitation prevention property and also has the excellent problem of inhibiting induced potential difference attenuation, and the service life of a product can be effectively prolonged.
With the above-described preferred embodiments according to the present invention as an illustration, the above-described descriptions can be used by persons skilled in the relevant art to make various changes and modifications without departing from the scope of the technical idea of the present invention. The technical scope of the present invention is not limited to the description, but must be determined according to the scope of claims.
Claims (2)
1. An anti-precipitation EPE co-extrusion packaging adhesive film is of a layered structure, and an outermost layer is an EVA resin layer, and is characterized in that,
The middle layer is a POE resin layer;
the POE resin layer comprises a modified cross-linking agent and a modified silane coupling agent as raw materials; wherein the method comprises the steps of
The modified cross-linking agent is obtained by reacting diisocyanate with a phenol derivative to form a carbamate chemical bond;
The modified silane coupling agent is obtained by sequentially reacting a phosphorus chloride derivative with enol, mercaptoalcohol, vinyl siloxane or mercaptopropyl siloxane; and
The modified silane coupling agent molecular structure simultaneously contains a-Si-O-Si-structure, an adamantane structure and a-C=C-structure;
the EVA resin layer comprises the following components in parts by weight:
100 parts of EVA resin;
0.5-1.5 parts of initiator;
0.5-1 part of cross-linking agent;
0.1-0.5 part of antioxidant;
0.1-0.5 part of light stabilizer;
0.2-0.6 part of coupling agent;
the POE resin layer comprises the following components in parts by weight:
100 parts of POE resin;
0.5-1.5 parts of initiator;
1.5-2.5 parts of modified cross-linking agent;
0.05-0.3 part of antioxidant;
0.05-0.3 part of light stabilizer;
0.6-1.8 parts of modified silane coupling agent;
the content of octene in the POE resin is 20-35wt%;
the phosphorus chloride derivative is bis (1-adamantyl) phosphorus chloride;
the antioxidant is a mixture of hindered phenol antioxidant and phosphite antioxidant according to the mass ratio of 1:1-3;
the light stabilizer is a mixture of hindered amine light stabilizer and cinnamate according to the mass ratio of 1:1-3;
the preparation method of the modified cross-linking agent comprises the following steps:
step S11, evenly mixing diisocyanate, dibutyl tin dilaurate and N, N-dimethylformamide;
Step S12, mixing a phenol derivative and N, N-dimethylformamide, and dripping the mixture into the reaction system in the step S11, so as to react until the hydroxyl in the reaction system disappears; then pentaerythritol triacrylate is added into the reaction system, and the reaction is carried out until isocyanate in the reaction system disappears, so as to obtain a modified crosslinking agent;
The dosage ratio of the diisocyanate, the phenol derivative, the pentaerythritol triacrylate to the N, N-dimethylformamide in the step S11 is as follows: 1mol:1mol: 1.1 to 1.2 mol:500-800mL;
The dosage of the dibutyl tin dilaurate is 0.3-0.5wt% of the total mass of the diisocyanate and the phenol derivative;
the diisocyanate comprises at least one of isophorone diisocyanate and dicyclohexylmethane-4, 4' -diisocyanate;
the phenol derivative is 4- (1-adamantyl) phenol;
the preparation method of the modified silane coupling agent comprises the following steps:
step S21, adding a phosphorus chloride derivative, enol and triethylamine into N, N-dimethylformamide, and stirring for reaction to obtain an intermediate product I; wherein the method comprises the steps of
The dosage ratio of the phosphorus chloride derivative, the enol, the triethylamine and the N, N-dimethylformamide is 1mol:1.1 to 1.2mol:1.1 to 1.2mol:500-800mL;
Step S22, reacting the intermediate product I with mercapto alcohol under the action of a photoinitiator to obtain an intermediate product II;
the dosage ratio of the intermediate product I to the mercapto alcohol is added according to the molar ratio of the carbon-carbon double bond to the mercapto group of 1:1;
The photoinitiator is used in an amount of 2wt% of the total mass of the reactants;
Step S23, performing a coupling reaction on the intermediate product II, acetic acid and a silane coupling agent to obtain a modified silane coupling agent;
the dosage ratio of the intermediate product II to the silane coupling agent is 1mol:1mol;
the ethanol water solution has the ethanol content of 95wt%;
the enol comprises at least one of 5-hexen-1-ol, 4-penten-1-ol, undecenol and 4-allylphenol;
the mercapto alcohol comprises at least one of 6-mercapto hex-1-ol, 3-mercapto-1-hexanol and dimercaptopropanol;
The silane coupling agent comprises at least one of vinyl triethoxysilane and gamma-mercaptopropyl triethoxysilane;
The photoinitiator is a free radical type I photoinitiator;
The initiator comprises at least one of tert-butyl peroxy-2-ethylhexyl carbonate, dibenzoyl peroxide, 2, 5-dimethyl-2, 5-bis (benzoyl peroxide) hexane and 1,1- (di-tert-butyl peroxide) -3, 5-trimethylcyclohexane.
2. The preparation method of the precipitation-preventing EPE co-extrusion packaging adhesive film is characterized by comprising the following steps of:
s1: mixing, namely adding and mixing the raw materials of each layer of the anti-precipitation EPE co-extrusion packaging adhesive film in the formula in a mixer according to the formula amount to obtain mixed raw materials for later use;
S2: co-extrusion is carried out to obtain the product,
Placing POE layer raw materials into a double-screw extruder, and carrying out melt blending;
placing EVA layer raw materials into a double-screw extruder, and melt blending;
Packaging the layered structure of the adhesive film, and simultaneously discharging, traction compounding and stretching to form a film through co-extrusion casting film dies of a plurality of double-screw extruders;
s3: the composite film is subjected to thickness measurement, edge pressing, shaping, trimming and rolling to obtain the anti-precipitation EPE co-extrusion packaging adhesive film.
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| CN116855191A (en) * | 2023-09-01 | 2023-10-10 | 苏州弘道新材料有限公司 | High-impact adhesive film and preparation method thereof |
| CN116948538A (en) * | 2023-07-14 | 2023-10-27 | 安徽隆芃新材料科技有限公司 | High-toughness photovoltaic EVA adhesive film and preparation process thereof |
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| JP6356383B2 (en) * | 2013-02-15 | 2018-07-11 | リンテック株式会社 | Adhesive composition, adhesive and adhesive sheet |
| CN114605927B (en) * | 2022-03-31 | 2023-08-11 | 江苏中来新材科技有限公司 | high-PID-resistance photovoltaic adhesive film, preparation method thereof and photovoltaic module |
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| CN116948538A (en) * | 2023-07-14 | 2023-10-27 | 安徽隆芃新材料科技有限公司 | High-toughness photovoltaic EVA adhesive film and preparation process thereof |
| CN116855191A (en) * | 2023-09-01 | 2023-10-10 | 苏州弘道新材料有限公司 | High-impact adhesive film and preparation method thereof |
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