CN117210142B - Ultraviolet-resistant battery packaging EVA adhesive film - Google Patents
Ultraviolet-resistant battery packaging EVA adhesive film Download PDFInfo
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- CN117210142B CN117210142B CN202311251457.5A CN202311251457A CN117210142B CN 117210142 B CN117210142 B CN 117210142B CN 202311251457 A CN202311251457 A CN 202311251457A CN 117210142 B CN117210142 B CN 117210142B
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- 239000002313 adhesive film Substances 0.000 title claims abstract description 57
- 238000004806 packaging method and process Methods 0.000 title claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 96
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 54
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 25
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 270
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 178
- 239000013067 intermediate product Substances 0.000 claims description 128
- 238000003756 stirring Methods 0.000 claims description 98
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 89
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 86
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 77
- 239000008367 deionised water Substances 0.000 claims description 74
- 229910021641 deionized water Inorganic materials 0.000 claims description 74
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 72
- 239000007864 aqueous solution Substances 0.000 claims description 50
- 238000002386 leaching Methods 0.000 claims description 50
- 238000001914 filtration Methods 0.000 claims description 49
- NGSWKAQJJWESNS-UHFFFAOYSA-N 4-coumaric acid Chemical compound OC(=O)C=CC1=CC=C(O)C=C1 NGSWKAQJJWESNS-UHFFFAOYSA-N 0.000 claims description 48
- 239000003963 antioxidant agent Substances 0.000 claims description 40
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 36
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 35
- 230000003078 antioxidant effect Effects 0.000 claims description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- NNMXSTWQJRPBJZ-UHFFFAOYSA-K europium(iii) chloride Chemical group Cl[Eu](Cl)Cl NNMXSTWQJRPBJZ-UHFFFAOYSA-K 0.000 claims description 27
- 238000001291 vacuum drying Methods 0.000 claims description 27
- 238000005406 washing Methods 0.000 claims description 26
- 239000000047 product Substances 0.000 claims description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 24
- 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 24
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 24
- 239000000706 filtrate Substances 0.000 claims description 24
- 239000012074 organic phase Substances 0.000 claims description 24
- 239000000376 reactant Substances 0.000 claims description 24
- -1 rare earth chloride Chemical class 0.000 claims description 23
- 239000012670 alkaline solution Substances 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 18
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 17
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 16
- 229920005989 resin Polymers 0.000 claims description 16
- 239000011347 resin Substances 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- 230000004224 protection Effects 0.000 claims description 12
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 claims description 11
- 239000007822 coupling agent Substances 0.000 claims description 11
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 7
- 238000004132 cross linking Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000003431 cross linking reagent Substances 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- RIPYNJLMMFGZSX-UHFFFAOYSA-N (5-benzoylperoxy-2,5-dimethylhexan-2-yl) benzenecarboperoxoate Chemical compound C=1C=CC=CC=1C(=O)OOC(C)(C)CCC(C)(C)OOC(=O)C1=CC=CC=C1 RIPYNJLMMFGZSX-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- DLSMLZRPNPCXGY-UHFFFAOYSA-N tert-butylperoxy 2-ethylhexyl carbonate Chemical compound CCCCC(CC)COC(=O)OOOC(C)(C)C DLSMLZRPNPCXGY-UHFFFAOYSA-N 0.000 claims 1
- 238000002834 transmittance Methods 0.000 abstract description 15
- 150000002910 rare earth metals Chemical class 0.000 abstract description 13
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 abstract description 11
- WBYWAXJHAXSJNI-VOTSOKGWSA-M trans-cinnamate Chemical group [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 230000006750 UV protection Effects 0.000 abstract description 2
- 230000003287 optical effect Effects 0.000 abstract description 2
- 125000003277 amino group Chemical group 0.000 abstract 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 71
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 71
- BLORRZQTHNGFTI-ZZMNMWMASA-L calcium-L-ascorbate Chemical compound [Ca+2].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] BLORRZQTHNGFTI-ZZMNMWMASA-L 0.000 description 37
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 34
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 20
- 238000012360 testing method Methods 0.000 description 20
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 description 15
- 230000032683 aging Effects 0.000 description 12
- 230000001678 irradiating effect Effects 0.000 description 11
- 150000007942 carboxylates Chemical class 0.000 description 10
- 238000002284 excitation--emission spectrum Methods 0.000 description 10
- 230000003313 weakening effect Effects 0.000 description 10
- 239000004342 Benzoyl peroxide Substances 0.000 description 7
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 7
- 235000019400 benzoyl peroxide Nutrition 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 6
- 238000004383 yellowing Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 229930016911 cinnamic acid Natural products 0.000 description 4
- 235000013985 cinnamic acid Nutrition 0.000 description 4
- 239000004611 light stabiliser Substances 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000002479 acid--base titration Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229940114081 cinnamate Drugs 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Landscapes
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention belongs to the technical field of EVA adhesive films, and particularly relates to an ultraviolet-resistant battery packaging EVA adhesive film. The conventional EVA photovoltaic film is subject to the effects of light, heat and oxygen in an outdoor environment, is easy to yellow, and is poor in light transmittance, so that the photoelectric conversion efficiency of the solar cell panel is reduced. According to the ultraviolet-resistant battery packaging EVA adhesive film, the formula system contains the self-made ultraviolet-resistant auxiliary agent, the molecular structure of the ultraviolet-resistant auxiliary agent contains a hindered amine structure, a cinnamate structure and a rare earth europium complex, and under the combined action of the hindered amine structure, the cinnamate structure and the rare earth europium complex, the EVA adhesive film has excellent ultraviolet resistance, better optical transparency, low yellowness index and good weather resistance, and the photoelectric conversion efficiency of a photovoltaic cell can be further improved.
Description
Technical Field
The invention belongs to the technical field of EVA adhesive films, and particularly relates to an ultraviolet-resistant battery packaging EVA adhesive film.
Background
The solar power generation technology mainly comprising solar photovoltaic panels is the most direct and effective means for efficiently utilizing solar energy. However, solar photovoltaic modules are subject to failure in complex environments such as light, heat, oxygen, and the like. EVA (ethylene-vinyl acetate copolymer) is the mainstream photovoltaic module packaging material in the market at present. In order to prolong the service life of the photovoltaic module and improve the ageing resistance of the EVA adhesive film, a method for modifying the adhesive film by adding additives such as an antioxidant, an ultraviolet absorber and the like on the basis of a pure EVA adhesive film has been developed.
The EVA photovoltaic film has higher requirement on the light stabilizer, and the light stabilizer which can be used for the solar EVA packaging adhesive film on the market at present is generally prepared by compounding a benzophenone or benzotriazole ultraviolet absorber with a hindered amine light stabilizer respectively. Benzophenone and benzotriazole ultraviolet absorbers are easy to react with free radicals to form a chromophore, and can be decomposed and disabled for a long time due to the long-term action of hot oxygen, so that the EVA adhesive film is subjected to yellowing, the high light transmittance of the EVA adhesive film is further affected, and finally the photoelectric conversion efficiency of the solar cell panel is reduced. A large number of researches show that the effect of light stabilization produced by the combination of the hindered amine light stabilizer and the cinnamic acid ester ultraviolet absorber is optimal.
Currently, in the market, the solar panel using EVA film as the packaging material of the solar panel is not ideal in photoelectric conversion efficiency in long-term outdoor use. The fluorescent rare earth complex has good fluorescent characteristic, high fluorescent intensity and long fluorescent life due to the transition effect of the 4f electron orbit. The novel rare earth complex light conversion material is developed by the teaching subject of Beijing university Huang Chunhui, the photoelectric conversion efficiency of the prepared solar silicon cell light conversion film can be remarkably improved, however, the solar silicon cell light conversion film still has yellowing or browning phenomenon in the long-term outdoor use process, and the photoelectric conversion efficiency of a photovoltaic cell is reduced until the photoelectric effect completely disappears.
Disclosure of Invention
The problems in the prior art are: the conventional EVA photovoltaic film is subject to the effects of light, heat and oxygen in an outdoor environment, is easy to yellow, and is poor in light transmittance, so that the photoelectric conversion efficiency of the solar cell panel is reduced. Aiming at the problems, the invention provides an ultraviolet-resistant battery packaging EVA adhesive film which comprises the following raw material components in parts by weight:
specifically, the EVA resin has a VA content of 33-35% and a Melt Index (MI) of 31-34.
Specifically, the thermal initiator comprises at least one of tert-butyl peroxy-2-ethylhexyl carbonate, 2, 5-dimethyl-2, 5-bis (benzoylperoxy) hexane or 1,1- (tert-butyl diperoxide) -3, 5-trimethylcyclohexane.
Specifically, the crosslinking agent comprises at least one of triallyl isocyanurate, trimethylolpropane trimethacrylate and ethoxylated trimethylolpropane triacrylate.
Specifically, the antioxidant comprises at least one of hindered phenol antioxidants and phosphite antioxidants.
Specifically, the preparation method of the ultraviolet resistant auxiliary agent comprises the following steps:
(1)N 2 under the protection, placing 4-hydroxy cinnamic acid, triethylamine and dichloromethane into a flask, stirring uniformly under ice bath conditions, dissolving acryloyl chloride into dichloromethane, placing into a constant pressure dropping funnel, dropwise adding the solution into the flask while stirring, continuously stirring for 8-12h at 0-5 ℃ after the dropwise adding, filtering the solution after the reaction is finished, adding 20wt% of dilute hydrochloric acid aqueous solution into the filtrate for washing for 3 times, adding saturated sodium bicarbonate aqueous solution for washing for 3 times, washing with deionized water for 3 times, standing for separating liquid, taking an organic phase, adding anhydrous sodium sulfate into the organic phase for drying, filtering to remove anhydrous sodium sulfate, taking filtrate, distilling under reduced pressure to remove dichloromethane, and vacuum drying the obtained product to constant weight at 50 ℃ to obtain an intermediate product I;
The dosage ratio of the 4-hydroxy cinnamic acid to triethylamine, dichloromethane, acryloyl chloride, dichloromethane, 20wt% of dilute hydrochloric acid aqueous solution, saturated sodium bicarbonate aqueous solution, deionized water and anhydrous sodium sulfate is as follows: 0.1mol:0.22mol:200mL:0.12mol:300mL:400mL:400mL:400mL:10g;
(2) Adding an intermediate product I, isocyanoethyl methacrylate, a photoinitiator and methylene dichloride into a flask, stirring and dissolving, placing a reaction system under a UV lamp, performing irradiation crosslinking, standing after the reaction is finished, and distilling under reduced pressure to remove the methylene dichloride to obtain an intermediate product II;
the dosage ratio of the intermediate product I to the isocyanoethyl methacrylate to the methylene dichloride is as follows: (10-50) g:10g:300mL;
the dosage of the photoinitiator is 2% of the total mass of the reactants;
(3) Adding an intermediate product II, dibutyltin dilaurate, a 2, 6-tetramethyl-4-piperidinol derivative and N, N-dimethylformamide into a flask, stirring uniformly, stirring at a constant temperature of 40-80 ℃ for reaction for 3-6 hours, removing the N, N-dimethylformamide by reduced pressure distillation after the reaction is finished, adding absolute ethyl alcohol into a reactant, filtering, taking insoluble matters, leaching the insoluble matters with the absolute ethyl alcohol for 2 times, leaching the insoluble matters with deionized water for 3 times, and then drying in vacuum at 50 ℃ until the weight is constant to obtain an intermediate product III;
The dosage ratio of the intermediate product II to the N, N-dimethylformamide, the absolute ethyl alcohol and the deionized water is 10g:100mL:300mL:100mL:100mL;
the molar ratio of the 2, 6-tetramethyl-4-piperidinol derivative to the isocyanoethyl methacrylate is 1:1;
the dosage of the dibutyl tin dilaurate is 0.5% of the total mass of the intermediate product II and the 2, 6-tetramethyl-4-piperidinol derivative;
(4) Adding intermediate products III and N, N-dimethylformamide into a three-mouth bottle, putting into a constant temperature tank, heating to 60-80 ℃, then adding rare earth chloride, fully and uniformly stirring, then dropwise adding alkaline solution with the mass concentration of 30wt% by using a dropping funnel, slowly dropwise adding, adjusting the pH value of the solution to be 6-7, carrying out constant temperature stirring reaction for 20-30h, cooling to room temperature after the reaction is finished, carrying out vacuum concentration, injecting absolute ethyl alcohol, filtering, taking insoluble matters, leaching the insoluble matters with absolute ethyl alcohol for 2 times, leaching with deionized water for 3 times, and then carrying out vacuum drying at 50 ℃ until the weight is constant, thus obtaining a target product IV, namely the ultraviolet resistant auxiliary agent;
the dosage ratio of the intermediate product III to the N, N-dimethylformamide, the absolute ethyl alcohol and the deionized water is as follows: 10g:500mL:1000mL:300mL:300mL;
The rare earth chloride is added according to the molar ratio of europium ions to carboxyl in the intermediate product III of 1:3.
Specifically, the photoinitiator comprises at least one of TPO, TPO-L, 651, 1173, 184.
In particular, the method comprises the steps of, the 2, 6-tetramethyl-4-piperidinol derivative comprises 2, 6-tetramethyl-4-piperidinol at least one of 1,2, 6-pentamethyl-4-piperidinol.
Specifically, the rare earth chloride is europium chloride.
Specifically, the alkaline solution comprises at least one of aqueous sodium hydroxide solution and ammonia water.
The chemical formula of the ultraviolet resistant auxiliary agent preparation process is as follows:
the invention has the following beneficial effects:
(1) The formula system of the EVA adhesive film comprises the self-made ultraviolet-resistant auxiliary agent, and the molecular structure of the ultraviolet-resistant auxiliary agent simultaneously comprises a hindered amine structure, a cinnamate structure and rare earth europium;
the hindered amine structure can generate nitroxide free radicals, has the capability of capturing the free radicals, and is beneficial to improving the heat resistance and photo-oxidative aging resistance, especially the ultraviolet light resistance stability, of the obtained EVA adhesive film;
the cinnamate has excellent ultraviolet absorption capacity and larger molar absorption coefficient, and is also beneficial to improving the ultraviolet resistance of the obtained EVA adhesive film;
The molecular chain of the ultraviolet-resistant auxiliary agent simultaneously contains a hindered amine structure and a cinnamate structure, the heat resistance and photo-oxidative aging resistance of the hindered amine structure and the UV absorption effect of the cinnamate structure have synergistic effect, the light transmittance of the adhesive film is better, the yellowness index is low, and the obtained EVA adhesive film has better weather resistance;
the ultraviolet-resistant auxiliary agent also contains rare earth europium complex in the molecular structure, and the rare earth europium can absorb ultraviolet rays of 230-320mm, so that the aging of the EVA adhesive film can be slowed down, and the weather resistance and the light stability of the EVA adhesive film are improved;
the rare earth europium can absorb ultraviolet rays, generate electron orbit energy level transition, release visible light and improve the photoelectric conversion efficiency of the photovoltaic cell;
the empty track of the rare earth europium can adsorb free acetic acid generated in the EVA decomposition process, and plays a role in inhibiting EVA decomposition in the EVA adhesive film;
after the rare earth europium is subjected to high molecular coordination modification, the compatibility between the rare earth europium and EVA matrix resin is improved, the dispersibility of the rare earth europium in EVA is improved, and the rare earth europium is very beneficial to further slowing down the aging of an EVA adhesive film and improving the weather resistance and the light stability of the EVA adhesive film;
(2) The antioxidant in the formula system of the EVA adhesive film is a composition compounded by hindered phenol antioxidants and phosphite antioxidants;
The hindered phenol antioxidant can be carried out in a destructive reaction manner from chain oxidation reaction and has a main antioxidant effect;
the phosphite antioxidant is combined with the residual initiator in the EVA adhesive film formula to inhibit the automatic catalytic action of oxidation, and the antioxidant and the ultraviolet-resistant auxiliary agent act synergistically, so that the EVA adhesive film has more excellent aging resistance and low yellowing index.
The specific embodiment is as follows:
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.
The EVA resin described in the examples below in 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 described in the following examples in the present invention is antioxidant 1076.
The phosphite antioxidant described in the following examples of the present invention is antioxidant 168.
The coupling agent described in the examples below in the present invention is vinyltris (. Beta. -methoxyethoxy) silane.
The carboxyl group content in the following examples and comparative examples of the present invention can be measured by acid-base titration.
Example 1
The ultraviolet-resistant battery packaging EVA adhesive film comprises the following raw materials in parts by weight:
100 parts of EVA resin;
1.1 parts of 2, 5-dimethyl-2, 5-bis (benzoyl peroxide) hexane;
0.48 parts of triallyl isocyanurate;
1 part of ethoxylated trimethylolpropane triacrylate;
0.04 parts of hindered phenol antioxidant;
0.08 part of phosphite antioxidant;
0.28 parts of ultraviolet resistant auxiliary agent;
0.5 part of coupling agent.
The preparation method of the ultraviolet resistant auxiliary agent comprises the following steps:
(1)N 2 under the protection, placing 4-hydroxy cinnamic acid, triethylamine and dichloromethane into a flask, stirring uniformly under ice bath conditions, dissolving acryloyl chloride into dichloromethane, placing into a constant pressure dropping funnel, dropwise adding into the flask while stirring, continuously stirring for 12 hours at 0 ℃ after the dropwise adding is finished, filtering reaction liquid by filter paper after the reaction is finished, adding 20wt% of dilute hydrochloric acid aqueous solution into filtrate to wash for 3 times, adding saturated sodium bicarbonate aqueous solution to wash for 3 times, washing by deionized water for 3 times, standing for separating liquid, taking an organic phase, adding anhydrous sodium sulfate into the organic phase to dry, filtering to remove anhydrous sodium sulfate, taking filtrate, distilling under reduced pressure to remove dichloromethane, and vacuum drying the obtained product to constant weight at 50 ℃ to obtain an intermediate product I.
The infrared data for intermediate I are as follows:
3512cm -1 : -OH vanishes; 3347cm -1 : -OH (carboxyl) present; 1760cm -1 : -c=o (carboxyl) present; 3011cm -1 、1501cm -1 、1594cm -1 : the benzene ring exists; 1738cm -1 : ester-c=o present; 1605cm -1 、810cm -1 : -c=c-present.
The dosage ratio of the 4-hydroxy cinnamic acid to triethylamine, dichloromethane, acryloyl chloride, dichloromethane, 20wt% of dilute hydrochloric acid aqueous solution, saturated sodium bicarbonate aqueous solution, deionized water and anhydrous sodium sulfate is as follows: 0.1mol:0.22mol:200mL:0.12mol:300mL:400mL:400mL:400mL:10g.
(2) Adding the intermediate product I, isocyanoethyl methacrylate, a photoinitiator and methylene dichloride into a flask, stirring and dissolving, and then placing the reaction system under a UV lamp at the energy of 400mJ/cm 2 Irradiating for 5min under the UV light intensity, standing, distilling under reduced pressure to remove dichloromethane,intermediate II (mn=28400, d=1.26) is obtained;
intermediate II infrared data were as follows:
3347cm -1 : -OH (carboxyl) present; 1760cm -1 : -c=o (carboxyl) present; 3011cm -1 、1501cm -1 、1594cm -1 : the benzene ring exists; 1738cm -1 : ester-c=o is present and enhanced; 1605cm -1 、810cm -1 : -c=c-vanishes; 2275cm -1 : -NCO present.
The dosage ratio of the intermediate product I to the isocyanoethyl methacrylate to the methylene dichloride is as follows: 40g:10g:300mL;
the dosage of the photo initiator TPO-L is 2% of the total mass of the reactants;
(3) Adding an intermediate product II, dibutyltin dilaurate, a 2, 6-tetramethyl-4-piperidinol derivative and N, N-dimethylformamide into a flask, stirring uniformly, stirring at a constant temperature of 60 ℃ for reacting for 5 hours, distilling under reduced pressure to remove the N, N-dimethylformamide after the reaction is finished, adding absolute ethyl alcohol into a reactant, filtering, taking insoluble matters, leaching the insoluble matters with the absolute ethyl alcohol for 2 times, leaching with deionized water for 3 times, and then drying in vacuum at 50 ℃ to constant weight to obtain an intermediate product III;
the infrared data for intermediate III are as follows:
3347cm -1 : -OH (carboxyl) present; 1760cm -1 : -c=o (carboxyl) present; 3011cm -1 、1501cm -1 、1594cm -1 : the benzene ring exists; 1738cm -1 : ester-c=o present; 2275cm -1 : -NCO vanishing; 1682cm -1 : amide-c=o present; 1525cm -1 : amide-NH-is present.
The dosage ratio of the intermediate product II to the N, N-dimethylformamide, the absolute ethyl alcohol and the deionized water is 10g:100mL:300mL:100mL:100mL;
the molar ratio of the 2, 6-tetramethyl-4-piperidinol derivative to the isocyanoethyl methacrylate is 1:1;
the dosage of the dibutyl tin dilaurate is 0.5% of the total mass of the intermediate product II and the 2, 6-tetramethyl-4-piperidinol derivative;
(4) Adding intermediate products III and N, N-dimethylformamide into a three-mouth bottle, putting into a constant temperature tank, heating to 70 ℃, then adding europium chloride, fully and uniformly stirring, then dropwise adding alkaline solution with the mass concentration of 30wt% by using a dropping funnel, slowly dropwise adding, adjusting the pH value of the solution to be=6, stirring at constant temperature for 28 hours, cooling to room temperature after the reaction is finished, concentrating in vacuum, injecting absolute ethyl alcohol, filtering, taking insoluble matters, leaching the insoluble matters for 2 times by using absolute ethyl alcohol, leaching the insoluble matters for 3 times by using deionized water, and then vacuum-drying to constant weight at 50 ℃ to obtain a target product IV, namely the ultraviolet-resistant auxiliary agent;
the infrared data of the ultraviolet resistant auxiliary agent are as follows:
3347cm -1 : -OH (carboxyl) weakening; 1760cm -1 : -c=o (carboxyl) disappears; 3011cm -1 、1501cm -1 、1594cm -1 : the benzene ring exists; 1738cm -1 : ester-c=o present; 1682cm -1 : amide-c=o present; 1525cm -1 : amide-NH-present; 1382cm -1 、1428cm -1 : the carboxylate is present.
Fluorescence excitation emission spectrum: 590nm and 615nm are Eu 3+ 615nm is the strongest characteristic emission peak.
The dosage ratio of the intermediate product III to the N, N-dimethylformamide, the absolute ethyl alcohol and the deionized water is as follows: 10g:500mL:1000mL:300mL:300mL.
The dosage of europium chloride is added according to the molar ratio of europium ions to carboxyl in the intermediate product III of 1:3.
The photoinitiator is TPO-L.
The 2, 6-tetramethyl-4-piperidinol derivative is 2, 6-tetramethyl-4-piperidinol.
The alkaline solution is sodium hydroxide aqueous solution.
Example 2
The ultraviolet-resistant battery packaging EVA adhesive film comprises the following raw materials in parts by weight:
100 parts of EVA resin;
1.1 parts of 2, 5-dimethyl-2, 5-bis (benzoyl peroxide) hexane;
0.48 parts of triallyl isocyanurate;
1 part of ethoxylated trimethylolpropane triacrylate;
0.04 parts of hindered phenol antioxidant;
0.08 part of phosphite antioxidant;
0.2 part of ultraviolet resistant auxiliary agent;
0.5 part of coupling agent.
The preparation method of the ultraviolet resistant auxiliary agent comprises the following steps:
(1)N 2 under the protection, placing 4-hydroxy cinnamic acid, triethylamine and dichloromethane into a flask, stirring uniformly under ice bath conditions, dissolving acryloyl chloride into dichloromethane, placing into a constant pressure dropping funnel, dropwise adding into the flask while stirring, continuously stirring for 8 hours at 5 ℃ after the dropwise adding, filtering reaction liquid by using filter paper after the reaction is finished, adding 20wt% of dilute hydrochloric acid aqueous solution into filtrate to wash for 3 times, adding saturated sodium bicarbonate aqueous solution to wash for 3 times, washing by using deionized water for 3 times, standing for separating liquid, taking an organic phase, adding anhydrous sodium sulfate into the organic phase to dry, filtering to remove anhydrous sodium sulfate, taking filtrate, distilling under reduced pressure to remove dichloromethane, and vacuum drying the obtained product to constant weight at 50 ℃ to obtain an intermediate product I;
The infrared data for intermediate I are as follows: 3512cm -1 : -OH vanishes; 3347cm -1 : -OH (carboxyl) present; 1760cm -1 : -c=o (carboxyl) present; 3011cm -1 、1501cm -1 、1594cm -1 : the benzene ring exists; 1738cm -1 : ester-c=o present; 1605cm -1 、810cm -1 : -c=c-present.
The dosage ratio of the 4-hydroxy cinnamic acid to triethylamine, dichloromethane, acryloyl chloride, dichloromethane, 20wt% of dilute hydrochloric acid aqueous solution, saturated sodium bicarbonate aqueous solution, deionized water and anhydrous sodium sulfate is as follows: 0.1mol:0.22mol:200mL:0.12mol:300mL:400mL:400mL:400mL:10g;
(2) Intermediate I, isocyanoethyl methacrylate, photoinitiator, and methylene chlorideAdding into a flask, stirring for dissolving, and placing the reaction system under a UV lamp at 400mJ/cm 2 Irradiating for 5min under UV light intensity, standing after the reaction is completed, and distilling under reduced pressure to remove dichloromethane to obtain an intermediate product II (Mn=28180, D=1.26);
the infrared data for intermediate II are as follows:
3347cm -1 : -OH (carboxyl) present; 1760cm -1 : -c=o (carboxyl) present; 3011cm -1 、1501cm -1 、1594cm -1 : the benzene ring exists; 1738cm -1 : ester-c=o is present and enhanced; 1605cm -1 、810cm -1 : -c=c-vanishes; 2275cm -1 : -NCO present.
The dosage ratio of the intermediate product I to the isocyanoethyl methacrylate to the methylene dichloride is as follows: 40g:10g:300mL;
The dosage of the photoinitiator is 2% of the total mass of the reactants;
(3) Adding an intermediate product II, dibutyltin dilaurate, a 2, 6-tetramethyl-4-piperidinol derivative and N, N-dimethylformamide into a flask, stirring uniformly, stirring at a constant temperature of 40 ℃ for reaction for 6 hours, removing the N, N-dimethylformamide by reduced pressure distillation after the reaction is finished, adding absolute ethyl alcohol into a reactant, filtering, taking insoluble matters, leaching the insoluble matters with the absolute ethyl alcohol for 2 times, leaching with deionized water for 3 times, and then vacuum-drying at 50 ℃ to constant weight to obtain an intermediate product III;
the intermediate III infrared data are as follows:
3347cm -1 : -OH (carboxyl) present; 1760cm -1 : -c=o (carboxyl) present; 3011cm -1 、1501cm -1 、1594cm -1 : the benzene ring exists; 1738cm -1 : ester-c=o present; 2275cm -1 : -NCO vanishing; 1682cm -1 : amide-c=o present; 1525cm -1 : amide-NH-is present.
The dosage ratio of the intermediate product II to the N, N-dimethylformamide, the absolute ethyl alcohol and the deionized water is 10g:100mL:300mL:100mL:100mL;
the molar ratio of the 2, 6-tetramethyl-4-piperidinol derivative to the isocyanoethyl methacrylate is 1:1;
the dosage of the dibutyl tin dilaurate is 0.5% of the total mass of the intermediate product II and the 2, 6-tetramethyl-4-piperidinol derivative;
(4) Adding intermediate products III and N, N-dimethylformamide into a three-mouth bottle, putting into a constant temperature tank, heating to 80 ℃, then adding europium chloride, fully and uniformly stirring, then dropwise adding alkaline solution with the mass concentration of 30wt% by using a dropping funnel, slowly dropwise adding, adjusting the pH value of the solution to be=6, stirring at constant temperature for reacting for 20 hours, cooling to room temperature after the reaction is finished, concentrating in vacuum, injecting absolute ethyl alcohol, filtering, taking insoluble matters, leaching the insoluble matters for 2 times by using absolute ethyl alcohol, leaching the insoluble matters for 3 times by using deionized water, and then vacuum-drying to constant weight at 50 ℃ to obtain a target product IV, namely the ultraviolet resistant auxiliary agent;
the infrared data of the ultraviolet resistant auxiliary agent are as follows:
3347cm -1 : -OH (carboxyl) weakening; 1760cm -1 : -c=o (carboxyl) disappears; 3011cm -1 、1501cm -1 、1594cm -1 : the benzene ring exists; 1738cm -1 : ester-c=o present; 1682cm -1 : amide-c=o present; 1525cm -1 : amide-NH-present; 1382cm -1 、1428cm -1 : the carboxylate is present.
Fluorescence excitation emission spectrum: 590nm and 615nm are Eu 3+ 615nm is the strongest characteristic emission peak.
The dosage ratio of the intermediate product III to the N, N-dimethylformamide, the absolute ethyl alcohol and the deionized water is as follows: 10g:500mL:1000mL:300mL:300mL;
the dosage of europium chloride is added according to the molar ratio of europium ions to carboxyl in the intermediate product III of 1:3.
Specifically, the photoinitiator comprises TPO.
Specifically, the 2, 6-tetramethyl-4-piperidinol derivative is 2, 6-tetramethyl-4-piperidinol.
Specifically, the alkaline solution is an aqueous sodium hydroxide solution.
Example 3
The ultraviolet-resistant battery packaging EVA adhesive film comprises the following raw materials in parts by weight:
100 parts of EVA resin;
1.1 parts of 2, 5-dimethyl-2, 5-bis (benzoyl peroxide) hexane;
0.48 parts of triallyl isocyanurate;
1 part of ethoxylated trimethylolpropane triacrylate;
0.04 parts of hindered phenol antioxidant;
0.08 part of phosphite antioxidant;
0.4 part of ultraviolet resistant auxiliary agent;
0.5 part of coupling agent.
The preparation method of the ultraviolet resistant auxiliary agent comprises the following steps:
(1)N 2 under the protection, placing 4-hydroxy cinnamic acid, triethylamine and dichloromethane into a flask, stirring uniformly under ice bath conditions, dissolving acryloyl chloride into dichloromethane, placing into a constant pressure dropping funnel, dropwise adding the solution into the flask while stirring, continuously stirring for 10 hours at 0 ℃ after the dropwise adding, filtering the reaction solution by using filter paper after the reaction is finished, adding 20wt% of dilute hydrochloric acid aqueous solution into the filtrate for washing for 3 times, adding saturated sodium bicarbonate aqueous solution for washing for 3 times, washing by using deionized water for 3 times, standing for separating liquid, taking an organic phase, adding anhydrous sodium sulfate into the organic phase for drying, filtering to remove anhydrous sodium sulfate, taking filtrate, distilling under reduced pressure to remove dichloromethane, and vacuum drying the obtained product to constant weight at 50 ℃ to obtain an intermediate product I;
The infrared data for intermediate I are as follows: 3512cm -1 : -OH vanishes; 3347cm -1 : -OH (carboxyl) present; 1760cm -1 : -c=o (carboxyl) present; 3011cm -1 、1501cm -1 、1594cm -1 : the benzene ring exists; 1738cm -1 : ester-c=o present; 1605cm -1 、810cm -1 : -c=c-present.
The dosage ratio of the 4-hydroxy cinnamic acid to triethylamine, dichloromethane, acryloyl chloride, dichloromethane, 20wt% of dilute hydrochloric acid aqueous solution, saturated sodium bicarbonate aqueous solution, deionized water and anhydrous sodium sulfate is as follows: 0.1mol:0.22mol:200mL:0.12mol:300mL:400mL:400mL:400mL:10g;
(2) Adding intermediate I, isocyanoethyl methacrylate, photoinitiator and methylene dichloride into a flask, stirring to dissolve, placing the reaction system under a UV lamp at 400mJ/cm 2 Irradiating for 10min under UV light intensity, standing after the reaction is completed, and distilling under reduced pressure to remove dichloromethane to obtain an intermediate product II (Mn=29708, D=1.25);
the infrared data for intermediate II are as follows: 3347cm -1 : -OH (carboxyl) present; 1760cm -1 : -c=o (carboxyl) present; 3011cm -1 、1501cm -1 、1594cm -1 : the benzene ring exists; 1738cm -1 : ester-c=o is present and enhanced; 1605cm -1 、810cm -1 : -c=c-vanishes; 2275cm -1 : -NCO present.
The dosage ratio of the intermediate product I to the isocyanoethyl methacrylate to the methylene dichloride is as follows: 40g:10g:300mL;
The dosage of the photoinitiator is 2% of the total mass of the reactants;
(3) Adding an intermediate product II, dibutyltin dilaurate, a 2, 6-tetramethyl-4-piperidinol derivative and N, N-dimethylformamide into a flask, stirring uniformly, stirring at a constant temperature of 80 ℃ for reaction for 3 hours, removing the N, N-dimethylformamide by reduced pressure distillation after the reaction is finished, adding absolute ethyl alcohol into a reactant, filtering, taking insoluble matters, leaching the insoluble matters with the absolute ethyl alcohol for 2 times, leaching with deionized water for 3 times, and then vacuum-drying at 50 ℃ to constant weight to obtain an intermediate product III;
the infrared data for intermediate III are as follows: 3347cm -1 : -OH (carboxyl) present; 1760cm -1 : -c=o (carboxyl) present; 3011cm -1 、1501cm -1 、1594cm -1 : the benzene ring exists; 1738cm -1 : ester-c=o present; 2275cm -1 : -NCO vanishing; 1682cm -1 : amide-c=o present; 1525cm -1 : amide-NH-is present.
The dosage ratio of the intermediate product II to the N, N-dimethylformamide, the absolute ethyl alcohol and the deionized water is 10g:100mL:300mL:100mL:100mL;
the molar ratio of the 2, 6-tetramethyl-4-piperidinol derivative to the isocyanoethyl methacrylate is 1:1;
the dosage of the dibutyl tin dilaurate is 0.5% of the total mass of the intermediate product II and the 2, 6-tetramethyl-4-piperidinol derivative;
(4) Adding intermediate products III and N, N-dimethylformamide into a three-mouth bottle, putting into a constant temperature tank, heating to 60 ℃, then adding europium chloride, fully and uniformly stirring, then dropwise adding alkaline solution with the mass concentration of 30wt% by using a dropping funnel, slowly dropwise adding, adjusting the pH value of the solution to be=6, stirring at constant temperature for reaction for 30 hours, cooling to room temperature after the reaction is finished, concentrating in vacuum, injecting absolute ethyl alcohol, filtering, taking insoluble matters, leaching the insoluble matters for 2 times by using absolute ethyl alcohol, leaching the insoluble matters for 3 times by using deionized water, and then vacuum-drying to constant weight at 50 ℃ to obtain a target product IV, namely the ultraviolet-resistant auxiliary agent;
the infrared data of the ultraviolet resistant auxiliary agent are as follows: 3347cm -1 : -OH (carboxyl) weakening; 1760cm -1 : -c=o (carboxyl) disappears; 3011cm -1 、1501cm -1 、1594cm -1 : the benzene ring exists; 1738cm -1 : ester-c=o present; 1682cm -1 : amide-c=o present; 1525cm -1 : amide-NH-present; 1382cm -1 、1428cm -1 : the carboxylate is present.
Fluorescence excitation emission spectrum: 590nm and 615nm are Eu 3+ 615nm is the strongest characteristic emission peak.
The dosage ratio of the intermediate product III to the N, N-dimethylformamide, the absolute ethyl alcohol and the deionized water is as follows: 10g:500mL:1000mL:300mL:300mL;
The dosage of europium chloride is added according to the molar ratio of europium ions to carboxyl in the intermediate product III of 1:3.
Specifically, the photoinitiator is 651.
Specifically, the 2, 6-tetramethyl-4-piperidinol derivative is 2, 6-tetramethyl-4-piperidinol.
Specifically, the alkaline solution is an aqueous sodium hydroxide solution.
Example 4
The ultraviolet-resistant battery packaging EVA adhesive film comprises the following raw materials in parts by weight:
100 parts of EVA resin;
1.1 parts of 2, 5-dimethyl-2, 5-bis (benzoyl peroxide) hexane;
0.48 parts of triallyl isocyanurate;
1 part of ethoxylated trimethylolpropane triacrylate;
0.017 parts of hindered phenol antioxidant;
0.033 parts of phosphite antioxidant;
0.28 parts of ultraviolet resistant auxiliary agent;
0.5 part of coupling agent.
The preparation method of the ultraviolet resistant auxiliary agent comprises the following steps:
(1)N 2 under the protection, placing 4-hydroxy cinnamic acid, triethylamine and dichloromethane into a flask, stirring uniformly under ice bath conditions, dissolving acryloyl chloride into dichloromethane, placing into a constant pressure dropping funnel, dropwise adding the solution into the flask while stirring, continuously stirring for 12 hours at 0 ℃ after the dropwise adding, filtering the reaction solution by using filter paper after the reaction is finished, adding 20wt% of dilute hydrochloric acid aqueous solution into the filtrate for washing for 3 times, adding saturated sodium bicarbonate aqueous solution for washing for 3 times, washing by using deionized water for 3 times, standing for separating liquid, taking an organic phase, adding anhydrous sodium sulfate into the organic phase for drying, filtering to remove anhydrous sodium sulfate, taking filtrate, distilling under reduced pressure to remove dichloromethane, and vacuum drying the obtained product to constant weight at 50 ℃ to obtain an intermediate product I;
The dosage ratio of the 4-hydroxy cinnamic acid to triethylamine, dichloromethane, acryloyl chloride, dichloromethane, 20wt% of dilute hydrochloric acid aqueous solution, saturated sodium bicarbonate aqueous solution, deionized water and anhydrous sodium sulfate is as follows: 0.1mol:0.22mol:200mL:0.12mol:300mL:400mL:400mL:400mL:10g;
(2) Adding intermediate product I, isocyanoethyl methacrylate, photoinitiator and methylene dichloride into a flask, stirring and dissolving, and placing the reaction system under a UV lampAt 400mJ/cm 2 Irradiating for 5min under UV light intensity, standing after the reaction is completed, and distilling under reduced pressure to remove dichloromethane to obtain an intermediate product II (Mn=28220, D=1.26);
the infrared data for intermediate II are as follows: 3347cm -1 : -OH (carboxyl) present; 1760cm -1 : -c=o (carboxyl) present; 3011cm -1 、1501cm -1 、1594cm -1 : the benzene ring exists; 1738cm -1 : ester-c=o is present and enhanced; 1605cm -1 、810cm -1 : -c=c-vanishes; 2275cm -1 : -NCO present.
The dosage ratio of the intermediate product I to the isocyanoethyl methacrylate to the methylene dichloride is as follows: 40g:10g:300mL;
the dosage of the photoinitiator is 2% of the total mass of the reactants;
(3) Adding an intermediate product II, dibutyltin dilaurate, a 2, 6-tetramethyl-4-piperidinol derivative and N, N-dimethylformamide into a flask, stirring uniformly, stirring at a constant temperature for reaction for 6 hours, removing the N, N-dimethylformamide by reduced pressure distillation after the reaction is finished, adding absolute ethyl alcohol into a reactant, filtering, taking insoluble matters, leaching the insoluble matters with the absolute ethyl alcohol for 2 times, leaching with deionized water for 3 times, and then drying in vacuum at 50 ℃ to constant weight to obtain an intermediate product III;
The infrared data for intermediate III are as follows: 3347cm -1 : -OH (carboxyl) present; 1760cm -1 : -c=o (carboxyl) present; 3011cm -1 、1501cm -1 、1594cm -1 : the benzene ring exists; 1738cm -1 : ester-c=o present; 2275cm -1 : -NCO vanishing; 1682cm -1 : amide-c=o present; 1525cm -1 : amide-NH-is present.
The dosage ratio of the intermediate product II to the N, N-dimethylformamide, the absolute ethyl alcohol and the deionized water is 10g:100mL:300mL:100mL:100mL;
the molar ratio of the 2, 6-tetramethyl-4-piperidinol derivative to the isocyanoethyl methacrylate is 1:1;
the dosage of the dibutyl tin dilaurate is 0.5% of the total mass of the intermediate product II and the 2, 6-tetramethyl-4-piperidinol derivative;
(4) Adding intermediate products III and N, N-dimethylformamide into a three-mouth bottle, putting into a constant temperature tank, heating to 70 ℃, then adding europium chloride, fully and uniformly stirring, then dropwise adding alkaline solution with the mass concentration of 30wt% by using a dropping funnel, slowly dropwise adding, adjusting the pH value of the solution to be=6, stirring at constant temperature for 28 hours, cooling to room temperature after the reaction is finished, concentrating in vacuum, injecting absolute ethyl alcohol, filtering, taking insoluble matters, leaching the insoluble matters for 2 times by using absolute ethyl alcohol, leaching the insoluble matters for 3 times by using deionized water, and then vacuum-drying to constant weight at 50 ℃ to obtain a target product IV, namely the ultraviolet-resistant auxiliary agent;
3347cm of the UV resistant auxiliary -1 : -OH (carboxyl) weakening; 1760cm -1 : -c=o (carboxyl) disappears; 3011cm -1 、1501cm -1 、1594cm -1 : the benzene ring exists; 1738cm -1 : ester-c=o present; 1682cm -1 : amide-c=o present; 1525cm -1 : amide-NH-present; 1382cm -1 、1428cm -1 : the carboxylate is present.
Fluorescence excitation emission spectrum: 590nm and 615nm are Eu 3+ 615nm is the strongest characteristic emission peak.
The dosage ratio of the intermediate product III to the N, N-dimethylformamide, the absolute ethyl alcohol and the deionized water is as follows: 10g:500mL:1000mL:300mL:300mL;
the dosage of europium chloride is added according to the molar ratio of europium ions to carboxyl in the intermediate product III of 1:3.
Specifically, the photoinitiator is TPO-L.
Specifically, the 2, 6-tetramethyl-4-piperidinol derivative is 2, 6-tetramethyl-4-piperidinol.
Specifically, the alkaline solution is an aqueous sodium hydroxide solution.
Example 5
The ultraviolet-resistant battery packaging EVA adhesive film comprises the following raw materials in parts by weight:
100 parts of EVA resin;
1.1 parts of 2, 5-dimethyl-2, 5-bis (benzoyl peroxide) hexane;
0.48 parts of triallyl isocyanurate;
1 part of ethoxylated trimethylolpropane triacrylate;
0.017 parts of hindered phenol antioxidant;
0.033 parts of phosphite antioxidant;
0.28 parts of ultraviolet resistant auxiliary agent;
0.5 part of coupling agent.
The preparation method of the ultraviolet resistant auxiliary agent comprises the following steps:
(1)N 2 under the protection, placing 4-hydroxy cinnamic acid, triethylamine and dichloromethane into a flask, stirring uniformly under ice bath conditions, dissolving acryloyl chloride into dichloromethane, placing into a constant pressure dropping funnel, dropwise adding the solution into the flask while stirring, continuously stirring for 12 hours at 0 ℃ after the dropwise adding, filtering the reaction solution by using filter paper after the reaction is finished, adding 20wt% of dilute hydrochloric acid aqueous solution into the filtrate for washing for 3 times, adding saturated sodium bicarbonate aqueous solution for washing for 3 times, washing by using deionized water for 3 times, standing for separating liquid, taking an organic phase, adding anhydrous sodium sulfate into the organic phase for drying, filtering to remove anhydrous sodium sulfate, taking filtrate, distilling under reduced pressure to remove dichloromethane, and vacuum drying the obtained product to constant weight at 50 ℃ to obtain an intermediate product I;
the infrared data for intermediate I are as follows: 3512cm -1 : -OH vanishes; 3347cm -1 : -OH (carboxyl) present; 1760cm -1 : -c=o (carboxyl) present; 3011cm -1 、1501cm -1 、1594cm -1 : the benzene ring exists; 1738cm -1 : ester-c=o
Presence; 1605cm -1 、810cm -1 : -c=c-present.
The dosage ratio of the 4-hydroxy cinnamic acid to the triethylamine to the dichloromethane, the acryloyl chloride, the dichloromethane, the 20wt% dilute hydrochloric acid aqueous solution, the saturated sodium bicarbonate aqueous solution, the deionized water and the anhydrous sodium sulfate is as follows: 0.1mol:0.22mol:200mL:0.12mol:300mL:400mL:400mL:400mL:10g;
(2) The intermediate product I,Adding isocyanoethyl methacrylate, photoinitiator, and dichloromethane into a flask, stirring to dissolve, placing the reaction system under UV lamp at 400mJ/cm 2 Irradiating for 5min under UV light intensity, standing after the reaction is completed, and distilling under reduced pressure to remove dichloromethane to obtain an intermediate product II (Mn=28110, D=1.26);
the infrared data for intermediate II are as follows: 3347cm -1 : -OH (carboxyl) present; 1760cm -1 : -c=o (carboxyl) present; 3011cm -1 、1501cm -1 、1594cm -1 : the benzene ring exists; 1738cm -1 : ester-c=o is present and enhanced; 1605cm -1 、810cm -1 : -c=c-vanishes; 2275cm -1 : -NCO present.
The dosage ratio of the intermediate product I to the isocyanoethyl methacrylate to the methylene dichloride is as follows: 40g:10g:300mL;
the dosage of the photoinitiator is 2% of the total mass of the reactants;
(3) Adding an intermediate product II, dibutyltin dilaurate, a 2, 6-tetramethyl-4-piperidinol derivative and N, N-dimethylformamide into a flask, stirring uniformly, stirring at a constant temperature of 70 ℃ for reaction for 4 hours, removing the N, N-dimethylformamide by reduced pressure distillation after the reaction is finished, adding absolute ethyl alcohol into a reactant, filtering, taking insoluble matters, leaching the insoluble matters with the absolute ethyl alcohol for 2 times, leaching with deionized water for 3 times, and then vacuum-drying at 50 ℃ to constant weight to obtain an intermediate product III;
The dosage ratio of the intermediate product II to the N, N-dimethylformamide, the absolute ethyl alcohol and the deionized water is 10g:100mL:300mL:100mL:100mL;
the molar ratio of the 2, 6-tetramethyl-4-piperidinol derivative to the isocyanoethyl methacrylate is 1:1;
the dosage of the dibutyl tin dilaurate is 0.5% of the total mass of the intermediate product II and the 2, 6-tetramethyl-4-piperidinol derivative;
(4) Adding intermediate products III and N, N-dimethylformamide into a three-mouth bottle, putting into a constant temperature tank, heating to 70 ℃, then adding europium chloride, fully and uniformly stirring, then dropwise adding alkaline solution with the mass concentration of 30wt% by using a dropping funnel, slowly dropwise adding, adjusting the pH value of the solution to be=6, stirring at constant temperature for 28 hours, cooling to room temperature after the reaction is finished, concentrating in vacuum, injecting absolute ethyl alcohol, filtering, taking insoluble matters, leaching the insoluble matters for 2 times by using absolute ethyl alcohol, leaching the insoluble matters for 3 times by using deionized water, and then vacuum-drying to constant weight at 50 ℃ to obtain a target product IV, namely the ultraviolet-resistant auxiliary agent;
the dosage ratio of the intermediate product III to the N, N-dimethylformamide, the absolute ethyl alcohol and the deionized water is as follows: 10g:500mL:1000mL:300mL:300mL;
The dosage of europium chloride is added according to the molar ratio of europium ions to carboxyl in the intermediate product III of 1:3.
Specifically, the photoinitiator is TPO-L.
Specifically, the 2, 6-tetramethyl-4-piperidinol derivative is 2, 6-tetramethyl-4-piperidinol.
Specifically, the alkaline solution is an aqueous sodium hydroxide solution.
Example 6
The ultraviolet-resistant battery packaging EVA adhesive film comprises the following raw materials in parts by weight:
100 parts of EVA resin;
1.1 parts of 2, 5-dimethyl-2, 5-bis (benzoyl peroxide) hexane;
0.48 parts of triallyl isocyanurate;
1 part of ethoxylated trimethylolpropane triacrylate;
0.04 parts of hindered phenol antioxidant;
0.08 part of phosphite antioxidant;
0.35 parts of ultraviolet resistant auxiliary agent;
0.5 part of coupling agent.
The preparation method of the ultraviolet resistant auxiliary agent comprises the following steps:
(1)N 2 under the protection, placing 4-hydroxy cinnamic acid, triethylamine and dichloromethane into a flask, stirring uniformly under ice bath condition, dissolving acryloyl chloride in dichloromethane, placing into a constant pressure dropping funnel, dropwise adding into the flask under stirring, and after the addition is finishedContinuously stirring for 12 hours at 0 ℃, filtering a reaction solution by using filter paper after the reaction is finished, adding 20wt% of dilute hydrochloric acid aqueous solution into the filtrate for washing for 3 times, adding saturated sodium bicarbonate aqueous solution for washing for 3 times, washing by using deionized water for 3 times, standing for separating liquid, taking an organic phase, adding anhydrous sodium sulfate into the organic phase for drying, filtering to remove the anhydrous sodium sulfate, taking the filtrate, distilling under reduced pressure to remove dichloromethane, and vacuum drying the obtained product to constant weight at 50 ℃ to obtain an intermediate product I;
The infrared data for intermediate I are as follows: 3512cm -1 : -OH vanishes; 3347cm -1 : -OH (carboxyl) present; 1760cm -1 : -c=o (carboxyl) present; 3011cm -1 、1501cm -1 、1594cm -1 : the benzene ring exists; 1738cm -1 : ester-c=o present; 1605cm -1 、810cm -1 : -c=c-present.
The dosage ratio of the 4-hydroxy cinnamic acid to triethylamine, dichloromethane, acryloyl chloride, dichloromethane, 20wt% of dilute hydrochloric acid aqueous solution, saturated sodium bicarbonate aqueous solution, deionized water and anhydrous sodium sulfate is as follows: 0.1mol:0.22mol:200mL:0.12mol:300mL:400mL:400mL:400mL:10g;
(2) Adding intermediate I, isocyanoethyl methacrylate, photoinitiator and methylene dichloride into a flask, stirring to dissolve, placing the reaction system under a UV lamp at 400mJ/cm 2 Irradiating for 5min under UV light intensity, standing after the reaction is completed, and distilling under reduced pressure to remove dichloromethane to obtain an intermediate product II (Mn=27080, D=1.28);
the infrared data for intermediate II are as follows: 3347cm -1 : -OH (carboxyl) present; 1760cm -1 : -c=o (carboxyl) present; 3011cm -1 、1501cm -1 、1594cm -1 : the benzene ring exists; 1738cm -1 : ester-c=o is present and enhanced; 1605cm -1 、810cm -1 : -c=c-vanishes; 2275cm -1 : -NCO present.
The dosage ratio of the intermediate product I to the isocyanoethyl methacrylate to the methylene dichloride is as follows: 20g:10g:300mL;
The dosage of the photoinitiator is 2% of the total mass of the reactants;
(3) Adding an intermediate product II, dibutyltin dilaurate, a 2, 6-tetramethyl-4-piperidinol derivative and N, N-dimethylformamide into a flask, stirring uniformly, stirring at a constant temperature of 60 ℃ for reacting for 5 hours, distilling under reduced pressure to remove the N, N-dimethylformamide after the reaction is finished, adding absolute ethyl alcohol into a reactant, filtering, taking insoluble matters, leaching the insoluble matters with the absolute ethyl alcohol for 2 times, leaching with deionized water for 3 times, and then drying in vacuum at 50 ℃ to constant weight to obtain an intermediate product III;
the dosage ratio of the intermediate product II to the N, N-dimethylformamide, the absolute ethyl alcohol and the deionized water is 10g:100mL:300mL:100mL:100mL;
the molar ratio of the 2, 6-tetramethyl-4-piperidinol derivative to the isocyanoethyl methacrylate is 1:1;
the dosage of the dibutyl tin dilaurate is 0.5% of the total mass of the intermediate product II and the 2, 6-tetramethyl-4-piperidinol derivative;
(4) Adding intermediate products III and N, N-dimethylformamide into a three-mouth bottle, putting into a constant temperature tank, heating to 70 ℃, then adding europium chloride, fully and uniformly stirring, then dropwise adding alkaline solution with the mass concentration of 30wt% by using a dropping funnel, slowly dropwise adding, adjusting the pH value of the solution to be 7, stirring at constant temperature for 28h for reaction, cooling to room temperature after the reaction is finished, concentrating in vacuum, injecting absolute ethyl alcohol, filtering, taking insoluble matters, leaching the insoluble matters for 2 times by using absolute ethyl alcohol, leaching the insoluble matters for 3 times by using deionized water, and then vacuum-drying to constant weight at 50 ℃ to obtain a target product IV, namely the ultraviolet resistant auxiliary agent;
The infrared data of the ultraviolet resistant auxiliary agent are as follows: 3347cm -1 : -OH (carboxyl) weakening; 1760cm -1 : -c=o (carboxyl) disappears; 3011cm -1 、1501cm -1 、1594cm -1 : the benzene ring exists; 1738cm -1 : ester-c=o present; 1682cm -1 : amide-c=o present; 1525cm -1 : amide-NH-present; 1382cm -1 、1428cm -1 : the carboxylate is present.
Fluorescence excitation emission spectrum: 590nm and 615nm are Eu 3+ 615nm is the strongest characteristic emission peak.
The dosage ratio of the intermediate product III to the N, N-dimethylformamide, the absolute ethyl alcohol and the deionized water is as follows: 10g:500mL:1000mL:300mL:300mL;
the dosage of europium chloride is added according to the molar ratio of europium ions to carboxyl in the intermediate product III of 1:3.
Specifically, the photoinitiator is TPO-L.
Specifically, the 2, 6-tetramethyl-4-piperidinol derivative is 2, 6-tetramethyl-4-piperidinol.
Specifically, the alkaline solution is an aqueous sodium hydroxide solution.
Example 7
The ultraviolet-resistant battery packaging EVA adhesive film comprises the following raw materials in parts by weight:
100 parts of EVA resin;
1.1 parts of 2, 5-dimethyl-2, 5-bis (benzoyl peroxide) hexane;
0.48 parts of triallyl isocyanurate;
1 part of ethoxylated trimethylolpropane triacrylate;
0.04 parts of hindered phenol antioxidant;
0.08 part of phosphite antioxidant;
0.3 part of ultraviolet resistant auxiliary agent;
0.5 part of coupling agent.
The preparation method of the ultraviolet resistant auxiliary agent comprises the following steps:
(1)N 2 under the protection, placing 4-hydroxy cinnamic acid, triethylamine and dichloromethane into a flask, stirring uniformly under ice bath condition, dissolving acryloyl chloride in dichloromethane, placing into a constant pressure dropping funnel, dropwise adding into the flask while stirring, continuously stirring at 0 ℃ for 12h after the dropwise adding, filtering the reaction solution with filter paper after the reaction is finished, adding 20wt% dilute hydrochloric acid aqueous solution into the filtrate, washing for 3 times, adding saturated sodium bicarbonate aqueous solution, washing for 3 times with deionized water, standing for separating liquid, taking an organic phase, adding anhydrous sodium sulfate into the organic phase, drying, filtering to remove anhydrous sodium sulfateSodium sulfate, taking filtrate, distilling under reduced pressure to remove dichloromethane, and vacuum drying the obtained product at 50 ℃ to constant weight to obtain an intermediate product I;
the infrared data for intermediate I are as follows: 3512cm -1 : -OH vanishes; 3347cm -1 : -OH (carboxyl) present; 1760cm -1 : -c=o (carboxyl) present; 3011cm -1 、1501cm -1 、1594cm -1 : the benzene ring exists; 1738cm -1 : ester-c=o present; 1605cm -1 、810cm -1 : -c=c-present.
The dosage ratio of the 4-hydroxy cinnamic acid to triethylamine, dichloromethane, acryloyl chloride, dichloromethane, 20wt% of dilute hydrochloric acid aqueous solution, saturated sodium bicarbonate aqueous solution, deionized water and anhydrous sodium sulfate is as follows: 0.1mol:0.22mol:200mL:0.12mol:300mL:400mL:400mL:400mL:10g;
(2) Adding intermediate I, isocyanoethyl methacrylate, photoinitiator and methylene dichloride into a flask, stirring to dissolve, placing the reaction system under a UV lamp at 400mJ/cm 2 Irradiating for 5min under UV light intensity, standing after the reaction is completed, and distilling under reduced pressure to remove dichloromethane to obtain an intermediate product II (Mn=27750, D=1.26);
the dosage ratio of the intermediate product I to the isocyanoethyl methacrylate to the methylene dichloride is as follows: 30g:10g:300mL;
the dosage of the photoinitiator is 2% of the total mass of the reactants;
(3) Adding an intermediate product II, dibutyltin dilaurate, a 2, 6-tetramethyl-4-piperidinol derivative and N, N-dimethylformamide into a flask, stirring uniformly, stirring at a constant temperature of 60 ℃ for reacting for 5 hours, distilling under reduced pressure to remove the N, N-dimethylformamide after the reaction is finished, adding absolute ethyl alcohol into a reactant, filtering, taking insoluble matters, leaching the insoluble matters with the absolute ethyl alcohol for 2 times, leaching with deionized water for 3 times, and then drying in vacuum at 50 ℃ to constant weight to obtain an intermediate product III;
the infrared data for intermediate III are as follows: 3347cm -1 : -OH (carboxyl) present; 1760cm -1 : -c=o (carboxyl) present; 3011cm -1 、1501cm -1 、1594cm -1 : the benzene ring exists; 1738cm -1 : ester-c=o present; 2275cm -1 : -NCO vanishing; 1682cm -1 : amide-c=o present; 1525cm -1 : amide-NH-is present.
The dosage ratio of the intermediate product II to the N, N-dimethylformamide, the absolute ethyl alcohol and the deionized water is 10g:100mL:300mL:100mL:100mL;
the molar ratio of the 2, 6-tetramethyl-4-piperidinol derivative to the isocyanoethyl methacrylate is 1:1;
the dosage of the dibutyl tin dilaurate is 0.5% of the total mass of the intermediate product II and the 2, 6-tetramethyl-4-piperidinol derivative;
(4) Adding intermediate products III and N, N-dimethylformamide into a three-mouth bottle, putting into a constant temperature tank, heating to 70 ℃, then adding europium chloride, fully and uniformly stirring, then dropwise adding alkaline solution with the mass concentration of 30wt% by using a dropping funnel, slowly dropwise adding, adjusting the pH value of the solution to be 7, stirring at constant temperature for 28h for reaction, cooling to room temperature after the reaction is finished, concentrating in vacuum, injecting absolute ethyl alcohol, filtering, taking insoluble matters, leaching the insoluble matters for 2 times by using absolute ethyl alcohol, leaching the insoluble matters for 3 times by using deionized water, and then vacuum-drying to constant weight at 50 ℃ to obtain a target product IV, namely the ultraviolet resistant auxiliary agent;
the infrared data of the ultraviolet resistant auxiliary agent are as follows: 3347cm -1 : -OH (carboxyl) weakening; 1760cm -1 : -c=o (carboxyl) disappears; 3011cm -1 、1501cm -1 、1594cm -1 : the benzene ring exists; 1738cm -1 : ester-c=o present; 1682cm -1 : amide-c=o present; 1525cm -1 : amide-NH-present; 1382cm -1 、1428cm -1 : the carboxylate is present.
Fluorescence excitation emission spectrum: 590nm and 615nm are Eu 3+ 615nm is the strongest characteristic emission peak.
The dosage ratio of the intermediate product III to the N, N-dimethylformamide, the absolute ethyl alcohol and the deionized water is as follows: 10g:500mL:1000mL:300mL:300mL;
the dosage of europium chloride is added according to the molar ratio of europium ions to carboxyl in the intermediate product III of 1:3.
Specifically, the photoinitiator is TPO-L.
Specifically, the 2, 6-tetramethyl-4-piperidinol derivative is 2, 6-tetramethyl-4-piperidinol.
Specifically, the alkaline solution is an aqueous sodium hydroxide solution.
Example 8
The ultraviolet-resistant battery packaging EVA adhesive film comprises the following raw materials in parts by weight:
100 parts of EVA resin;
0.5 part of 1,1- (tert-butyl diperoxide) -3, 5-trimethylcyclohexane;
0.6 parts of triallyl isocyanurate;
0.6 parts of trimethylolpropane trimethacrylate;
0.8 parts of ethoxylated trimethylolpropane triacrylate;
0.04 parts of hindered phenol antioxidant;
0.08 part of phosphite antioxidant;
0.28 parts of ultraviolet resistant auxiliary agent;
0.3 parts of coupling agent.
The preparation method of the ultraviolet resistant auxiliary agent comprises the following steps:
(1)N 2 under the protection, placing 4-hydroxy cinnamic acid, triethylamine and dichloromethane into a flask, stirring uniformly under ice bath conditions, dissolving acryloyl chloride into dichloromethane, placing into a constant pressure dropping funnel, dropwise adding into the flask while stirring, continuously stirring for 12 hours at 5 ℃ after the dropwise adding, filtering reaction liquid by using filter paper after the reaction is finished, adding 20wt% of dilute hydrochloric acid aqueous solution into filtrate to wash for 3 times, adding saturated sodium bicarbonate aqueous solution to wash for 3 times, washing by using deionized water for 3 times, standing for separating liquid, taking an organic phase, adding anhydrous sodium sulfate into the organic phase to dry, filtering to remove anhydrous sodium sulfate, taking filtrate, distilling under reduced pressure to remove dichloromethane, and vacuum drying the obtained product to constant weight at 50 ℃ to obtain an intermediate product I;
infrared number of intermediate IAccording to the following: 3512cm -1 : -OH vanishes; 3347cm -1 : -OH (carboxyl) present; 1760cm -1 : -c=o (carboxyl) present; 3011cm -1 、1501cm -1 、1594cm -1 : the benzene ring exists; 1738cm -1 : ester-c=o present; 1605cm -1 、810cm -1 : -c=c-present.
The dosage ratio of the 4-hydroxy cinnamic acid to triethylamine, dichloromethane, acryloyl chloride, dichloromethane, 20wt% of dilute hydrochloric acid aqueous solution, saturated sodium bicarbonate aqueous solution, deionized water and anhydrous sodium sulfate is as follows: 0.1mol:0.22mol:200mL:0.12mol:300mL:400mL:400mL:400mL:10g;
(2) Adding intermediate I, isocyanoethyl methacrylate, photoinitiator and methylene dichloride into a flask, stirring to dissolve, placing the reaction system under a UV lamp at 400mJ/cm 2 Irradiating for 20min under UV light intensity, standing after the reaction is completed, and distilling under reduced pressure to remove dichloromethane to obtain an intermediate product II (Mn=26820, D=1.29);
the infrared data for intermediate II are as follows: 3347cm -1 : -OH (carboxyl) present; 1760cm -1 : -c=o (carboxyl) present; 3011cm -1 、1501cm -1 、1594cm -1 : the benzene ring exists; 1738cm -1 : ester-c=o is present and enhanced; 1605cm -1 、810cm -1 : -c=c-vanishes; 2275cm -1 : -NCO present.
The dosage ratio of the intermediate product I to the isocyanoethyl methacrylate to the methylene dichloride is as follows: 10g:10g:300mL;
the dosage of the photoinitiator is 2% of the total mass of the reactants;
(3) Adding an intermediate product II, dibutyltin dilaurate, a 2, 6-tetramethyl-4-piperidinol derivative and N, N-dimethylformamide into a flask, stirring uniformly, stirring at a constant temperature of 60 ℃ for reacting for 5 hours, distilling under reduced pressure to remove the N, N-dimethylformamide after the reaction is finished, adding absolute ethyl alcohol into a reactant, filtering, taking insoluble matters, leaching the insoluble matters with the absolute ethyl alcohol for 2 times, leaching with deionized water for 3 times, and then drying in vacuum at 50 ℃ to constant weight to obtain an intermediate product III;
The infrared data for intermediate III are as follows: 3534cm -1 : -OH is present; 3347cm -1 : -OH (carboxyl) present; 1760cm -1 : -c=o (carboxyl) present; 3011cm -1 、1501cm -1 、1594cm -1 : the benzene ring exists; 1738cm -1 : ester-c=o present; 2275cm -1 : -NCO vanishing; 1682cm -1 : amide-c=o present; 1525cm -1 : amide-NH-is present.
The dosage ratio of the intermediate product II to the N, N-dimethylformamide, the absolute ethyl alcohol and the deionized water is 10g:100mL:300mL:100mL:100mL;
the molar ratio of the 2, 6-tetramethyl-4-piperidinol derivative to the isocyanoethyl methacrylate is 1:1;
the dosage of the dibutyl tin dilaurate is 0.5% of the total mass of the intermediate product II and the 2, 6-tetramethyl-4-piperidinol derivative;
(4) Adding intermediate products III and N, N-dimethylformamide into a three-mouth bottle, putting into a constant temperature tank, heating to 70 ℃, then adding europium chloride, fully and uniformly stirring, then dropwise adding alkaline solution with the mass concentration of 30wt% by using a dropping funnel, slowly dropwise adding, adjusting the pH value of the solution to be 7, stirring at constant temperature for 28h for reaction, cooling to room temperature after the reaction is finished, concentrating in vacuum, injecting absolute ethyl alcohol, filtering, taking insoluble matters, leaching the insoluble matters for 2 times by using absolute ethyl alcohol, leaching the insoluble matters for 3 times by using deionized water, and then vacuum-drying to constant weight at 50 ℃ to obtain a target product IV, namely the ultraviolet resistant auxiliary agent;
The infrared data of the ultraviolet resistant auxiliary agent are as follows: 3534cm -1 : -OH is present; 3347cm -1 : -OH (carboxyl) weakening; 1760cm -1 : -c=o (carboxyl) disappears; 3011cm -1 、1501cm -1 、1594cm -1 : the benzene ring exists; 1738cm -1 : ester-c=o present; 1682cm -1 : amide-c=o present; 1525cm -1 : amide-NH-present; 1382cm -1 、1428cm -1 : the carboxylate is present.
Fluorescence excitation emission spectrum: 590nm and 615nm are Eu 3+ Features of (2)The 615nm spectrum is the strongest characteristic emission peak.
The dosage ratio of the intermediate product III to the N, N-dimethylformamide, the absolute ethyl alcohol and the deionized water is as follows: 10g:500mL:1000mL:300mL:300mL;
the dosage of europium chloride is added according to the molar ratio of europium ions to carboxyl in the intermediate product III of 1:3.
Specifically, the photoinitiator is 1173.
Specifically, the 2, 6-tetramethyl-4-piperidinol derivative is 1,2, 6-pentamethyl-4-piperidinol.
Specifically, the alkaline solution is ammonia water.
Example 9
The ultraviolet-resistant battery packaging EVA adhesive film comprises the following raw materials in parts by weight:
100 parts of EVA resin;
1.5 parts of tert-butyl peroxy-2-ethylhexyl carbonate;
0.2 parts of trimethylolpropane trimethacrylate;
0.8 parts of ethoxylated trimethylolpropane triacrylate;
0.04 parts of hindered phenol antioxidant;
0.08 part of phosphite antioxidant;
0.28 parts of ultraviolet resistant auxiliary agent;
0.6 part of coupling agent.
The preparation method of the ultraviolet resistant auxiliary agent comprises the following steps:
(1)N 2 under the protection, placing 4-hydroxy cinnamic acid, triethylamine and dichloromethane into a flask, stirring uniformly under ice bath condition, dissolving acryloyl chloride in dichloromethane, placing into a constant pressure dropping funnel, dropwise adding into the flask while stirring, continuously stirring at 5 ℃ for 8 hours after the dropwise adding, filtering the reaction solution with filter paper after the reaction is finished, adding 20wt% dilute hydrochloric acid aqueous solution into the filtrate, washing for 3 times, adding saturated sodium bicarbonate aqueous solution, washing for 3 times with deionized water, standing for separating liquid, taking an organic phase, adding anhydrous sodium sulfate into the organic phase, drying, filtering to remove anhydrous sodium sulfate, taking filtrate, and reducingThe methylene dichloride is removed by pressure distillation, and the obtained product is dried to constant weight in vacuum at 50 ℃ to obtain an intermediate product I;
the infrared data for intermediate I are as follows: 3512cm -1 : -OH vanishes; 3347cm -1 : -OH (carboxyl) present; 1760cm -1 : -c=o (carboxyl) present; 3011cm -1 、1501cm -1 、1594cm -1 : the benzene ring exists; 1738cm -1 : ester-c=o present; 1605cm -1 、810cm -1 : -c=c-present.
The dosage ratio of the 4-hydroxy cinnamic acid to triethylamine, dichloromethane, acryloyl chloride, dichloromethane, 20wt% of dilute hydrochloric acid aqueous solution, saturated sodium bicarbonate aqueous solution, deionized water and anhydrous sodium sulfate is as follows: 0.1mol:0.22mol:200mL:0.12mol:300mL:400mL:400mL:400mL:10g;
(2) Adding intermediate I, isocyanoethyl methacrylate, photoinitiator and methylene dichloride into a flask, stirring to dissolve, placing the reaction system under a UV lamp at 400mJ/cm 2 Irradiating for 17min under UV light intensity, standing after the reaction is completed, and distilling under reduced pressure to remove dichloromethane to obtain an intermediate product II (Mn=3040, D=1.26);
the infrared data for intermediate II are as follows: 3347cm -1 : -OH (carboxyl) present; 1760cm -1 : -c=o (carboxyl) present; 3011cm -1 、1501cm -1 、1594cm -1 : the benzene ring exists; 1738cm -1 : ester-c=o is present and enhanced; 1605cm -1 、810cm -1 : -c=c-vanishes; 2275cm -1 : -NCO present.
The dosage ratio of the intermediate product I to the isocyanoethyl methacrylate to the methylene dichloride is as follows: 50g:10g:300mL;
the dosage of the photoinitiator is 2% of the total mass of the reactants;
(3) Adding an intermediate product II, dibutyltin dilaurate, a 2, 6-tetramethyl-4-piperidinol derivative and N, N-dimethylformamide into a flask, stirring uniformly, stirring at a constant temperature of 60 ℃ for reacting for 5 hours, distilling under reduced pressure to remove the N, N-dimethylformamide after the reaction is finished, adding absolute ethyl alcohol into a reactant, filtering, taking insoluble matters, leaching the insoluble matters with the absolute ethyl alcohol for 2 times, leaching with deionized water for 3 times, and then drying in vacuum at 50 ℃ to constant weight to obtain an intermediate product III;
The infrared data for intermediate III are as follows: 3534cm -1 : -OH is present; 3347cm -1 : -OH (carboxyl) present; 1760cm -1 : -c=o (carboxyl) present; 3011cm -1 、1501cm -1 、1594cm -1 : the benzene ring exists; 1738cm -1 : ester-c=o present; 2275cm -1 : -NCO vanishing; 1682cm -1 : amide-c=o present; 1525cm -1 : amide-NH-is present.
The dosage ratio of the intermediate product II to the N, N-dimethylformamide, the absolute ethyl alcohol and the deionized water is 10g:100mL:300mL:100mL:100mL;
the molar ratio of the 2, 6-tetramethyl-4-piperidinol derivative to the isocyanoethyl methacrylate is 1:1;
the dosage of the dibutyl tin dilaurate is 0.5% of the total mass of the intermediate product II and the 2, 6-tetramethyl-4-piperidinol derivative;
(4) Adding intermediate products III and N, N-dimethylformamide into a three-mouth bottle, putting into a constant temperature tank, heating to 70 ℃, then adding europium chloride, fully and uniformly stirring, then dropwise adding alkaline solution with the mass concentration of 30wt% by using a dropping funnel, slowly dropwise adding, adjusting the pH value of the solution to be 7, stirring at constant temperature for 28h for reaction, cooling to room temperature after the reaction is finished, concentrating in vacuum, injecting absolute ethyl alcohol, filtering, taking insoluble matters, leaching the insoluble matters for 2 times by using absolute ethyl alcohol, leaching the insoluble matters for 3 times by using deionized water, and then vacuum-drying to constant weight at 50 ℃ to obtain a target product IV, namely the ultraviolet resistant auxiliary agent;
The infrared data of the ultraviolet resistant auxiliary agent are as follows: 3534cm -1 : -OH is present; 3347cm -1 : -OH (carboxyl) weakening; 1760cm -1 : -c=o (carboxyl) disappears; 3011cm -1 、1501cm -1 、1594cm -1 : the benzene ring exists; 1738cm -1 : ester-c=o present; 1682cm -1 : amide-c=o present; 1525cm -1 : amide-NH-present;1382cm -1 、1428cm -1 : the carboxylate is present.
Fluorescence excitation emission spectrum: 590nm and 615nm are Eu 3+ 615nm is the strongest characteristic emission peak.
The dosage ratio of the intermediate product III to the N, N-dimethylformamide, the absolute ethyl alcohol and the deionized water is as follows: 10g:500mL:1000mL:300mL:300mL;
the dosage of europium chloride is added according to the molar ratio of europium ions to carboxyl in the intermediate product III of 1:3.
The photoinitiator was 184.
The 2, 6-tetramethyl-4-piperidinol derivative is 1,2, 6-pentamethyl-4-piperidinol.
The alkaline solution is ammonia water.
The ultraviolet-resistant battery packaging EVA adhesive films of the embodiments 1-9 are prepared according to the following steps:
s1: mixing: mixing the raw materials in a mixer according to the formula amount, and mixing and stirring the raw materials for 2 hours at the temperature of 35 ℃ and at the speed of 95rpm to obtain a mixed raw material;
s2: extrusion: putting the mixed raw material obtained in the step S1 into a double-screw extruder, melting, blending and extruding at the rotation speed of 45rpm at the temperature of 82 ℃ in a first area, 93 ℃ in a second area and 87 ℃ in a third area, discharging and casting through a casting film die head, and cooling through a casting roller;
S3: film forming: and (3) measuring thickness, pressing edges, shaping, trimming and rolling to obtain the ultraviolet-resistant battery packaging EVA adhesive film with the thickness of 500 mu m.
Comparative example 1 the same as example 1 was followed except that the uv resistant auxiliary in comparative example 1 was intermediate III obtained during the preparation of the uv resistant auxiliary of example 1.
Comparative example 2 the same as example 1, except that the uv resistant auxiliary in comparative example 2 was prepared as follows:
(1)N 2 under the protection, placing 4-hydroxy cinnamic acid, triethylamine and dichloromethane into a flask, stirring uniformly under ice bath condition, dissolving acryloyl chloride in dichloromethane, placing into a constant pressure dropping funnel, and dropwise adding under stirringAdding into a flask, continuously stirring at 0 ℃ for 12 hours after the dripping is finished, filtering a reaction solution by using filter paper after the reaction is finished, adding 20wt% of dilute hydrochloric acid aqueous solution into the filtrate for 3 times, adding saturated sodium bicarbonate aqueous solution for 3 times, washing by using deionized water for 3 times, standing for liquid separation, taking an organic phase, adding anhydrous sodium sulfate into the organic phase for drying, filtering to remove anhydrous sodium sulfate, taking the filtrate, distilling under reduced pressure to remove dichloromethane, and vacuum drying the obtained product to constant weight at 50 ℃ to obtain an intermediate product I.
The infrared data for intermediate I are as follows:
3512cm -1 : -OH vanishes; 3347cm -1 : -OH (carboxyl) present; 1760cm -1 : -c=o (carboxyl) present; 3011cm -1 、1501cm -1 、1594cm -1 : the benzene ring exists; 1738cm -1 : ester-c=o present; 1605cm -1 、810cm -1 : -c=c-present.
The dosage ratio of the 4-hydroxy cinnamic acid to triethylamine, dichloromethane, acryloyl chloride, dichloromethane, 20wt% of dilute hydrochloric acid aqueous solution, saturated sodium bicarbonate aqueous solution, deionized water and anhydrous sodium sulfate is as follows: 0.1mol:0.22mol:200mL:0.12mol:300mL:400mL:400mL:400mL:10g.
(2) Adding intermediate I, photoinitiator TPO-L and dichloromethane into a flask, stirring to dissolve, and placing under a UV lamp at 400mJ/cm 2 Irradiating for 5min under UV light intensity, standing, and distilling under reduced pressure to remove dichloromethane to obtain intermediate II (Mn=32610, D=1.29);
the dosage ratio of the intermediate product I to the dichloromethane is as follows: 40g:300mL;
the dosage of the photo-initiator TPO-L is 2% of the total mass of the reactants;
the infrared data for intermediate II are as follows:
3347cm -1 : -OH (carboxyl) present; 1760cm -1 : -c=o (carboxyl) present; 3011cm -1 、1501cm -1 、1594cm -1 : the benzene ring exists; 1738cm -1 : ester-c=o present; 1605cm -1 、810cm -1 : -c=c-vanishes.
(3) Adding intermediate products II, N-dimethylformamide into a three-mouth bottle, putting into a constant temperature tank, heating to 70 ℃, then adding europium chloride into a reaction system, fully and uniformly stirring, dropwise adding 30wt% of sodium hydroxide aqueous solution by using a dropping funnel, adjusting the pH value of the solution to be=6, and carrying out constant temperature stirring reaction for 28h; standing, cooling to room temperature, vacuum concentrating, injecting absolute ethyl alcohol, filtering to obtain insoluble substances, leaching with absolute ethyl alcohol for 2 times, leaching with deionized water for 3 times, and vacuum drying at 50deg.C to constant weight to obtain target product IV, namely ultraviolet resistant auxiliary agent;
The dosage ratio of the intermediate products III, N-dimethylformamide, absolute ethyl alcohol and deionized water is as follows: 10g:500mL:1000mL:300mL:300mL;
the dosage of the europium chloride is 1:3 according to the molar ratio of europium ions to carboxyl in the intermediate product III;
the infrared data of the ultraviolet resistant auxiliary agent are as follows:
3347cm -1 : -OH (carboxyl) weakening; 1760cm -1 : -c=o (carboxyl) disappears; 3011cm -1 、1501cm -1 、1594cm -1 : the benzene ring exists; 1738cm -1 : ester-c=o present; 1382cm -1 、1428cm -1 : the carboxylate is present.
Fluorescence excitation emission spectrum: 590nm and 615nm are Eu 3+ 615nm is the strongest characteristic emission peak.
Comparative example 3 the same as example 1, except that the uv resistant auxiliary in comparative example 3 was prepared as follows:
(1) Adding acrylic acid, isocyanoethyl methacrylate, photoinitiator TPO-L and dichloromethane into a flask, stirring to dissolve, and placing under UV lamp at 400mJ/cm 2 Irradiating for 5min under UV light intensity, standing, and distilling under reduced pressure to remove dichloromethane to obtain intermediate product I;
the dosage ratio of the acrylic acid to the isocyanoethyl methacrylate to the methylene dichloride is as follows: 40g:10g:300mL;
the dosage of the photo-initiator TPO-L is 2% of the total mass of the reactants;
said intermediate product I The infrared data are as follows: 3347cm -1 : -OH (carboxyl) present; 1760cm -1 : -c=o (carboxyl) present; 1738cm -1 : ester-c=o present; 1605cm -1 、810cm -1 : -c=c-vanishes; 2275cm -1 : -NCO present.
(2) Adding the intermediate product I, dibutyl tin dilaurate, 2, 6-tetramethyl-4-piperidinol and N, N-dimethylformamide into a flask, stirring at 60 ℃ for reaction for 5 hours, removing the N, N-dimethylformamide by reduced pressure distillation after the reaction is finished, adding absolute ethyl alcohol, filtering, taking insoluble matters, leaching with absolute ethyl alcohol for 2 times, leaching with deionized water for 3 times, and vacuum drying at 50 ℃ to constant weight to obtain an intermediate product II (Mn=24485, D=1.29);
the dosage ratio of the intermediate product I to the N, N-dimethylformamide, the absolute ethyl alcohol and the deionized water is 10g:100mL:300mL:100mL:100mL;
the molar ratio of the 2, 6-tetramethyl-4-piperidinol derivative to the isocyanoethyl methacrylate is 1:1;
the dosage of the dibutyl tin dilaurate is 0.5% of the total mass of the intermediate product I and the 2, 6-tetramethyl-4-piperidinol;
the intermediate II infrared data are as follows:
3347cm -1 : -OH (carboxyl) present; 1760cm -1 : -c=o (carboxyl) present; 1738cm -1 : ester-c=o present; 2275cm -1 : -NCO vanishing; 1682cm -1 : amide-c=o present; 1525cm -1 : amide-NH-is present.
(3) Adding intermediate products II, N-dimethylformamide into a three-mouth bottle, putting into a constant temperature tank, heating to 70 ℃, then adding europium chloride, fully and uniformly stirring, dropwise adding 30wt% sodium hydroxide solution into a dropping funnel, adjusting the pH value of the solution to be=6, stirring at constant temperature for 28 hours, standing, cooling to room temperature, concentrating in vacuum, injecting absolute ethyl alcohol, filtering, taking insoluble substances, leaching with absolute ethyl alcohol for 2 times, leaching with deionized water for 3 times, and drying in vacuum to constant weight at 50 ℃ to obtain a target product IV, namely an ultraviolet resistant auxiliary agent;
the dosage ratio of the intermediate products III, N-dimethylformamide, absolute ethyl alcohol and deionized water is as follows: 10g:500mL:1000mL:300mL:300mL;
the dosage of the europium chloride is 1:3 according to the molar ratio of europium ions to carboxyl in the intermediate product III;
the infrared data of the ultraviolet resistant auxiliary agent are as follows: 3347cm -1 : -OH (carboxyl) weakening; 1760cm -1 : -c=o (carboxyl) disappears; 1738cm -1 : ester-c=o present; 1682cm -1 : amide-c=o present; 1525cm -1 : amide-NH-present; 1382cm -1 、1428cm -1 : the carboxylate is present.
Fluorescence excitation emission spectrum: 590nm and 615nm are Eu 3+ 615nm is the strongest characteristic emission peak.
Comparative example 4 the same as in example 1, except that the uv resistant auxiliary in comparative example 4 was a mixture of intermediate III obtained in example 1 and europium chloride, the molar ratio of europium ions to carboxyl groups in intermediate III being 1:3.
Comparative example 5 the same as in example 1, except that the uv resistant auxiliary in comparative example 5 is a mixture of 2, 6-tetramethyl-4-piperidinol, cinnamic acid, europium chloride; the mass ratio of the 2, 6-tetramethyl-4-piperidinol to the cinnamic acid is 1:2, and the molar ratio of the cinnamic acid to the europium chloride is 3:1.
Comparative example 6 the same as example 1 except that no phosphite antioxidant was added in comparative example 6, and the hindered phenol antioxidant was added in 0.12 parts by weight.
Comparative example 7 was the same as example 1 except that in comparative example 7, no hindered phenol type antioxidant was added, and 0.12 parts by weight of phosphite type antioxidant was added.
Performance testing
The EVA films obtained in examples 1 to 9 and comparative examples 1 to 7 of the present invention were subjected to the relevant performance test, and the test results are shown in Table 1.
The test method comprises the following steps:
(1) Transmittance: the test was carried out with reference to the method described in GB/T29848 2013 ethylene-vinyl acetate copolymer (EVA) adhesive film for packaging photovoltaic modules.
(2) Degree of crosslinking: after the EVA adhesive film is subjected to crosslinking reaction, xylene extraction is adopted to measure the crosslinking degree. Cutting EVA adhesive film into 1mm size, weighing to m 0 Placing in a stainless steel mesh bag, immersing in boiling xylene, extracting for 4h, and extracting the uncrosslinked EVA into the xylene to leave undissolved EVA adhesive film ml.
Crosslinking degree = crosslinked EVA film m 1/total EVA weight m 0 ×100％
(3) Wet heat aging resistance: and carrying out a wet heat aging test on the EVA adhesive film. Conditions are as follows: test conditions: +85 ℃, 85% relative humidity, test time 1000hr.
The visible light transmittance before and after the test was measured, and the retention rate of the visible light transmittance was calculated as follows:
retention of visible light transmittance = average light transmittance after test/average light transmittance before test x 100%.
The yellowing index (. DELTA.YI) before and after the test was determined in accordance with GB 2409.
(4) Ultraviolet aging resistance: and carrying out ultraviolet irradiation aging test on the EVA adhesive film 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, and the irradiation intensity is 15 kW.h/m 2 The ultraviolet irradiation test time is 2000hr.
The visible light transmittance before and after the test was measured, and the retention rate of the visible light transmittance was calculated as follows:
retention of visible light transmittance = average light transmittance after test/average light transmittance before test x 100%.
The yellowing index (. DELTA.YI) before and after the test was determined in accordance with GB 2409.
(5) Photoelectric conversion power gain: the measurement was performed using an EL tester. Orderly stacking the photovoltaic glass, the adhesive film, the battery piece, the adhesive film and the photovoltaic backboard from top to bottom, laminating for 15min at 140 ℃, taking out and cooling, testing the power of the bare chip, and recording as P0.1; laminating the common EVA adhesive film to obtain a component, testing the power of the component, and recording the power as P1; the new die power was tested, recorded as P0.2, laminated with a light-converting film, and tested for power, recorded as P2, and then the power gain pm= (P2/P0.2) (/ P1/P0.1).
TABLE 1
From table 1, comparing example 1 with comparative examples 1 to 3, it is seen that the uv-resistant battery packaging EVA film obtained by the present invention has a remarkable advantage in long-term weather resistance and is more excellent in optical properties such as photoelectric conversion gain.
As can be seen from comparing example 1 with comparative example 4, the ultraviolet resistant auxiliary agent used in the EVA adhesive film obtained by the invention has excellent compatibility with EVA matrix resin after being chemically modified by rare earth ions, good dispersibility, and better physical properties of the obtained EVA adhesive film.
As can be seen from a comparison of example 1 and comparative example 5, the ultraviolet-resistant auxiliary agent used in the EVA adhesive film obtained by the invention has a macromolecular structure, has better compatibility with EVA matrix resin, low migration and longer lasting in light and heat aging resistance.
As can be seen from comparison of example 1 and comparative examples 5-6, the EVA adhesive film raw material obtained by the invention has better antioxidation effect by compounding the hindered phenol antioxidant and the phosphite antioxidant.
In conclusion, the ultraviolet-resistant battery packaging EVA adhesive film has excellent ultraviolet aging resistance and yellowing resistance through the formula design by adopting the self-made ultraviolet-resistant auxiliary agent, solves the weather resistance problem, can effectively utilize ultraviolet rays to further improve the photoelectric conversion efficiency of a photovoltaic battery board, and effectively prolongs the service life of a photovoltaic module.
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 (8)
1. The ultraviolet-resistant battery packaging EVA adhesive film is characterized by comprising the following raw material components in parts by weight:
100 parts of EVA resin;
0.5-1.5 parts of thermal initiator;
1-2 parts of a cross-linking agent;
0.05-0.15 part of antioxidant;
0.2-0.4 part of ultraviolet resistant auxiliary agent;
0.3-0.6 part of coupling agent;
the antioxidant is a mixture composed of hindered phenol antioxidants and phosphite antioxidants;
the preparation method of the ultraviolet resistant auxiliary agent comprises the following steps:
（1）N 2 under the protection, placing 4-hydroxy cinnamic acid, triethylamine and dichloromethane I into a flask, stirring uniformly under ice bath conditions, dissolving acryloyl chloride in dichloromethane II, placing in a constant pressure dropping funnel, dropwise adding the solution into the flask while stirring, continuously stirring for 8-12h at 0-5 ℃ after the dropwise adding is finished, filtering the reaction solution by filter paper after the reaction is finished, adding 20wt% of dilute hydrochloric acid aqueous solution into the filtrate for washing 3 times, adding saturated sodium bicarbonate aqueous solution for washing 3 times, washing with deionized water for 3 times, standing for separating liquid, taking an organic phase, adding anhydrous sodium sulfate into the organic phase for drying, filtering to remove anhydrous sodium sulfate, taking filtrate, distilling under reduced pressure to remove dichloromethane, and vacuum drying the obtained product to constant weight at 50 ℃ to obtain an intermediate product I;
The dosage ratio of the 4-hydroxy cinnamic acid to triethylamine, dichloromethane one, acryloyl chloride, dichloromethane two, 20wt% of dilute hydrochloric acid aqueous solution, saturated sodium bicarbonate aqueous solution, deionized water and anhydrous sodium sulfate is as follows: 0.1mol:0.22mol:200mL:0.12mol:300mL:400mL:400mL:400mL:10g;
(2) Adding an intermediate product I, isocyanoethyl methacrylate, a photoinitiator and methylene dichloride into a flask, stirring and dissolving, placing a reaction system under a UV lamp, performing irradiation crosslinking, standing after the reaction is finished, and distilling under reduced pressure to remove the methylene dichloride to obtain an intermediate product II;
the dosage ratio of the intermediate product I to the isocyanoethyl methacrylate to the methylene dichloride is as follows: (10-50) g:10g:300mL;
the dosage of the photoinitiator is 2% of the total mass of the reactants;
(3) Adding an intermediate product II, dibutyltin dilaurate, a 2, 6-tetramethyl-4-piperidinol derivative and N, N-dimethylformamide into a flask, stirring uniformly, stirring at a constant temperature of 40-80 ℃ for reaction for 3-6 hours, removing the N, N-dimethylformamide by reduced pressure distillation after the reaction is finished, adding absolute ethyl alcohol I into a reactant, filtering, taking insoluble matters, leaching the insoluble matters twice with absolute ethyl alcohol for 2 times, leaching the insoluble matters with deionized water for 3 times, and then drying in vacuum at 50 ℃ to constant weight to obtain an intermediate product III;
The dosage ratio of the intermediate product II to the N, N-dimethylformamide, the absolute ethyl alcohol I, the absolute ethyl alcohol II and the deionized water is 10g:100mL:300mL:100mL:100mL;
the molar ratio of the 2, 6-tetramethyl-4-piperidinol derivative to the isocyanoethyl methacrylate is 1:1;
the dosage of the dibutyl tin dilaurate is 0.5% of the total mass of the intermediate product II and the 2, 6-tetramethyl-4-piperidinol derivative;
(4) Adding intermediate products III and N, N-dimethylformamide into a three-mouth bottle, putting into a constant temperature tank, heating to 60-80 ℃, then adding rare earth chloride, fully and uniformly stirring, then dropwise adding alkaline solution with the mass concentration of 30wt% by using a dropping funnel, slowly dropwise adding, adjusting the pH value of the solution to be 6-7, carrying out constant temperature stirring reaction for 20-30h, cooling to room temperature after the reaction is finished, carrying out vacuum concentration, injecting absolute ethyl alcohol III, filtering, taking insoluble substances, leaching the insoluble substances with absolute ethyl alcohol for 2 times, leaching with deionized water for 3 times, and then carrying out vacuum drying at 50 ℃ to constant weight to obtain a target product IV, namely the ultraviolet resistant auxiliary agent;
the dosage ratio of the intermediate product III to the N, N-dimethylformamide, the third absolute ethyl alcohol, the fourth absolute ethyl alcohol and the deionized water is as follows: 10g:500mL:1000mL:300mL:300mL;
The rare earth chloride is added according to the molar ratio of europium ions to carboxyl in the intermediate product III of 1:3.
2. The ultraviolet-resistant battery packaging EVA adhesive film according to claim 1, wherein the EVA resin has a VA content of 33-35% and a melt index of 31-34.
3. The ultraviolet-resistant battery packaging EVA film of claim 1, wherein the thermal initiator comprises at least one of t-butyl peroxy-2-ethylhexyl carbonate, 2, 5-dimethyl-2, 5-bis (benzoylperoxy) hexane or 1,1- (t-butyl diperoxide) -3, 5-trimethylcyclohexane.
4. The ultraviolet-resistant battery packaging EVA film of claim 1, wherein the cross-linking agent comprises at least one of triallyl isocyanurate, trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate.
5. The ultraviolet-resistant battery packaging EVA film of claim 1, wherein the photoinitiator comprises at least one of TPO, TPO-L, 651, 1173, 184.
6. The ultraviolet-resistant battery packaging EVA adhesive film of claim 1, wherein the adhesive film comprises a transparent film, the 2, 6-tetramethyl-4-piperidinol derivative comprises 2, 6-tetramethyl-4-piperidinol at least one of 1,2, 6-pentamethyl-4-piperidinol.
7. The ultraviolet-resistant battery packaging EVA film of claim 1, wherein the rare earth chloride is europium chloride.
8. The ultraviolet-resistant battery packaging EVA film of claim 1, wherein the alkaline solution comprises at least one of aqueous sodium hydroxide solution and aqueous ammonia.
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| WO2023155276A1 (en) * | 2022-02-15 | 2023-08-24 | 广东汇齐新材料有限公司 | Eva hot melt adhesive film capable of blocking ultraviolet rays and preparation method therefor |
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| CN102965039A (en) * | 2012-12-17 | 2013-03-13 | 无锡量紫谷新材料科技发展有限公司 | Light-conversion EVA (Ethylene Vinyl-Acetate Copolymer) adhesive film for solar battery and preparation method thereof |
| JP2017025334A (en) * | 2016-10-12 | 2017-02-02 | 日東電工株式会社 | Sealing material composition for solar cell, sealing material layer for solar cell using the same, and solar cell module |
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