CN111607233A - Silicon-containing high-transparency flame-retardant EVA light conversion film and preparation method thereof - Google Patents
Silicon-containing high-transparency flame-retardant EVA light conversion film and preparation method thereof Download PDFInfo
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- CN111607233A CN111607233A CN202010606872.8A CN202010606872A CN111607233A CN 111607233 A CN111607233 A CN 111607233A CN 202010606872 A CN202010606872 A CN 202010606872A CN 111607233 A CN111607233 A CN 111607233A
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- eva
- light conversion
- conversion film
- flame
- retardant
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 76
- 239000003063 flame retardant Substances 0.000 title claims abstract description 70
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title description 8
- 229910052710 silicon Inorganic materials 0.000 title description 8
- 239000010703 silicon Substances 0.000 title description 8
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 89
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 88
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 235000019400 benzoyl peroxide Nutrition 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 12
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract 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 claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 30
- 239000000047 product Substances 0.000 claims description 30
- 239000002244 precipitate Substances 0.000 claims description 29
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 26
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- 239000000706 filtrate Substances 0.000 claims description 19
- 238000010992 reflux Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 13
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 239000003208 petroleum Substances 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 239000005047 Allyltrichlorosilane Substances 0.000 claims description 9
- HKFSBKQQYCMCKO-UHFFFAOYSA-N trichloro(prop-2-enyl)silane Chemical compound Cl[Si](Cl)(Cl)CC=C HKFSBKQQYCMCKO-UHFFFAOYSA-N 0.000 claims description 9
- FCMZRNUHEXJWGB-UHFFFAOYSA-N trichloro(cyclopentyl)silane Chemical compound Cl[Si](Cl)(Cl)C1CCCC1 FCMZRNUHEXJWGB-UHFFFAOYSA-N 0.000 claims description 7
- 239000005457 ice water Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 5
- 239000012043 crude product Substances 0.000 claims description 5
- 230000005284 excitation Effects 0.000 claims description 5
- 229920001519 homopolymer Polymers 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- JERHCAZKZXMKMU-UHFFFAOYSA-N 4-[4,6-bis(3,5-dimethylpyrazol-1-yl)-1,3,5-triazin-2-yl]-n,n-diethylaniline Chemical compound C1=CC(N(CC)CC)=CC=C1C1=NC(N2C(=CC(C)=N2)C)=NC(N2C(=CC(C)=N2)C)=N1 JERHCAZKZXMKMU-UHFFFAOYSA-N 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000000748 compression moulding Methods 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims 2
- VFKZTMPDYBFSTM-KVTDHHQDSA-N Mitobronitol Chemical compound BrC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CBr VFKZTMPDYBFSTM-KVTDHHQDSA-N 0.000 claims 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims 1
- NZZIMKJIVMHWJC-UHFFFAOYSA-N dibenzoylmethane Chemical group C=1C=CC=CC=1C(=O)CC(=O)C1=CC=CC=C1 NZZIMKJIVMHWJC-UHFFFAOYSA-N 0.000 claims 1
- 239000012528 membrane Substances 0.000 claims 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims 1
- 229960004889 salicylic acid Drugs 0.000 claims 1
- 238000012360 testing method Methods 0.000 abstract description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 7
- 239000001301 oxygen Substances 0.000 abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- 238000002834 transmittance Methods 0.000 abstract description 7
- 238000002485 combustion reaction Methods 0.000 abstract description 4
- 230000002194 synthesizing effect Effects 0.000 abstract 2
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229920000877 Melamine resin Polymers 0.000 description 5
- 238000007731 hot pressing Methods 0.000 description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 4
- 239000000347 magnesium hydroxide Substances 0.000 description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000779 smoke Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 description 3
- 238000005352 clarification Methods 0.000 description 3
- 239000002198 insoluble material Substances 0.000 description 3
- 229920005610 lignin Polymers 0.000 description 3
- -1 polysiloxane Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- WCGUUGGRBIKTOS-GPOJBZKASA-N (3beta)-3-hydroxyurs-12-en-28-oic acid Chemical compound C1C[C@H](O)C(C)(C)[C@@H]2CC[C@@]3(C)[C@]4(C)CC[C@@]5(C(O)=O)CC[C@@H](C)[C@H](C)[C@H]5C4=CC[C@@H]3[C@]21C WCGUUGGRBIKTOS-GPOJBZKASA-N 0.000 description 2
- 239000004114 Ammonium polyphosphate Substances 0.000 description 2
- 239000004831 Hot glue Substances 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- CFOAUMXQOCBWNJ-UHFFFAOYSA-N [B].[Si] Chemical compound [B].[Si] CFOAUMXQOCBWNJ-UHFFFAOYSA-N 0.000 description 2
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 2
- 239000002313 adhesive film Substances 0.000 description 2
- VCNTUJWBXWAWEJ-UHFFFAOYSA-J aluminum;sodium;dicarbonate Chemical compound [Na+].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O VCNTUJWBXWAWEJ-UHFFFAOYSA-J 0.000 description 2
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 2
- 229920001276 ammonium polyphosphate Polymers 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- BIOOACNPATUQFW-UHFFFAOYSA-N calcium;dioxido(dioxo)molybdenum Chemical compound [Ca+2].[O-][Mo]([O-])(=O)=O BIOOACNPATUQFW-UHFFFAOYSA-N 0.000 description 2
- 229910001647 dawsonite Inorganic materials 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000012796 inorganic flame retardant Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229940096998 ursolic acid Drugs 0.000 description 2
- PLSAJKYPRJGMHO-UHFFFAOYSA-N ursolic acid Natural products CC1CCC2(CCC3(C)C(C=CC4C5(C)CCC(O)C(C)(C)C5CCC34C)C2C1C)C(=O)O PLSAJKYPRJGMHO-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000006683 Mannich reaction Methods 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 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
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/10—Block- or graft-copolymers containing polysiloxane sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0091—Complexes with metal-heteroatom-bonds
Abstract
The invention relates to a high transparent flame retardant ethylene-vinyl acetate (EVA) light conversion film grafted with POSS and a preparation method thereof, which comprises the steps of firstly synthesizing hepta-cyclopentyl silsesquioxane trisilicon alcohol, then synthesizing allyl silsesquioxane, reacting the allyl silsesquioxane with EVA under the condition of adding BPO (dibenzoyl peroxide) to obtain EVA-g-T8 (a POSS) graft polymer, and blending the EVA graft polymer with a light conversion agent to prepare the flame retardant EVA light conversion film grafted with POSS. The light transmittance of the flame-retardant EVA light conversion film prepared by the invention can reach 93.5%, the limit oxygen index can reach 38.2% through UL 94V-0 grade test, the fluorescence intensity is enhanced by 28.5% compared with that of an EVA film directly doped with POSS, and the flame-retardant EVA light conversion film hardly has a dripping phenomenon in the combustion test process.
Description
Technical Field
The invention belongs to the field of flame-retardant high polymer materials, and particularly relates to a POSS (polyhedral oligomeric silsesquioxane) -grafted flame-retardant EVA material and application thereof in a light conversion film.
Background
EVA is ethylene-vinyl acetate copolymer, can be obtained by copolymerization of ethylene and vinyl acetate, is a general high molecular polymer, and has a molecular formula of (C)2H4)x.(C4H6O2)yThe material has the advantages of high light transmittance, good flexibility, low melting temperature, good melt fluidity, strong bonding performance and the like, and is the most widely applied solar cell packaging material at present. However, EVA itself is extremely flammable, has a limiting oxygen index of only about 18%, and generates a large amount of molten droplets when burned, which greatly limits further applications of EVA.
At present, people have developed a certain research aiming at the problem of EVA flame retardance, and most of the EVA flame retardants commonly used in the early stage are halogen flame retardants, such as Shenshu (Shenshu, a dawsonite compounded zinc fluoborate flame-retardant EVA cable material and a preparation method thereof [ P ]. Chuzhou: CN106243477A, 2016-12-21.) the method of compounding dawsonite with zinc fluoborate is adopted to prepare the flame-retardant EVA cable material, although the flame-retardant EVA cable material can obtain obvious flame-retardant effect, a large amount of toxic gas which is not beneficial to environmental protection can be released in the combustion process, so that the flame-retardant EVA cable material is gradually replaced by the halogen-free flame retardant.
The rubber sheath material is prepared by using more inorganic nano flame retardants such as magnesium hydroxide and aluminum hydroxide, wherein EVA resin is used as a main body, magnesium hydroxide is used as a flame retardant to prepare the rubber sheath material, and the ratio of EVA to magnesium hydroxide is 1: 1.1-1.3 (Xuyayuan, Chenming, Qin Jianwei, Deng Najun, Huang Chao. low smoke halogen-free flame retardant EVA rubber sheath material for mining cables and a preparation method thereof [ P ]. tin-free: CN108102206A, 2018-06-01 ]); the major rock and the like adopt a series of inorganic flame retardants of magnesium hydroxide, aluminum hydroxide, hydrotalcite, magnesium sulfate whisker and calcium sulfate whisker to prepare the ceramifiable EVA cable material with obvious flame retardant and smoke suppression effects (tremiengshi, heyday, Yangshan, Gangjing, a ceramifiable EVA halogen-free flame retardant cable material and a preparation method thereof [ P ]. Tianjin: CN108164805A, 2018-06-15.). These inorganic flame retardants have a certain effect, but the flame retardant effect is only obvious when the addition amount is very large, which affects the properties of the EVA material itself, especially the transparency.
The phosphorus-nitrogen flame retardant is also a widely used halogen-free flame retardant, and the ursolic acid and the like mainly take lignin, aldehyde, melamine, alkali, aluminum salt, red phosphorus and a dispersing agent as raw materials, and the melamine modified lignin/aluminum hydroxide double-coated red phosphorus flame retardant is prepared by combining a Mannich reaction and a chemical coprecipitation method, and has good flame retardant and smoke suppression effects when being applied to EVA resin (the ursolic acid is a melamine modified lignin/aluminum hydroxide double-coated red phosphorus flame retardant and the application thereof in the EVA resin [ P ]. Fuzhou: CN109054100A, 2018-12-21.); wujiandong and the like design a halogen-free flame retardant consisting of ammonium polyphosphate, pentaerythritol, melamine and red phosphorus and are used for preparing an EVA hot melt adhesive film for wall cloth (Wujiandong, Cai Yunmei, Yangyan, Zhanlin, a halogen-free flame retardant EVA hot melt adhesive film for wall cloth and a preparation method thereof [ P ]. Fushan: CN108893068A, 2018-11-27.). Among the flame retardants, unsafe factors exist in the storage and combustion processes of red phosphorus, the heat stability of phosphorus-nitrogen flame retardants such as ammonium polyphosphate and melamine is not enough, foaming, flame retardant decomposition and other phenomena are easily generated during processing and injection molding, and the problem of mold corrosion also exists.
The silicon flame retardant is a commonly used environment-friendly flame retardant, the most commonly used silicon flame retardant is polysiloxane and silicate, the polysiloxane has good reaction activity and substrate compatibility, and can be connected with a large number of active functional groups, such as double bonds, epoxy groups, amino groups and the like, so that the silicon flame retardant not only can generate self-polymerization, but also can be connected into a material polymer chain through the active functional groups, and thus, the silicon flame retardant endows the material with new properties. The halogen-free flame-retardant composite material prepared by selecting silane coupling agent KH-792, nitrogen-containing silicon-boron halogen-free flame retardant NBSi synthesized by boric acid and phosphorus-containing flame retardant DOPO to compound with the synergistic flame-retardant PP/EVA composite material has better mechanical, processing, flame-retardant and thermal stability, but still belongs to an additive flame retardant, and the DOPO addition amount is very high (Xiayin, Ninglong, Zhangyue. preparation method of the nitrogen-containing silicon-boron halogen-free flame retardant and DOPO synergistic flame-retardant PP/EVA composite material [ P ]. Dalian: CN106543562A, 2017-03-29.).
Therefore, an experimental scheme for grafting the silicon-containing compound molecule to the EVA is tried to be designed, so that the flame retardant property of the EVA is fundamentally improved, and the light conversion property of the EVA light conversion film is basically not influenced.
Disclosure of Invention
Aiming at the problems, the invention utilizes the silicon halogen-free flame retardant and the EVA grafting, can obviously improve the comprehensive mechanical property and the flame retardant property of the EVA, and meets the application requirement of the specific field of flame retardance.
The invention aims to solve the problems and provides a simple, convenient and flexible method which is environment-friendly and has good flame retardant effect and does not influence the light transmittance of an EVA light conversion film.
To achieve the aim, the invention firstly prepares heptapoly-cyclopentylsilsesquioxane trisilicol (T7) by refluxing and hydrolyzing cyclopentyltrichlorosilane in acetone, and synthesizes allyl silsesquioxane by a vertex-angle capping method through T7 and allyl trichlorosilane (the preparation process is shown as formula 1).
The EVA and allylsilsesquioxane were then reacted with the addition of BPO (dibenzoyl peroxide) to give the crude EVA-g-T8 graft polymer (see formula 2 for preparation).
Refining EVA-g-T8 graft polymer, mixing with light conversion agent by a plasticator, and molding by a press vulcanizer.
The technical scheme adopted by the invention comprises the following specific steps:
a high-transparency flame-retardant EVA light conversion film is prepared by blending an ethylene-vinyl acetate grafted allyl silsesquioxane T8 polymer EVA-g-T8, a grafted polymer EVA-g-T8 and a light conversion agent through a solution grafting method.
The preparation method of the high-transparency flame-retardant EVA light conversion film comprises the following steps:
step 1, adding acetone into a three-neck flask, adding cyclopentyl trichlorosilane, dropwise adding distilled water into the three-neck flask at a speed of 30-50 drops per minute by using a dropping funnel, stirring vigorously, heating and refluxing after the dropwise adding of the distilled water is finished, reacting for 48-72 hours, vacuumizing and filtering a product after the reaction is finished, cleaning the product by using acetone, dissolving the product in pyridine after drying, filtering out insoluble substances, pouring the filtrate into frozen concentrated hydrochloric acid, filtering, and drying at 40-60 ℃ to obtain hepta-cyclopentyl silsesquioxane trisilicitol;
step 2, dispersing heptapoly-cyclopentyl silsesquioxane trisilicitol obtained in the step 1 into THF, adding the dispersed heptapoly-cyclopentyl silsesquioxane trisilicitol into a flask, adding triethylamine, fully stirring and uniformly mixing, dropwise adding allyl trichlorosilane, filtering out precipitates after violently stirring for 3-5 h, carrying out the whole reaction in an ice water bath, concentrating a transparent filtrate from which the precipitates are filtered out, putting the transparent filtrate into a large amount of anhydrous ethanol, precipitating the product in a white particle form, drying and weighing to obtain a product, namely, allyl silsesquioxane T8;
step 3, adding EVA, allyl silsesquioxane T8 and benzoyl peroxide BPO into a flask, performing nitrogen protection, adding toluene subjected to reflux condensation treatment at one time by using an injector, placing a reaction bottle into an oil bath, heating to 50-70 ℃, stirring for 15-25 min under the protection of nitrogen until the added raw materials are gradually dissolved, slowly raising the temperature to 80-100 ℃, dropwise adding the reaction liquid into ice methanol after 6-8 h, stirring to generate light yellow flocculent precipitate after the reaction is finished, repeatedly washing the product obtained by suction filtration for 2-4 times by using methanol, and performing vacuum drying for 12-36 h at 75-100 ℃ to obtain a crude product EVA-g-T8 graft polymer;
step 4, putting the dried EVA-g-T8 graft polymer into a flask, adding toluene, heating and refluxing to dissolve the EVA, then performing suction filtration to remove insoluble substances (mainly EVA cross-linked products), dripping the filtrate into a large amount of petroleum ether to generate white flocculent precipitates, well dissolving T8 and homopolymers thereof in the petroleum ether to remove the white flocculent precipitates, and drying the precipitates obtained by filtration in a vacuum drying oven at the temperature of 40-60 ℃ for 12-30 h to obtain the refined EVA-g-T8 graft polymer;
and 5, carrying out double-roller open mixing on the EVA-g-T8 graft polymer and the light conversion agent by a plasticator according to a proportion, wherein the mixing temperature is cold roller room temperature, the mixing time is 3-5 min, and carrying out compression molding on the mixed material in a flat-plate vulcanizing machine.
According to the preparation method of the high-transparency flame-retardant EVA light conversion film, the molar ratio of the materials in the step 2 is heptapoly-cyclopentylsilsesquioxane trisilicol, allyl trichlorosilane and triethylamine is 1: 1-1.06: 8.3-10.2.
In the preparation method of the high-transparency flame-retardant EVA light conversion film, in the step 3, the EVA is an ethylene-vinyl acetate copolymer with the VA content of 10-40 wt%.
According to the preparation method of the high-transparency flame-retardant EVA light conversion film, in the step 3, the mass ratio of VA to T8 in EVA is 1: 2-10, and the mass ratio of T8 to BPO is 1: 20.
In the preparation method of the high-transparency flame-retardant EVA light conversion film, benzoyl peroxide BPO is used as an initiator in the reaction of the step 3, and double bonds are opened by allyl silsesquioxane under the action of free radicals decomposed by the initiator to combine with main chain free radicals losing H in an EVA structure to generate a grafting reaction.
In the preparation method of the highly transparent flame-retardant EVA light conversion film, the light conversion agent in the step 5 is one of a series of rare earth organic complexes, such as Eu (TTA)3Dpbt、Eu(SA)3phen、Eu(DBM)3phen, and the like.
In the preparation method of the high-transparency flame-retardant EVA light conversion film, the mass fraction of the light conversion agent in the step 5 is 0.5-3%.
According to the preparation method of the high-transparency flame-retardant EVA light conversion film, in the step 5, a proper mold is selected according to relevant standards, a mixed material sample is poured into the mold, when the temperature of a flat vulcanizing machine rises to 150-200 ℃, the mold is placed into the flat vulcanizing machine, hot pressing is carried out for 400-600 s under 10-15 MPa, then cold pressing is carried out for 300-500 s, a sample slice is prepared, and the slice is cut into sample strips required by testing on a pneumatic slicer by using a standard size cutter so as to be used for testing various performances.
Compared with the prior art, the invention has the beneficial effects that:
the invention utilizes the advantages of low toxicity, high flame retardance, high efficiency, molten drop inhibition and smoke inhibition of the silicon flame retardant to improve the flame retardance of the EVA adhesive film. The invention synthesizes the allyl silsesquioxane by using a vertex angle-cap method, successfully connects the allyl silsesquioxane on an EVA molecular chain by using a solution grafting method, improves the flame retardant property of EVA in a level manner, and provides a method which is environment-friendly, has good flame retardant effect and does not influence the light transmittance of an EVA light conversion film.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1
Synthesis of Mono-and allylsilsesquioxane (T8)
1) 250ml of acetone was charged into a 500ml three-necked flask, 15g of cyclopentyltrichlorosilane was charged, and 80ml of distilled water was added dropwise thereto at a rate of 30 drops per minute by means of a dropping funnel with vigorous stirring, for about 1 hour. And after the dropwise addition of the distilled water is finished, heating and refluxing, and reacting for 48 hours. In the whole process, the reaction system is changed from white to light yellow to orange yellow to red. After the reaction was completed, the product was vacuum filtered and washed with acetone, dried and dissolved in 20ml of pyridine, the insoluble matter was filtered off, the filtrate was poured into 50ml of frozen concentrated hydrochloric acid, filtered and dried at 35 ℃ to obtain hepta-cyclopentylsilsesquioxane trisilol as a white powder.
2) 5.20g of heptacyclopentylsilsesquioxane trissilanol are placed in a 250ml flask, 100ml of THF are added, 5.05g of triethylamine are added, 1.05g of allyltrichlorosilane are added dropwise, stirring vigorously for 2.5h and the precipitate is filtered off. The whole reaction is carried out in an ice-water bath, the transparent filtrate from which the precipitate is filtered is concentrated and put into a large amount of absolute ethyl alcohol, and the product is precipitated in the form of white particles. Dried and weighed to obtain the product, allylsilsesquioxane T8.
Preparation of EVA-g-T8 graft polymer
The flask was charged with 2.89g EVA (10 wt% VA), 0.578g (0.615mmol) T8 and 2.976g (12.3mmol) BPO under nitrogen, and 15mL of reflux-treated toluene was added in one portion via syringe. And (3) placing the reaction bottle in an oil bath, heating to 50 ℃, stirring for 15min under the protection of nitrogen until the added raw materials are gradually dissolved, slowly heating to 70 ℃, gradually changing the reaction system from colorless clarification to light brown yellow, and after 6h, dropwise adding the reaction liquid into 300mL of glacial methanol after the reaction is finished, and stirring to generate light yellow flocculent precipitate. Repeatedly washing the product obtained by suction filtration through a Buchner funnel with methanol for three times, and carrying out vacuum drying at 70 ℃ for 12h to obtain a crude product EVA-g-T8 graft polymer.
The dried EVA-g-T8 graft polymer was placed in a flask, 20mL of toluene was added, heated under reflux to completely dissolve it, and then the insoluble material (mainly the crosslinked product of EVA) was removed by suction filtration. Dripping the filtrate into a large amount of petroleum ether to generate white flocculent precipitate, removing the T8 and the homopolymer thereof which can be well dissolved in the petroleum ether, and drying the precipitate obtained by filtering in a vacuum drying oven at 40 ℃ for 12h to obtain the refined EVA-g-T8 graft polymer.
Preparation of EVA light conversion material
EVA-g-T8 graft Polymer (99.5 parts) and 0.5 part by mass of light-converting agent Eu (TTA)3Mixing Dpbt with a plasticator at cold roll room temperature for 3 min. And pouring the mixed material sample into a mold, putting the mold into a flat vulcanizing machine when the temperature of the flat vulcanizing machine reaches 150 ℃, hot-pressing for 400s under 10MPa, and then cold-pressing for 300s to prepare a sample sheet. The sheets were cut into strips for testing using a standard size cutter on a pneumatic microtome for use in testing various properties.
Example 2
Synthesis of Mono-and allylsilsesquioxane (T8)
1) 250ml of acetone was charged into a 500ml three-necked flask, 16g of cyclopentyltrichlorosilane was charged, and 90ml of distilled water was added dropwise thereto at a rate of 35 drops per minute by means of a dropping funnel with vigorous stirring, and the process was about 1 hour. And after the dropwise addition of the distilled water is finished, heating and refluxing, and reacting for 60 hours. In the whole process, the reaction system is changed from white to light yellow to orange yellow to red. After the reaction was completed, the product was vacuum filtered and washed with acetone, dried and dissolved in 25ml of pyridine, the insoluble matter was filtered off, the filtrate was poured into 60ml of frozen concentrated hydrochloric acid, filtered and dried at 40 ℃ to obtain hepta-cyclopentylsilsesquioxane trisilol as a white powder.
2) 5.20g of heptacyclopentylsilsesquioxane trissilanol are placed in a 250ml flask, 110ml of THF are added, 6g of triethylamine are added, 1.085g of allyltrichlorosilane are added dropwise, stirring vigorously for 3h and the precipitate is filtered off. The whole reaction was carried out in an ice-water bath. The clear filtrate from which the precipitate was filtered off was put into a large amount of anhydrous ethanol, and the product precipitated in the form of white particles. Dried and weighed to obtain the product, allylsilsesquioxane T8.
Preparation of EVA-g-T8 graft polymer
The flask was charged with 0.83g EVA (28 wt% VA), 1.156g (1.23mmol) T8 and 5.953g (24.6mmol) BPO under nitrogen, and 30mL of reflux-treated toluene was added in one portion via syringe. And (3) placing the reaction bottle in an oil bath, heating to 65 ℃, stirring for 25min under the protection of nitrogen until the added raw materials are gradually dissolved, slowly heating to 85 ℃, gradually changing the reaction system from colorless clarification to light brown yellow, and after 7h, dropwise adding the reaction liquid into 450mL of glacial methanol after the reaction is finished, and stirring to generate light yellow flocculent precipitate. Repeatedly washing the product obtained by suction filtration through a Buchner funnel with methanol for three times, and carrying out vacuum drying at 85 ℃ for 30h to obtain a crude product EVA-g-T8 graft polymer.
The dried EVA-g-T8 graft polymer was placed in a flask, 35mL of toluene was added, heated under reflux to dissolve it, and then the insoluble material (mainly crosslinked EVA) was removed by suction filtration. Dripping the filtrate into a large amount of petroleum ether to generate white flocculent precipitate, removing the T8 and the homopolymer thereof which can be well dissolved in the petroleum ether, and drying the precipitate obtained by filtering in a vacuum drying oven at 60 ℃ for 20h to obtain the refined EVA-g-T8 graft polymer.
Preparation of EVA light conversion material
EVA-g-T8 graft polymer (98.5 parts) and 1.5 parts by mass of light-converting agent Eu (SA)3phen adopts a plasticator to carry out double-roller open mixing, the mixing temperature is cold roller room temperature, and the mixing time is 4 min. And pouring the mixed material sample into a mold, putting the mold into a flat vulcanizing machine when the temperature of the flat vulcanizing machine reaches 180 ℃, carrying out hot pressing for 500s under 12MPa, and then carrying out cold pressing for 400s to prepare a sample sheet. The sheets were cut into strips for testing using a standard size cutter on a pneumatic microtome for use in testing various properties.
Example 3
Synthesis of Mono-and allylsilsesquioxane (T8)
1) 250ml of acetone was charged into a 500ml three-necked flask, 18g of cyclopentyltrichlorosilane was charged, and 100ml of distilled water was added dropwise thereto at a rate of 50 drops per minute by means of a dropping funnel with vigorous stirring, and the process was about 1 hour. And after the dropwise addition of the distilled water is finished, heating and refluxing, and reacting for 72 hours. In the whole process, the reaction system is changed from white to light yellow to orange yellow to red. After the reaction was completed, the product was vacuum filtered and washed with acetone, dried and dissolved in 30ml of pyridine, the insoluble matter was filtered off, the filtrate was poured into 65ml of frozen concentrated hydrochloric acid, filtered and dried at 50 ℃ to obtain hepta-cyclopentylsilsesquioxane trisilol as a white powder.
2) 5.20g of heptacyclopentylsilsesquioxane trissilanol are placed in a 250ml flask, 120ml of THF are added, 6.2g of triethylamine are added, 1.116g of allyltrichlorosilane are added dropwise, stirring vigorously for 5h and the precipitate is filtered off. The whole reaction was carried out in an ice-water bath. The clear filtrate from which the precipitate was filtered off was put into a large amount of anhydrous ethanol, and the product precipitated in the form of white particles. Drying and weighing to obtain the product, namely the allylsilsesquioxane.
Preparation of EVA-g-T8 graft polymer
The flask was charged with 0.44g EVA (40 wt% VA), 1.734g (1.845mmol) T8 and 8.93g (36.9mmol) BPO under nitrogen, and 30mL toluene treated by reflux condensation was added in one portion via syringe. And (3) placing the reaction bottle in an oil bath, heating to 70 ℃, stirring for 30min under the protection of nitrogen until the added raw materials are gradually dissolved, slowly heating to 90 ℃, gradually changing the reaction system from colorless clarification to light brown yellow, after 9h, dropwise adding the reaction liquid into 600mL of glacial methanol after the reaction is finished, and stirring to generate light yellow flocculent precipitate. Repeatedly washing the product obtained by suction filtration through a Buchner funnel with methanol for three times, and carrying out vacuum drying at 90 ℃ for 36h to obtain a crude product EVA-g-T8 graft polymer.
The dried EVA-g-T8 graft polymer was placed in a flask, 40mL of toluene was added, heated under reflux to dissolve it, and then the insoluble material (mainly crosslinked EVA) was removed by suction filtration. Dripping the filtrate into a large amount of petroleum ether to generate white flocculent precipitate, removing the T8 and the homopolymer thereof which can be well dissolved in the petroleum ether, and drying the precipitate obtained by filtering in a vacuum drying oven at 60 ℃ for 30h to obtain the refined EVA-g-T8 graft polymer.
Preparation of EVA light conversion material
EVA-g-T8 graft polymer (97 parts) and 3 parts of light conversion agent Eu (DBM)3phen adopts a plasticator to carry out double-roller open mixing, the mixing temperature is cold roller room temperature, and the mixing time is 5 min. And pouring the mixed material sample into a mold, putting the mold into a flat vulcanizing machine when the temperature of the flat vulcanizing machine reaches 200 ℃, hot-pressing for 600s under 15MPa, and then cold-pressing for 500s to prepare a sample sheet. The sheets were cut into strips for testing using a standard size cutter on a pneumatic microtome for use in testing various properties.
Example 4
Synthesis of Mono-and allylsilsesquioxane (T8)
1) 250ml of acetone was charged into a 500ml three-necked flask, 18g of cyclopentyltrichlorosilane was charged, and 100ml of distilled water was added dropwise thereto at a rate of 50 drops per minute by means of a dropping funnel with vigorous stirring, and the process was about 1 hour. And after the dropwise addition of the distilled water is finished, heating and refluxing, and reacting for 72 hours. In the whole process, the reaction system is changed from white to light yellow to orange yellow to red. After the reaction was completed, the product was vacuum filtered and washed with acetone, dried and dissolved in 30ml of pyridine, the insoluble matter was filtered off, the filtrate was poured into 65ml of frozen concentrated hydrochloric acid, filtered and dried at 50 ℃ to obtain hepta-cyclopentylsilsesquioxane trisilol as a white powder.
2) 5.20g of heptacyclopentylsilsesquioxane trissilanol are placed in a 250ml flask, 120ml of THF are added, 6.2g of triethylamine are added, 1.116g of allyltrichlorosilane are added dropwise, stirring vigorously for 5h and the precipitate is filtered off. The whole reaction was carried out in an ice-water bath. The clear filtrate from which the precipitate was filtered off was concentrated and put into a large amount of anhydrous ethanol, and the product precipitated as white particles. Drying and weighing to obtain the product, namely the allylsilsesquioxane.
Preparation of EVA and T8 blend Material
Into the flask were added 2.89g of EVA (10 wt% VA), 0.578g (0.615mmol) of T8 under nitrogen, and 30mL of toluene treated by reflux condensation was added in one portion with a syringe, and the mixture was stirred well and mixed well.
Preparation of EVA light conversion material
98.5 parts of the blending material obtained in the step two and 1.5 parts of light conversion agent Eu (SA) in mass fraction3phen adopts a plasticator to carry out double-roller open mixing, the mixing temperature is cold roller room temperature, and the mixing time is 3 min. And pouring the mixed material sample into a mold, putting the mold into a flat vulcanizing machine when the temperature of the flat vulcanizing machine reaches 150 ℃, hot-pressing for 400s under 10MPa, and then cold-pressing for 300s to prepare a sample sheet. The sheets were cut into strips for testing using a standard size cutter on a pneumatic microtome for use in testing various properties.
Test method
1. Limiting oxygen index test
According to ASTM D2863-09, the test specimens were tested by HC-2CZ oxygen index tester, Nanjing Shangyuan Analyzer Co., Ltd, the specimens of fixed specifications were set on a jig and ignited under conditions of different oxygen concentrations, the minimum oxygen concentration for supporting the combustion of the specimens was measured, and the flow rate of the oxygen-nitrogen mixed gas was 10L/min.
2. Vertical burning test
The prepared EVA sample strips were tested for flame retardancy by UL-94 vertical burning test using a model CZF-6 horizontal vertical burning tester from Jiangning district analytical instruments, Nanjing, and the vertical burning test (UL-94) was performed on test specimens vertically suspended above cotton wool (for identifying drips) and defined according to US national standard UL-94-2006.
3. Light transmittance test
Selecting an ultraviolet-visible spectrophotometer UV3600, taking air as a background, sticking an EVA adhesive film on a light-transmitting opening, covering a light path, and testing the light transmittance of the material in a light region of 200-800 nm.
4. Fluorescence property test
The testing instrument is an ultraviolet-fluorescence spectrophotometer Varian, a cut sample is attached to a sample table, an excitation spectrum is tested in an ultraviolet region of 250-500 nm, and the wavelength lambda of the maximum excitation peak is searchedexThen at λexWave (wave)
Measuring emission spectrum under long excitation, and finding out maximum emission peak position lambdaem。
5. Measurement of film tensile Property
The film thickness is 0.2mm, according to the determination of the tensile properties of the plastic film of International Standard ISO 1184-1983.
Table 1 composite performance test data
| Example 1 | Example 2 | Example 3 | Example 4 | |
| Oxygen index LOI/%) | 35.9 | 38.2 | 37.4 | 24.1 |
| UL-94 | V-0 | V-0 | V-0 | V-2 |
| Transmittance (a) | 93.5 | 91.5 | 92.6 | 85.8 |
| Intensity of fluorescence | 81.3 | 85.9 | 90.7 | 63.5 |
| Tensile Strength/Mp | 27.6 | 26.8 | 26.5 | 22.1 |
Claims (8)
1. The utility model provides a high transparent fire-retardant EVA membrane that turns round, characterized by: the high-transparency flame-retardant EVA light conversion film is prepared by blending an ethylene-vinyl acetate grafted allyl silsesquioxane T8 polymer EVA-g-T8 grafted polymer and a light conversion agent through a solution grafting method.
2. The preparation method of the high-transparency flame-retardant EVA light conversion film is characterized by comprising the following steps of:
step 1, adding acetone into a three-neck flask, adding cyclopentyl trichlorosilane, dropwise adding distilled water into the three-neck flask at a speed of 30-50 drops per minute by using a dropping funnel, stirring vigorously, heating and refluxing after the dropwise adding of the distilled water is finished, reacting for 48-72 hours, vacuumizing and filtering a product after the reaction is finished, cleaning the product by using acetone, dissolving the product in pyridine after drying, filtering out insoluble substances, pouring the filtrate into frozen concentrated hydrochloric acid, filtering, and drying at 40-60 ℃ to obtain hepta-cyclopentyl silsesquioxane trisilicitol;
step 2, dispersing heptapoly-cyclopentyl silsesquioxane trisilicitol obtained in the step 1 into THF, adding the dispersed heptapoly-cyclopentyl silsesquioxane trisilicitol into a flask, adding triethylamine, fully stirring and uniformly mixing, dropwise adding allyl trichlorosilane, filtering out precipitates after violently stirring for 3-5 h, carrying out the whole reaction in an ice water bath, concentrating a transparent filtrate from which the precipitates are filtered out, putting the transparent filtrate into a large amount of anhydrous ethanol, precipitating the product in a white particle form, drying and weighing to obtain a product, namely, allyl silsesquioxane T8;
step 3, adding EVA, allyl silsesquioxane T8 and benzoyl peroxide BPO into a flask, performing nitrogen protection, adding toluene subjected to reflux condensation treatment at one time by using an injector, placing a reaction bottle into an oil bath, heating to 50-70 ℃, stirring for 15-25 min under the protection of nitrogen until the added raw materials are gradually dissolved, slowly raising the temperature to 80-100 ℃, dropwise adding the reaction liquid into ice methanol after 6-8 h, stirring to generate light yellow flocculent precipitate after the reaction is finished, repeatedly washing the product obtained by suction filtration for 2-4 times by using methanol, and performing vacuum drying for 12-36 h at 75-100 ℃ to obtain a crude product EVA-g-T8 graft polymer;
step 4, putting the dried EVA-g-T8 graft polymer into a flask, adding toluene, heating and refluxing to dissolve the EVA, then performing suction filtration to remove insoluble substances (mainly EVA cross-linked products), dripping the filtrate into a large amount of petroleum ether to generate white flocculent precipitates, well dissolving T8 and homopolymers thereof in the petroleum ether to remove the white flocculent precipitates, and drying the precipitates obtained by filtration in a vacuum drying oven at the temperature of 40-60 ℃ for 12-30 h to obtain the refined EVA-g-T8 graft polymer;
and 5, carrying out double-roller open mixing on the EVA-g-T8 graft polymer and the light conversion agent by a plasticator according to a proportion, wherein the mixing temperature is cold roller room temperature, the mixing time is 3-5 min, and carrying out compression molding on the mixed material in a flat-plate vulcanizing machine.
3. The method for preparing the highly transparent flame-retardant EVA light conversion film according to claim 2, wherein the method comprises the following steps: the molar ratio of the materials in the step 2 is heptapoly-cyclopentylsilsesquioxane trisilicol, allyl trichlorosilane and triethylamine which are 1: 1-1.06: 8.3-10.2.
4. The method for preparing the highly transparent flame-retardant EVA light conversion film according to claim 2, wherein the method comprises the following steps: in the step 3, the EVA is an ethylene-vinyl acetate copolymer with the VA content of 10-40 wt%.
5. The method for preparing the highly transparent flame-retardant EVA light conversion film according to claim 2, wherein the method comprises the following steps: in the step 3, the mass ratio of VA to T8 in the EVA is 1: 2-10, and the mass ratio of T8 to BPO is 1: 20.
6. The method for preparing the highly transparent flame-retardant EVA light conversion film according to claim 2, wherein the method comprises the following steps: the light conversion agent in the step 5 is Eu (TTA)3Dpbt、Eu(SA)3phen or Eu (DBM)3phen。
7. The highly transparent flame retardant EVA light conversion film of claim 6The preparation method is characterized in that: eu (TTA)3The dpbt has better excitation in the ultraviolet region of 200-400 nm, Eu (SA)3phen has better excitation in the ultraviolet region of 300-330 nm, Eu (DBM)3phen has better excitation in an ultraviolet region of 250-400 nm, wherein TTA is α -thienyl formyl trifluoroacetone, SA is salicylic acid, phen is phenanthroline, DBM is dibenzoyl methane, and dpbt is 2- (N, N-diethylaniline-4-yl) -4, 6-bis (3, 5-dimethylpyrazol-1-yl) -1, 3, 5-triazine.
8. The method for preparing the highly transparent flame-retardant EVA light conversion film according to claim 2, wherein the method comprises the following steps: the mass fraction of the light conversion agent in the step 5 is 0.5-3%.
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| CN113930169A (en) * | 2021-11-01 | 2022-01-14 | 南京工程学院 | Heat-resistant EVA (ethylene vinyl acetate) adhesive film and preparation method thereof |
| CN117700915A (en) * | 2023-11-02 | 2024-03-15 | 上海鑫亮塑胶制品股份有限公司 | Matte environment-friendly PP composite material and processing technology thereof |
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| CN117700915A (en) * | 2023-11-02 | 2024-03-15 | 上海鑫亮塑胶制品股份有限公司 | Matte environment-friendly PP composite material and processing technology thereof |
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