CN107603510A - Phosphoric acrylic ester fire retardant, fire-retardant EVA adhesive film and preparation method thereof - Google Patents
Phosphoric acrylic ester fire retardant, fire-retardant EVA adhesive film and preparation method thereof Download PDFInfo
- Publication number
- CN107603510A CN107603510A CN201710845887.8A CN201710845887A CN107603510A CN 107603510 A CN107603510 A CN 107603510A CN 201710845887 A CN201710845887 A CN 201710845887A CN 107603510 A CN107603510 A CN 107603510A
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- China
- Prior art keywords
- acrylic ester
- formula
- retardant
- phosphoric acrylic
- fire
- Prior art date
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 67
- -1 acrylic ester Chemical class 0.000 title claims abstract description 66
- 239000002313 adhesive film Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 15
- 239000011230 binding agent Substances 0.000 claims abstract description 9
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001125 extrusion Methods 0.000 claims description 35
- 239000010410 layer Substances 0.000 claims description 33
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 28
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 claims description 28
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000011347 resin Substances 0.000 claims description 24
- 229920005989 resin Polymers 0.000 claims description 24
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 21
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 18
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 18
- 229910000077 silane Inorganic materials 0.000 claims description 18
- 238000004132 cross linking Methods 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 17
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 16
- 150000002978 peroxides Chemical class 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- 239000004611 light stabiliser Substances 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 14
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 13
- 239000004408 titanium dioxide Substances 0.000 claims description 12
- 239000006096 absorbing agent Substances 0.000 claims description 11
- 239000012528 membrane Substances 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 10
- 229920002554 vinyl polymer Polymers 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 8
- 239000011698 potassium fluoride Substances 0.000 claims description 8
- 235000003270 potassium fluoride Nutrition 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 239000000741 silica gel Substances 0.000 claims description 7
- 229910002027 silica gel Inorganic materials 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000010828 elution Methods 0.000 claims description 6
- 239000012044 organic layer Substances 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 238000010898 silica gel chromatography Methods 0.000 claims description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 238000010348 incorporation Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- KZTWONRVIPPDKH-UHFFFAOYSA-N 2-(piperidin-1-yl)ethanol Chemical compound OCCN1CCCCC1 KZTWONRVIPPDKH-UHFFFAOYSA-N 0.000 claims description 3
- YOCHOHIOBBCVFR-UHFFFAOYSA-N 3-tert-butyl-2,2-dimethyloctane Chemical compound CCCCCC(C(C)(C)C)C(C)(C)C YOCHOHIOBBCVFR-UHFFFAOYSA-N 0.000 claims description 3
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical group N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 claims description 3
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 claims description 3
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000001925 cycloalkenes Chemical class 0.000 claims description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical group CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 229940116351 sebacate Drugs 0.000 claims description 3
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 claims description 3
- 239000004258 Ethoxyquin Substances 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 2
- 239000012792 core layer Substances 0.000 claims description 2
- DECIPOUIJURFOJ-UHFFFAOYSA-N ethoxyquin Chemical compound N1C(C)(C)C=C(C)C2=CC(OCC)=CC=C21 DECIPOUIJURFOJ-UHFFFAOYSA-N 0.000 claims description 2
- 229940093500 ethoxyquin Drugs 0.000 claims description 2
- 235000019285 ethoxyquin Nutrition 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- 125000004417 unsaturated alkyl group Chemical group 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims 1
- VZZJVOCVAZHETD-UHFFFAOYSA-N diethylphosphane Chemical compound CCPCC VZZJVOCVAZHETD-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 6
- 230000032683 aging Effects 0.000 abstract description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 16
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 8
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 8
- 235000019341 magnesium sulphate Nutrition 0.000 description 8
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 5
- 230000003595 spectral effect Effects 0.000 description 5
- 229930040373 Paraformaldehyde Natural products 0.000 description 4
- 238000007689 inspection Methods 0.000 description 4
- 150000004002 naphthaldehydes Chemical class 0.000 description 4
- BAQNULZQXCKSQW-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[Ti+4].[Ti+4] BAQNULZQXCKSQW-UHFFFAOYSA-N 0.000 description 4
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 4
- 229920002866 paraformaldehyde Polymers 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- 239000008247 solid mixture Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 4
- 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 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical class OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 description 2
- 239000004831 Hot glue Substances 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229940126678 chinese medicines Drugs 0.000 description 2
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 2
- 125000004980 cyclopropylene group Chemical group 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N diethylenediamine Natural products C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
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- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical group OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 description 1
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- SLNMJVMGIXUXFI-UHFFFAOYSA-N CCOP(C(c1ccccc1)O)(OCC)=O Chemical compound CCOP(C(c1ccccc1)O)(OCC)=O SLNMJVMGIXUXFI-UHFFFAOYSA-N 0.000 description 1
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
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- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000003340 retarding agent Substances 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229940124543 ultraviolet light absorber Drugs 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a kind of phosphoric acrylic ester fire retardant, with the structure as shown in formula I, further relate to a kind of preparation method of phosphoric acrylic ester fire retardant, diethyl phosphonate as shown in formula II reacts midbody compound of the generation as shown in formula IV with the aldehyde compound as shown in formula II in the presence of acid binding agent, midbody compound as shown in formula IV and phosphoric acrylic ester of the methacrylic chloride reaction generation as shown in formula I as shown in formula V, the invention further relates to a kind of using fire-retardant EVA adhesive film of the phosphoric acrylic ester fire retardant and preparation method thereof.The phosphoric acrylic ester fire retardant effect of the present invention is good, can be on graft reaction to EVA strands, so that the original caking property of EVA adhesive film and ageing resistace are constant, to increase certain anti-flammability.
Description
Technical field
The present invention relates to a kind of phosphoric acrylic ester fire retardant and preparation method thereof, a kind of application fire retardant it is fire-retardant
EVA adhesive film and preparation method thereof, belong to technical field of polymer materials.
Background technology
Solar photovoltaic assembly, abbreviation PV components, it is the core in solar photovoltaic generation system.It is by advance
Arrange one set up battery, ultra-thin tempering clear glass, packaging adhesive film and form.Some photovoltaic modulies are installed solid with fluid sealant
It is scheduled on framework and forms solar panel, generally regulation solar panel application life is in 30 years, so as to use component
Packaging plastic proposes very high requirement, is resistant to high and low temperature environment, moistureproof, anticorrosive, resistance to ultraviolet and wet and heat ageing resistant, Yi Jiliang
Good insulation and fire resistance.Existing laminate product has to insulate well, the anti-aging and performance of environmental change, still,
It is a significant deficiency of solar photovoltaic assembly without fire resistance.
With the significantly development of distributed power generation, increasing photovoltaic module is applied in the more field of resident,
Such as factory building, public building, villa, office block etc..Along with the opto-electronic conversion of crystal silicon solar batteries, component can be significantly improved
Internal temperature, because mismatch or hot spot effect can bring overheat and causes the danger of fire.
Traditional glued membrane is modified, and is in polyolefin elastomer, as added substantial amounts of small molecule fire retardant in EVA or POE.Such as
Chinese patent literature CN1401721 discloses a kind of polyolefin hot-melt adhesive and the composite junction using the hot melt adhesive
Structure film, wherein with the addition of hydroxide.Chinese patent literature CN102936483A discloses a kind of single-component organic silicon sun
Energy photovoltaic module fluid sealant and preparation method thereof, wherein silicon-series five-retardant is added, expanded graphite, the small molecule addition of phosphorus nitrogen system
Agent.These additives are added in the glued membrane after cross-linking modified, due to the poor compatibility of micromolecule additive and EVA, long-term
In ultraviolet and hydrothermal aging, aging blemiss occurs between boundary.Fire retardant is optionally selected, on the one hand without preferable fire-retardant effect
Fruit, such as be difficult to reach vertical combustion UL-94V-0 levels；On the other hand, certainly will influence compatibility between the other components of glued membrane and
Concertedness, in turn results in caking property reduction, and aged properties decay is serious.
The content of the invention
, can be with graft reaction to EVA strands the technical problem to be solved in the present invention is to provide a kind of good flame retardation effect
Phosphoric acrylic ester fire retardant, and the preparation method of the fire retardant, and the fire-retardant EVA adhesive film containing the fire retardant, with
And the preparation method of the glued membrane.
The present invention is to solve a kind of technical scheme that above-mentioned technical problem proposes to be：A kind of phosphoric acrylic ester fire retardant,
With the structure as shown in formula I,
Wherein, R is hydrogen atom, aliphatic group or aryl.
The alkyl that above-mentioned R is C1~C8 (can be methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, sec-butyl, uncle
Butyl etc.), C3~C8 cycloalkyl (can be cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, cyclooctyl etc.), C2~C8 not
Saturated hydrocarbyl (can be vinyl, acrylic, pi-allyl etc.), C3~C8 cycloolefin (can be cyclopropylene, cyclobutane, ring
Amylene etc.) or C6~C10 aryl (can be phenyl, tolyl, xylyl, naphthyl etc.).
The present invention is to solve the another technical solution that above-mentioned technical problem proposes to be：A kind of phosphoric acrylic ester fire retardant
Preparation method, diethyl phosphonate as shown in formula II and the aldehyde compound as shown in formula II are anti-in the presence of acid binding agent
The midbody compound as shown in formula IV should be generated,
Midbody compound as shown in formula IV is with the methacrylic chloride reaction generation as shown in formula V as shown in formula I
Phosphoric acrylic ester,
The above-mentioned preferred paraformaldehyde of aldehyde compound, para-acetaldehyde, propionic aldehyde, butyraldehyde, or benzaldehyde, naphthaldehyde.
Above-mentioned acid binding agent is triethylamine, potassium fluoride or cesium fluoride, the diethyl phosphonate, aldehyde compound, acid binding agent
Mol ratio be 1:1:1~5, the reaction temperature for generating midbody compound is 0 DEG C~30 DEG C, reaction time 1h~5h.
The mol ratio of above-mentioned diethyl phosphonate and methacrylic chloride is 1:1~1.1, generate the anti-of phosphoric acrylic ester
It is 0 DEG C~30 DEG C to answer temperature, reaction time 1h~12h.
Generate the solid product obtained by phosphoric acrylic ester, 6mol/L aqueous hydrochloric acid solution, 1mo l/L is respectively adopted
Sodium bicarbonate aqueous solution is washed, and after liquid separation, organic layer is dried with magnesium sulfate, then is dried in vacuo；Then gained solid uses silica gel
Column chromatography purification obtains phosphoric acrylic ester finished product, and the particle diameter of silica gel is 70~230 mesh, and elution is mutually ethyl acetate and oil
Ether is according to mass ratio 1:The mixed liquor of 1 mixing.
The present invention is to solve a kind of technical scheme that above-mentioned technical problem proposes to be：A kind of fire-retardant EVA adhesive film has ABA tri-
Rotating fields, top layer include the component of following mass percent：EVA resin 96.5%~98.5%, nanometer basic zirconium phosphate 0.05%~
0.1%, peroxide 0.5%~1%, crosslinking coagent 0.5%~1%, silane coupler 0.2%~0.6%, UV Absorption
Agent 0.1%~0.5%, light stabilizer 0.1%~0.5%；
Sandwich layer includes the component of following mass percent：EVA resin 74%~82.5%, titanium dioxide 7~8%, phosphorous third
Olefin(e) acid ester fire retardant 9%~15%, peroxide 0.5%~1%, crosslinking coagent 0.5%~1%, silane coupler 0.2%~
0.6%, UV absorbers 0.1%~0.5%, light stabilizer 0.1%~0.5%；
The phosphoric acrylic ester fire retardant has the structure as shown in formula I,
Wherein, R is hydrogen atom, aliphatic group or aryl.
Core layer thickness is 400 μm~500 μm, and skin depth is 50 μm~100 μm；The peroxide is 2,5- diformazans
The di-t-butyl hexane peroxide of base -2,5, peroxidating -2- ethylhexyl carbonates tert-pentyl ester and peroxidating -2- ethylhexyl carbonate uncles
One or more in butyl ester；
The crosslinking coagent is isocyanic acid triallyl, three (2- ethoxys)-isocyanuric acid triacrylates, trihydroxy methyl
Propane triacrylate, pentaerythritol triacrylate and one kind or more in ethoxyquin trimethylolpropane trimethacrylate
Kind；
The silane coupler is vinyltrimethoxy silane, the vinyltriacetoxy silane, (β-first of vinyl three
Epoxide ethyoxyl) it is one or more in silane；
The light stabilizer be double (1- octyloxies -2,2,6,6- tetramethyl -4- piperidyls) sebacates, it is double (2,2,6,
6- tetramethyl -4- piperidyls) in sebacate and poly-succinic (4 hydroxyls -2,2, the piperidine ethanol fat of 6,6- tetramethyl -1) one
Kind is a variety of；
The UV absorbers are 2- [4,6- double (2,4- 3,5-dimethylphenyl) -1,3,5-triazines -2- bases] -5- (pungent oxygen
Base) phenol；
VA contents in the EVA resin are 20%~30%；
The particle diameter of nanometer basic zirconium phosphate is 200nm~300nm.
The present invention is to solve the another technical solution that above-mentioned technical problem proposes to be：A kind of above-mentioned fire-retardant EVA adhesive film
Preparation method, comprise the following steps：
Step S1, EVA resin and nanometer basic zirconium phosphate are mixed into extrusion basic zirconium phosphate master batch is made, by EVA resin and titanium dioxide
Titanium dioxide master batch is made in mixing extrusion；
Step S2, the glued membrane of ABA three-deckers is prepared using extrusion equipment and multilayer extrusion die head；Basic zirconium phosphate master batch is used for
Extrusion is mixed with other components top layer is made, sandwich layer is made for mixing extrusion with other components in titanium dioxide master batch.
Mixed in above-mentioned steps S1 using vertical double helical ribbon mixer, driving power is 3KW~120KW, during mixing
Between be 3min~10min；
Extruded in the step S1 using extruding machine with two screw rods engaging in the same direction, pair of extruding machine with two screw rods engaging in the same direction
Screw speed is 40r/min~60r/min, and each section of temperature respectively is 140 DEG C, 150 DEG C, 170 DEG C, 180 DEG C, 180 DEG C；
Prepared by the top layer in the step S2 uses extruding machine with two screw rods engaging in the same direction, screw diameter 95mm, and screw rod turns
Speed is 30r/min~60r/min, and each section of temperature respectively is 75 DEG C, 80 DEG C, 84 DEG C, 85 DEG C, 85 DEG C；
Prepared by the sandwich layer in the step S2 uses single screw extrusion machine, screw diameter 130mm, screw speed 30r/
Min~60r/min, each section of temperature respectively are 75 DEG C, 80 DEG C, 84 DEG C, 85 DEG C, 85 DEG C.
The present invention has positive effect：
(1) phosphoric acrylic ester fire retardant of the invention is using diethyl phosphonate, aldehyde, acryloyl chloride as raw material, triethylamine,
Potassium fluoride or cesium fluoride are acid binding agent, are reacted under low temperature and can obtain phosphoric acrylic ester, synthetic method is simple, and cost is low.Contain
Phosphorus acrylate as fire retarding agent can carry out free radical grafting reaction with EVA resin, crosslinking coagent under peroxide initiation, not deposit
The migration precipitation and poor compatibility the defects of.So that EVA resin is not before the original caking property of glued membrane and ageing resistace is changed
Put, glued membrane has certain anti-flammability in itself, can be used for the higher photovoltaic art of fire-retardant fireproof requirement.
(2) EVA adhesive film of the invention contains top layer and contains a nanometer basic zirconium phosphate, by under the processing of top layer Strong shear, adding
Basic zirconium phosphate master batch can reduce reunion, and fire retardant coordinates the flame-retardant and anti-dripping effect of nanometer basic zirconium phosphate, retarding heat and caloic
Transmit, further improve the anti-flammability of EVA adhesive film.
Brief description of the drawings
Fig. 1 is the nucleus magnetic hydrogen spectrum figure of the phosphoric acrylic ester fire retardant of the embodiment of the present invention 1.
Fig. 2 is the nuclear-magnetism carbon spectrogram of the phosphoric acrylic ester fire retardant of the embodiment of the present invention 1.
Fig. 3 is the infrared spectrogram of the phosphoric acrylic ester fire retardant of the embodiment of the present invention 1.
Fig. 4 is the thermogravimetric curve after the fire-retardant EVA adhesive film solidification of application examples 1 of the present invention.
The schematic flow sheet of the preparation method of the fire-retardant EVA adhesive film of Fig. 5 addition embodiments 1.
Embodiment
Unless otherwise defined, anticipated known to all specialties used in text and scientific words and one skilled in the art
Justice is identical.Such as：C1~C8 alkyl refers to the alkyl that carbon chain lengths are 1~8, such as：Methyl, ethyl, propyl group, isopropyl, fourth
Base, isobutyl group, sec-butyl, the tert-butyl group, amyl group, hexyl, heptyl, octyl group etc..C3~C8 cycloalkyl refer to carbon chain lengths for 3~
8 cycloalkyl, such as：Cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, cyclooctyl etc..C2~C8 unsaturated alkyl refers to carbochain
Length is 2~8 alkyl containing double or triple bonds, such as：Vinyl, acrylic, pi-allyl.C3~C8 cycloolefin refers to carbon
Chain length is 3~8 cyclic hydrocarbon radical containing double bond, such as：Cyclopropylene, cyclobutane, cyclopentene.Aryl refer to carbon chain lengths for 6~
10 aromatic hydrocarbon, such as：Phenyl, tolyl, xylyl, naphthyl etc..
Embodiment 1
Phosphoric acrylic ester (diethoxyphosphoryl) the methyl methacrylate-DEPMM's of the present embodiment
Reaction equation is as follows：
Preparation method is that diethyl phosphonate (DEP) is added drop-wise to the dichloromethane of paraformaldehyde and triethylamine (TEA)
In mixed solution.Wherein DEP, paraformaldehyde, triethylamine in molar ratio 1:1:1 ratio, reaction temperature is 120 DEG C, during reaction
Between 4h.After having reacted, after magnesium sulfate is dried, rotary evaporation removes solvent and can obtain midbody compound.
Gained midbody compound and 800ppm 4- metoxyphenols are dissolved in chloroform solvent, and 4- metoxyphenols rise
Reaction is not participated in the effect of regulation Ph values and solubilising, and the chloroformic solution of acryloyl chloride is added drop-wise to midbody compound and three at 0 DEG C
In ethamine chloroformic solution.Wherein, the mol ratio of diethyl phosphonate and methacrylic chloride is 1:1.1, reaction time at room temperature
12h.Solid mixture after having reacted, with 6mol/L aqueous hydrochloric acid solution, 1mol/L sodium bicarbonate aqueous solution washs, liquid separation
Afterwards, organic layer is dried with magnesium sulfate, then is dried in vacuo；Then gained solid obtains phosphorous propylene using silica gel column chromatography purification
Acid esters finished product, the particle diameter of silica gel is 70~230 mesh, and elution is mutually ethyl acetate and petroleum ether according to mass ratio 1:1 mixing mixes
Close liquid.Product carries out hydrogen spectral test and infrared inspection, yield 71%.
The nucleus magnetic hydrogen spectrum figure of product as shown in figure 1,1H NMR:1.35 (6H, t, J=7.1), 1.97 (3H, s), 4.11
(4H, m), 4.41 (2H, d, JHP=8.7), 5.65 (1H, s), 6.18 (1H, s).Wherein chemical shift is second in δ=1.35ppm
Methyl CH in epoxide3- characteristic peak, δ=4.11ppm are methylene CH on ethyoxyl2- characteristic peak, δ=1.97ppm is phosphonate ester
Upper methylene CH2- characteristic peak, δ=5.65ppm are the-CH that phenyl hypo acid is connected with carbonyl2-CH2The characteristic peak of-upper proton, δ=
4.11ppm is methylene CH on phosphonate ester2The characteristic peak of proton on-characteristic peak phenyl ring, δ=4.41ppm are methylene on vinyl
Base CH2- characteristic peak, δ=6.18ppm be vinyl on methine characteristic peak.Above-mentioned peak value illustrates, both contains third in structure
Olefin(e) acid ester, contain diethyl phosphonate structure again.
The nuclear-magnetism carbon spectrogram of product as shown in Fig. 213C NMR:16.0 (2C, d, JCP=5.9), 17.7,56.5 (d, JCP
=169.2), 62.3 (2C, JCP=6.5), 126.3,134.9,165.7 (d, J=8.5).Wherein chemical shift is in δ=16ppm
It is the characteristic peak of C on diethyl methyl, δ=17.7ppm is the characteristic peak of C on methyl by vinyl, and δ=56.5ppm is
For the characteristic peak of C on the methylene of ethyl, δ=62.3ppm is the characteristic peak of C on the methylene being connected with phosphonate ester, and δ=
On 165.7ppm vinyl on methine C characteristic peak, on δ=126.3ppm vinyl on methylene C characteristic peak；Above-mentioned peak
Value illustrates, both contains diethyl phosphonate, and the structure containing acrylate in structure.
The infrared spectrogram of product is as shown in figure 3, IR:2983,2864,1730,1640,1593,1268,1035,970,
760.Wherein in wave number 2983cm-1Locate as CH3C-H stretching vibration absworption peak, in wave number 2864cm-1Locate as CH2C-H
Stretching vibration absworption peak, wave number 1730cm-1Locate the stretching vibration peak for C=O, wave number 1593cm-1Locate as CH2Stretching vibration inhale
Receive peak, wave number 1268cm-1Locate the stretching vibration absworption peak for P-O-C, wave number 1035cm-1Locate as CH2=CH- stretching vibration is inhaled
Receive peak；Wave number 970cm-1Locate as C-O-C flexural vibrations absworption peaks.Above-mentioned peak value illustrates, both contains diethyl phosphonate in structure,
Structure containing acrylate again.
Embodiment 2
Phosphoric acrylic ester 1- (diethoxyphosphoryl) the butyl methacrylate-D of the present embodiment
EPBMM reaction equation is as follows：
Preparation method be by diethyl phosphonate (DEP) be added drop-wise to butyraldehyde and cesium fluoride (CsF) dichloromethane mix it is molten
In liquid.Wherein DEP, butyraldehyde, cesium fluoride in molar ratio 1:1:2 ratio, 25 DEG C of reaction temperature, react 1h.After having reacted, sulfuric acid
After magnesium is dried, rotary evaporation removes solvent and can obtain midbody compound.
Gained midbody compound and 800ppm 4- metoxyphenols are dissolved in chloroform solvent, the chloroform of acryloyl chloride
Solution is added drop-wise in midbody compound and cesium fluoride chloroformic solution at 0 DEG C.Wherein, diethyl phosphonate and methacrylic chloride
Mol ratio be 1:1.1, reaction time 12h at room temperature.Solid mixture after having reacted, with 6mol/L aqueous hydrochloric acid solution,
1mol/L sodium bicarbonate aqueous solution washing, after liquid separation, organic layer is dried with magnesium sulfate, then is dried in vacuo；Then gained solid
Phosphoric acrylic ester finished product is obtained using silica gel column chromatography purification, the particle diameter of silica gel is 70~230 mesh, and elution is mutually acetic acid second
Ester and petroleum ether are according to mass ratio 1:The mixed liquor of 1 mixing.Product carries out hydrogen spectral test and infrared inspection, yield 82%.
Embodiment 3
Phosphoric acrylic ester (diethoxyphosphoryl) (phenyl) the methyl methacry of the present embodiment
Late-DEPPMM reaction equation is as follows：
Preparation method be by diethyl phosphonate (DEP) be added drop-wise to benzaldehyde and potassium fluoride (KF) dichloromethane mix it is molten
In liquid.DEP, benzaldehyde, potassium fluoride in molar ratio 1:1:5 ratio, 25 DEG C of reaction temperature, react 1h.After having reacted, magnesium sulfate
Dry, rotary evaporation removes solvent and can obtain midbody compound.
Gained midbody compound and 800ppm 4- metoxyphenols are dissolved in chloroform solvent, the chloroform of acryloyl chloride
Solution is added drop-wise in midbody compound and potassium fluoride chloroformic solution at 0 DEG C.Wherein, diethyl phosphonate and methacrylic chloride
Mol ratio be 1:1.1, reaction time 12h at room temperature.Solid mixture after having reacted, with 6mol/L aqueous hydrochloric acid solution,
1mol/L sodium bicarbonate aqueous solution washing, after liquid separation, organic layer is dried with magnesium sulfate, then is dried in vacuo；Then gained solid
Phosphoric acrylic ester finished product is obtained using silica gel column chromatography purification, the particle diameter of silica gel is 70~230 mesh, and elution is mutually acetic acid second
Ester and petroleum ether are according to mass ratio 1:The mixed liquor of 1 mixing.Product carries out hydrogen spectral test and infrared inspection, yield 83%.
Embodiment 4
Phosphoric acrylic ester (diethoxyphosphoryl) (naphthalen-2-yl) methyl of the present embodiment
Methacrylate-DEPNMM reaction equation is as follows：
Preparation method be by diethyl phosphonate (DEP) be added drop-wise to naphthaldehyde and potassium fluoride (KF) dichloromethane mix it is molten
Liquid.DEP, naphthaldehyde, potassium fluoride in molar ratio 1:1:5 ratio, 25 DEG C of reaction temperature, reaction time 1h.After having reacted, sulfuric acid
Magnesium is dried, and rotary evaporation removes solvent and can obtain midbody compound.
Gained midbody compound and 800ppm 4- metoxyphenols are dissolved in chloroform solvent, the chloroform of acryloyl chloride
Solution is added drop-wise in midbody compound and potassium fluoride chloroformic solution at 0 DEG C.Wherein, diethyl phosphonate and methacrylic chloride
Mol ratio be 1:1.1, reaction time 12h at room temperature.Solid mixture after having reacted, with 6mol/L aqueous hydrochloric acid solution,
1mol/L sodium bicarbonate aqueous solution washing, after liquid separation, organic layer is dried with magnesium sulfate, then is dried in vacuo；Then gained solid
Phosphoric acrylic ester finished product is obtained using silica gel column chromatography purification, the particle diameter of silica gel is 70~230 mesh, and elution is mutually acetic acid second
Ester and petroleum ether are according to mass ratio 1:The mixed liquor of 1 mixing.Product carries out hydrogen spectral test and infrared inspection, yield 83%.
Whole production to the gained of embodiment 1 to 4 carries out hydrogen spectrum and infrared spectrum detection, and gained compound structure characterizes wave spectrum number
According to as shown in table 1.
The flame retardant mechanism of 1 embodiment of table 1 to 4 characterizes spectral data
Application examples 1
The fire-retardant EVA adhesive film of the application example has ABA three-deckers, and top layer includes the component of following mass percent：EVA
Resin 96.5%, nanometer basic zirconium phosphate 0.1%, peroxide 1%, crosslinking coagent 1%, silane coupler 0.6%, UV Absorption
Agent 0.4%, light stabilizer 0.4%.
Sandwich layer includes the component of following mass percent：EVA resin 74%, titanium dioxide 8%, phosphoric acrylic ester fire retardant
15%, peroxide 1%, crosslinking coagent 1%, silane coupler 0.6%, UV absorbers 0.2%, light stabilizer 0.2%.
Peroxide is the di-t-butyl hexane peroxide of 2,5- dimethyl -2,5.Crosslinking coagent is isocyanic acid triallyl.
Light stabilizer is double (1- octyloxies -2,2,6,6- tetramethyl -4- piperidyls) sebacates.UV absorbers are 2- [4,6-
Double (2,4- 3,5-dimethylphenyls) -1.Silane coupler is vinyltrimethoxy silane.
VA contents in EVA resin are 30%.The particle diameter of nanometer basic zirconium phosphate is 200nm~300nm.Phosphoric acrylic ester hinders
Fire agent using embodiment 1 phosphoric acrylic ester 1- (diethoxyphosphoryl) butyl metha crylate-
DEPBMM。
As shown in figure 5, the preparation method of the fire-retardant EVA adhesive film of the application example, comprises the following steps：
Step S1, EVA resin and nanometer basic zirconium phosphate are mixed into extrusion basic zirconium phosphate master batch is made, by EVA resin and titanium dioxide
Titanium dioxide master batch is made in mixing extrusion；
Step S2, the glued membrane of ABA three-deckers is prepared using extrusion equipment and multilayer extrusion die head；Basic zirconium phosphate master batch is used for
Extrusion is mixed with other components top layer is made, sandwich layer is made for mixing extrusion with other components in titanium dioxide master batch.
Mixed in step S1 using vertical double helical ribbon mixer, driving power 120KW, incorporation time 3min；
Extruded in step S1 using extruding machine with two screw rods engaging in the same direction, the twin-screw of extruding machine with two screw rods engaging in the same direction
Rotating speed is 60r/min, and each section of temperature respectively is 140 DEG C, 150 DEG C, 170 DEG C, 180 DEG C, 180 DEG C；
Prepared by the top layer in step S2 uses extruding machine with two screw rods engaging in the same direction, screw diameter 95mm, and screw speed is
60r/min, each section of temperature respectively are 75 DEG C, 80 DEG C, 84 DEG C, 85 DEG C, 85 DEG C；
Prepared by the sandwich layer in step S2 uses single screw extrusion machine, screw diameter 130mm, screw speed 60r/min,
Each section of temperature respectively is 75 DEG C, 80 DEG C, 84 DEG C, 85 DEG C, 85 DEG C.
Thermogravimetric curve after the fire-retardant EVA adhesive film solidification of the application example, as shown in Figure 4.
Application examples 2
The fire-retardant EVA adhesive film of the application example has ABA three-deckers, and top layer includes the component of following mass percent：EVA
Resin 98.5%, nanometer basic zirconium phosphate 0.05%, peroxide 0.5%, crosslinking coagent 0.5%, silane coupler 0.2% are ultraviolet
Light absorber 0.1%, light stabilizer 0.15%.
Sandwich layer includes the component of following mass percent：EVA resin 82.5%, titanium dioxide 7%, phosphoric acrylic ester is fire-retardant
Agent 9%, peroxide 0.5%, crosslinking coagent 0.5%, silane coupler 0.2%, UV absorbers 0.1%, light stabilizer
0.2%.
Peroxide is peroxidating -2- ethylhexyl carbonate tert-pentyl esters.Crosslinking coagent is three (2- ethoxys)-isocyanuric acids
Triacrylate.Light stabilizer is double (2,2,6,6- tetramethyl -4- piperidyls) sebacates.UV absorbers are 3,5- tri-
Piperazine -2- bases] -5- (octyloxy) phenol.Silane coupler is vinyltriacetoxy silane.
VA contents in EVA resin are 25%.The particle diameter of nanometer basic zirconium phosphate is 200nm~300nm.Phosphoric acrylic ester hinders
Fire agent using embodiment 1 phosphoric acrylic ester 1- (diethoxyphosphoryl) butyl metha crylate-
DEPBMM。
As shown in figure 5, the preparation method of the fire-retardant EVA adhesive film of the application example, comprises the following steps：
Step S1, EVA resin and nanometer basic zirconium phosphate are mixed into extrusion basic zirconium phosphate master batch is made, by EVA resin and titanium dioxide
Titanium dioxide master batch is made in mixing extrusion；
Step S2, the glued membrane of ABA three-deckers is prepared using extrusion equipment and multilayer extrusion die head；Basic zirconium phosphate master batch is used for
Extrusion is mixed with other components top layer is made, sandwich layer is made for mixing extrusion with other components in titanium dioxide master batch.
Mixed in step S1 using vertical double helical ribbon mixer, driving power 3KW, incorporation time 10min；
Extruded in step S1 using extruding machine with two screw rods engaging in the same direction, the twin-screw of extruding machine with two screw rods engaging in the same direction
Rotating speed is 40r/min, and each section of temperature respectively is 140 DEG C, 150 DEG C, 170 DEG C, 180 DEG C, 180 DEG C；
Prepared by the top layer in step S2 uses extruding machine with two screw rods engaging in the same direction, screw diameter 95mm, and screw speed is
30r/min, each section of temperature respectively are 75 DEG C, 80 DEG C, 84 DEG C, 85 DEG C, 85 DEG C；
Prepared by the sandwich layer in step S2 uses single screw extrusion machine, screw diameter 130mm, screw speed 30r/min,
Each section of temperature respectively is 75 DEG C, 80 DEG C, 84 DEG C, 85 DEG C, 85 DEG C.
Application examples 3
The fire-retardant EVA adhesive film of the application example has ABA three-deckers, and top layer includes the component of following mass percent：EVA
Resin 97.5%, nanometer basic zirconium phosphate 0.1%, peroxide 0.8%, crosslinking coagent 0.7%, silane coupler 0.4%, ultraviolet light
Absorbent 0.2%, light stabilizer 0.3%.
Sandwich layer includes the component of following mass percent：EVA resin 78%, titanium dioxide 7.5%, phosphoric acrylic ester is fire-retardant
Agent 12%, peroxide 0.8%, crosslinking coagent 0.8%, silane coupler 0.4%, UV absorbers 0.2%, light stabilizer
0.2%.
Peroxide is the peroxidating -2- ethylhexyl carbonate tert-butyl esters.Crosslinking coagent is trimethylolpropane tris acrylic acid
Ester.Light stabilizer is poly-succinic (4 hydroxyls -2,2, the piperidine ethanol fat of 6,6- tetramethyl -1).UV absorbers are 3,5- tri-
Piperazine -2- bases] -5- (octyloxy) phenol.Silane coupler is vinyl three ('beta '-methoxy ethyoxyl) silane.
VA contents in EVA resin are 20%.The particle diameter of nanometer basic zirconium phosphate is 200nm~300nm.Phosphoric acrylic ester hinders
Fire phosphoric acrylic ester (diethoxyphosphoryl) the methyl methacr ylate-DEPMM that agent uses embodiment 1.
As shown in figure 5, the preparation method of the fire-retardant EVA adhesive film of the application example, comprises the following steps：
Step S1, EVA resin and nanometer basic zirconium phosphate are mixed into extrusion basic zirconium phosphate master batch is made, by EVA resin and titanium dioxide
Titanium dioxide master batch is made in mixing extrusion；
Step S2, the glued membrane of ABA three-deckers is prepared using extrusion equipment and multilayer extrusion die head；Basic zirconium phosphate master batch is used for
Extrusion is mixed with other components top layer is made, sandwich layer is made for mixing extrusion with other components in titanium dioxide master batch.
Mixed in step S1 using vertical double helical ribbon mixer, driving power 50KW, incorporation time 5min；
Extruded in step S1 using extruding machine with two screw rods engaging in the same direction, the twin-screw of extruding machine with two screw rods engaging in the same direction
Rotating speed is 50r/min, and each section of temperature respectively is 140 DEG C, 150 DEG C, 170 DEG C, 180 DEG C, 180 DEG C；
Prepared by the top layer in step S2 uses extruding machine with two screw rods engaging in the same direction, screw diameter 95mm, and screw speed is
45r/min, each section of temperature respectively are 75 DEG C, 80 DEG C, 84 DEG C, 85 DEG C, 85 DEG C；
Prepared by the sandwich layer in step S2 uses single screw extrusion machine, screw diameter 130mm, screw speed 45r/min,
Each section of temperature respectively is 75 DEG C, 80 DEG C, 84 DEG C, 85 DEG C, 85 DEG C.
Application examples 4
The fire-retardant EVA adhesive film remainder of the application example is identical with application examples 1, and difference is：Phosphoric acrylic ester
Fire retardant uses phosphoric acrylic ester 1- (diethoxyphosphoryl) the butyl met hacrylate- of embodiment 2
DEPBMM。
Application examples 5
The fire-retardant EVA adhesive film remainder of the application example is identical with application examples 2, and difference is：Phosphoric acrylic ester
Fire retardant uses phosphoric acrylic ester (diethoxyphosphoryl) (phenyl) the meth yl of embodiment 3
methacrylate-DEPPMM。
Application examples 6
The fire-retardant EVA adhesive film remainder of the application example is identical with application examples 3, and difference is：Phosphoric acrylic ester
Fire retardant uses phosphoric acrylic ester (diethoxyphosphoryl) (naphthalen-2-yl) methyl of embodiment 4
methacrylate-DEPNMM。
Diethyl phosphonate, paraformaldehyde, 4- metoxyphenols, butyraldehyde, benzaldehyde, naphthaldehyde, triethylamine, potassium fluoride,
Cesium fluoride, magnesium sulfate, analysis is pure, purchased from Chinese medicines group chemical reagent Chengdu Co., Ltd.Sodium acid carbonate, hydrochloric acid, petroleum ether, second
Acetoacetic ester, chloroform, dichloromethane, analysis is pure, purchases from Chengdu Ke Long chemical reagent works.Column chromatography silica gel, purchase from Chinese medicines group
Learn reagent Chengdu Co., Ltd.Concentration is that chemistry is pure to agents useful for same unless otherwise specified in the present invention.
Phosphoric acrylic ester structure and purity provided by the invention, the thickness of fire-retardant EVA adhesive film, thermal weight loss, peel strength,
The testing standard of specific insulation, ageing properties and fire resistance is as follows：
Film thickness：Using ISO:4593-1993 standards, are determined using digimatic micrometer.
Oxygen index (OI)：Using GB/T2406-2009 standards, tested using JF-3 oxygen index measurers.
Tensile property：By GB/T1040-2006 standard testings, using the type universal testing machines of Instron 1185, clamping length
Spend for 150mm, draw speed 100mm/min.
Percent thermal shrinkage：Using GB/T13542.2-2009 standard detections；Taken from flame-retardant polyamide film two piece 100 ×
100mm sample, and do and longitudinally, laterally mark, determine laterally and longitudinally length L0.Film is placed on to 135 DEG C of baking naturally
Kept respectively in case 1 hour, sample is then taken out from baking oven, sample is cooled to room temperature.Redeterminate laterally and longitudinally length
L1, then shrinkage factor (%)=(L0-L1)/L0× 100%.
Vertical combustion：By ANSL-UL94-2009 standards, tested using CZF-5 types Vertical combustion instrument.
Fire-retardant EVA adhesive film made from application examples 1 to 6 is tested using above-mentioned detection method, its test result is such as
Shown in table 2.
The fire-retardant EVA adhesive film performance data table of table 2
Note：MD is longitudinal direction, and TD is laterally.
Obviously, above-described embodiment is only intended to clearly illustrate example of the present invention, and is not to the present invention
The restriction of embodiment.For those of ordinary skill in the field, it can also be made on the basis of the above description
Its various forms of changes or variation.There is no necessity and possibility to exhaust all the enbodiments.And these belong to this hair
Among the obvious changes or variations that bright spirit is extended out is still in protection scope of the present invention.
Claims (10)
- A kind of 1. phosphoric acrylic ester fire retardant, it is characterised in that：With the structure as shown in formula I,Wherein, R is hydrogen atom, aliphatic group or aryl.
- 2. phosphoric acrylic ester fire retardant according to claim 1, it is characterised in that：The R is C1~C8 alkyl, C3 ~C8 cycloalkyl, C2~C8 unsaturated alkyl, C3~C8 cycloolefin or C6~C10 aryl.
- A kind of 3. preparation method of phosphoric acrylic ester fire retardant, it is characterised in that：Diethyl phosphonate as shown in formula II with Aldehyde compound as shown in formula II reacts midbody compound of the generation as shown in formula IV in the presence of acid binding agent,Midbody compound as shown in formula IV reacts life with the methacrylic chloride as shown in formula V in the presence of acid binding agent Into the phosphoric acrylic ester as shown in formula I,
- 4. the preparation method of phosphoric acrylic ester fire retardant according to claim 3, it is characterised in that：The acid binding agent is Triethylamine, potassium fluoride or cesium fluoride, the diethyl phosphonate, aldehyde compound, the mol ratio of acid binding agent are 1:1:1~5, it is raw Reaction temperature into midbody compound is 0 DEG C~30 DEG C, reaction time 1h~5h.
- 5. the preparation method of phosphoric acrylic ester fire retardant according to claim 3, it is characterised in that：The diethyl phosphine The mol ratio of acid esters and methacrylic chloride is 1:1~1.1, the reaction temperature for generating phosphoric acrylic ester is 0 DEG C~120 DEG C, Reaction time 1h~12h.
- 6. the preparation method of phosphoric acrylic ester fire retardant according to claim 3, it is characterised in that：Generate phosphorous propylene Solid product obtained by acid esters, aqueous hydrochloric acid solution, sodium bicarbonate aqueous solution washing, after liquid separation, organic layer sulphur is respectively adopted Sour magnesium is dried, then is dried in vacuo；Then gained solid obtains phosphoric acrylic ester finished product, silica gel using silica gel column chromatography purification Particle diameter be 70~230 mesh, elution is mutually ethyl acetate and petroleum ether according to mass ratio 1:The mixed liquor of 1 mixing.
- A kind of 7. fire-retardant EVA adhesive film, it is characterised in that：With ABA three-deckers, top layer includes the group of following mass percent Point：EVA resin 96.5%~98.5%, nanometer basic zirconium phosphate 0.05%~0.1%, peroxide 0.5%~1%, crosslinking coagent 0.5%~1%, silane coupler 0.2%~0.6%, UV absorbers 0.1%~0.5%, light stabilizer 0.1%~ 0.5%；Sandwich layer includes the component of following mass percent：EVA resin 74%~82.5%, titanium dioxide 7~8%, phosphorous acrylic acid Ester fire retardant 9%~15%, peroxide 0.5%~1%, crosslinking coagent 0.5%~1%, silane coupler 0.2%~ 0.6%, UV absorbers 0.1%~0.5%, light stabilizer 0.1%~0.5%；The phosphoric acrylic ester fire retardant has the structure as shown in formula I,Wherein, R is hydrogen atom, aliphatic group or aryl.
- 8. fire-retardant EVA adhesive film according to claim 7, it is characterised in that：Core layer thickness is 400 μm~500 μm, and top layer is thick Spend for 50 μm~100 μm；The peroxide is the di-t-butyl hexane peroxide of 2,5- dimethyl -2,5, peroxidating -2- ethyls One or more in hexyl carbonic acid tert-pentyl ester and the peroxidating -2- ethylhexyl carbonate tert-butyl esters；The crosslinking coagent is isocyanic acid triallyl, three (2- ethoxys)-isocyanuric acid triacrylates, trimethylolpropane One or more in triacrylate, pentaerythritol triacrylate and ethoxyquin trimethylolpropane trimethacrylate；The silane coupler is vinyltrimethoxy silane, the vinyltriacetoxy silane, ('beta '-methoxy of vinyl three Ethyoxyl) it is one or more in silane；The light stabilizer is double (1- octyloxies -2,2,6,6- tetramethyl -4- piperidyls) sebacate, double (2,2,6,6- tetra- Methyl -4- piperidyls) sebacate and one kind in poly-succinic (4 hydroxyls -2,2, the piperidine ethanol fat of 6,6- tetramethyl -1) or It is a variety of；The UV absorbers are 2- [4,6- double (2,4- 3,5-dimethylphenyl) -1,3,5-triazines -2- bases] -5- (octyloxy) Phenol；VA contents in the EVA resin are 20%~30%；The particle diameter of nanometer basic zirconium phosphate is 200nm~300nm.
- 9. a kind of preparation method of fire-retardant EVA adhesive film as claimed in claim 7, it is characterised in that comprise the following steps：Step S1, EVA resin and nanometer basic zirconium phosphate are mixed into extrusion basic zirconium phosphate master batch is made, EVA resin and titanium dioxide are mixed Titanium dioxide master batch is made in extrusion；Step S2, the glued membrane of ABA three-deckers is prepared using extrusion equipment and multilayer extrusion die head；Basic zirconium phosphate master batch is used for and it Top layer is made for component mixing extrusion in he, and sandwich layer is made for mixing extrusion with other components in titanium dioxide master batch.
- 10. the preparation method of fire-retardant EVA adhesive film according to claim 9, it is characterised in that：Using vertical in the step S1 Formula double helical ribbon mixer is mixed, and driving power is 3KW~120KW, and incorporation time is 3min~10min；Extruded in the step S1 using extruding machine with two screw rods engaging in the same direction, the twin-screw of extruding machine with two screw rods engaging in the same direction Rotating speed is 40r/min~60r/min, and each section of temperature respectively is 140 DEG C, 150 DEG C, 170 DEG C, 180 DEG C, 180 DEG C；Prepared by the top layer in the step S2 uses extruding machine with two screw rods engaging in the same direction, screw diameter 95mm, and screw speed is 30r/min~60r/min, each section of temperature respectively are 75 DEG C, 80 DEG C, 84 DEG C, 85 DEG C, 85 DEG C；Prepared by the sandwich layer in the step S2 uses single screw extrusion machine, screw diameter 130mm, screw speed 30r/min ~60r/min, each section of temperature respectively are 75 DEG C, 80 DEG C, 84 DEG C, 85 DEG C, 85 DEG C.
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| CN112662260A (en) * | 2020-12-29 | 2021-04-16 | 山西中涂交通科技股份有限公司 | Flame-retardant anti-skid road surface coating for tunnel |
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| CN108753205A (en) * | 2018-06-28 | 2018-11-06 | 安徽尼古拉电子科技有限公司 | A kind of military project electronic component flame-retardant hot-melt adhesive and preparation method thereof |
| CN112662260A (en) * | 2020-12-29 | 2021-04-16 | 山西中涂交通科技股份有限公司 | Flame-retardant anti-skid road surface coating for tunnel |
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Effective date of registration: 20231227 Address after: No. 87, Industrial Avenue, Lai'an County Development Zone, Chuzhou City, Anhui Province 239000 Patentee after: Laian Baijia Shiji Film Technology Co.,Ltd. Address before: 213000 Lijia town industrial concentration area, Wujin District, Changzhou City, Jiangsu Province Patentee before: CHANGZHOU BBETTER FILM TECHNOLOGIES CO.,LTD. |