CN111777642B - Halogen-free flame-retardant unsaturated polyester composition, polyester product, preparation method and application thereof - Google Patents
Halogen-free flame-retardant unsaturated polyester composition, polyester product, preparation method and application thereof Download PDFInfo
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- CN111777642B CN111777642B CN202010918758.9A CN202010918758A CN111777642B CN 111777642 B CN111777642 B CN 111777642B CN 202010918758 A CN202010918758 A CN 202010918758A CN 111777642 B CN111777642 B CN 111777642B
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- China
- Prior art keywords
- resin
- unsaturated polyester
- halogen
- free flame
- formula
- Prior art date
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 92
- 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 88
- 229920006305 unsaturated polyester Polymers 0.000 title claims abstract description 63
- 239000000203 mixture Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229920000728 polyester Polymers 0.000 title claims description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 67
- 239000011574 phosphorus Substances 0.000 claims abstract description 67
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000000034 method Methods 0.000 claims abstract description 26
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 23
- 229920005989 resin Polymers 0.000 claims description 105
- 239000011347 resin Substances 0.000 claims description 105
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 150000001875 compounds Chemical class 0.000 claims description 30
- 239000003054 catalyst Substances 0.000 claims description 25
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 20
- 229920006337 unsaturated polyester resin Polymers 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 19
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 claims description 18
- 239000003999 initiator Substances 0.000 claims description 16
- 238000005266 casting Methods 0.000 claims description 15
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims description 14
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 12
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- 230000009477 glass transition Effects 0.000 claims description 11
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 10
- 238000009987 spinning Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 9
- 150000002903 organophosphorus compounds Chemical class 0.000 claims description 9
- 229920006395 saturated elastomer Polymers 0.000 claims description 9
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 8
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-diisopropylethylamine Substances CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 8
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 238000006482 condensation reaction Methods 0.000 claims description 6
- 229920006267 polyester film Polymers 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 5
- 239000003377 acid catalyst Substances 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 238000002347 injection Methods 0.000 claims description 5
- 239000007924 injection Substances 0.000 claims description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 4
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 claims description 3
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 claims description 3
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 3
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 3
- 239000002841 Lewis acid Substances 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- BLCKNMAZFRMCJJ-UHFFFAOYSA-N cyclohexyl cyclohexyloxycarbonyloxy carbonate Chemical compound C1CCCCC1OC(=O)OOC(=O)OC1CCCCC1 BLCKNMAZFRMCJJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 3
- 238000009998 heat setting Methods 0.000 claims description 3
- 150000007517 lewis acids Chemical class 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- HGXJDMCMYLEZMJ-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOOC(=O)C(C)(C)C HGXJDMCMYLEZMJ-UHFFFAOYSA-N 0.000 claims description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 60
- 239000000178 monomer Substances 0.000 description 44
- 230000015572 biosynthetic process Effects 0.000 description 20
- 238000003786 synthesis reaction Methods 0.000 description 20
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 18
- 238000003756 stirring Methods 0.000 description 18
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 14
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 description 11
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 10
- 229960001867 guaiacol Drugs 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- JXASPPWQHFOWPL-UHFFFAOYSA-N Tamarixin Natural products C1=C(O)C(OC)=CC=C1C1=C(OC2C(C(O)C(O)C(CO)O2)O)C(=O)C2=C(O)C=C(O)C=C2O1 JXASPPWQHFOWPL-UHFFFAOYSA-N 0.000 description 8
- 239000000654 additive Substances 0.000 description 8
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 7
- RECUKUPTGUEGMW-UHFFFAOYSA-N carvacrol Chemical compound CC(C)C1=CC=C(C)C(O)=C1 RECUKUPTGUEGMW-UHFFFAOYSA-N 0.000 description 7
- HHTWOMMSBMNRKP-UHFFFAOYSA-N carvacrol Natural products CC(=C)C1=CC=C(C)C(O)=C1 HHTWOMMSBMNRKP-UHFFFAOYSA-N 0.000 description 7
- 235000007746 carvacrol Nutrition 0.000 description 7
- WYXXLXHHWYNKJF-UHFFFAOYSA-N isocarvacrol Natural products CC(C)C1=CC=C(O)C(C)=C1 WYXXLXHHWYNKJF-UHFFFAOYSA-N 0.000 description 7
- GCUCJPGAYGXRBK-UHFFFAOYSA-N (4-hydroxy-2-methylphenyl)-(4-hydroxyphenyl)methanone Chemical compound CC1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 GCUCJPGAYGXRBK-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 6
- 235000010292 orthophenyl phenol Nutrition 0.000 description 6
- 150000003017 phosphorus Chemical class 0.000 description 6
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 6
- RDIHXOPGCARGNN-UHFFFAOYSA-N (4-hydroxy-3-methoxyphenyl)-(4-hydroxyphenyl)methanone Chemical compound C1=C(O)C(OC)=CC(C(=O)C=2C=CC(O)=CC=2)=C1 RDIHXOPGCARGNN-UHFFFAOYSA-N 0.000 description 5
- -1 compound 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide Chemical class 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- MGSRCZKZVOBKFT-UHFFFAOYSA-N thymol Chemical compound CC(C)C1=CC=C(C)C=C1O MGSRCZKZVOBKFT-UHFFFAOYSA-N 0.000 description 4
- CAGTWOWYUAJOKA-UHFFFAOYSA-N (3-hexyl-4-hydroxyphenyl)-(4-hydroxyphenyl)methanone Chemical compound CCCCCCC1=C(C=CC(=C1)C(=O)C2=CC=C(C=C2)O)O CAGTWOWYUAJOKA-UHFFFAOYSA-N 0.000 description 3
- GPXDDMIABKXBBJ-UHFFFAOYSA-N (4-hydroxy-3-phenoxyphenyl)-(4-hydroxyphenyl)methanone Chemical compound C1=CC=C(C=C1)OC2=C(C=CC(=C2)C(=O)C3=CC=C(C=C3)O)O GPXDDMIABKXBBJ-UHFFFAOYSA-N 0.000 description 3
- HEZJDNTULNCSOZ-UHFFFAOYSA-N (4-hydroxyphenyl)-(4-hydroxy-2-propylphenyl)methanone Chemical compound CCCC1=C(C=CC(O)=C1)C(=O)C1=CC=C(O)C=C1 HEZJDNTULNCSOZ-UHFFFAOYSA-N 0.000 description 3
- MFYQVPRXBWKYHQ-UHFFFAOYSA-N (4-hydroxyphenyl)-(4-hydroxy-3-phenylphenyl)methanone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C(C=2C=CC=CC=2)=C1 MFYQVPRXBWKYHQ-UHFFFAOYSA-N 0.000 description 3
- AMKPQMFZCBTTAT-UHFFFAOYSA-N 3-ethylaniline Chemical compound CCC1=CC=CC(N)=C1 AMKPQMFZCBTTAT-UHFFFAOYSA-N 0.000 description 3
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 3
- 229910015900 BF3 Inorganic materials 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- KZVLNAGYSAKYMG-UHFFFAOYSA-N pyridine-2-sulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=N1 KZVLNAGYSAKYMG-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 3
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 description 3
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 2
- DGZPXFZRRFSTBK-UHFFFAOYSA-N (3-cycloheptyl-4-hydroxyphenyl)-(4-hydroxyphenyl)methanone Chemical compound C1CCCC(CC1)C2=C(C=CC(=C2)C(=O)C3=CC=C(C=C3)O)O DGZPXFZRRFSTBK-UHFFFAOYSA-N 0.000 description 2
- GDJBCEMWBAZUSR-UHFFFAOYSA-N (3-cyclopropyl-4-hydroxyphenyl)-(4-hydroxyphenyl)methanone Chemical compound C1CC1C2=C(C=CC(=C2)C(=O)C3=CC=C(C=C3)O)O GDJBCEMWBAZUSR-UHFFFAOYSA-N 0.000 description 2
- CWPKKBWXSJQVOM-UHFFFAOYSA-N (3-hexoxy-4-hydroxyphenyl)-(4-hydroxyphenyl)methanone Chemical compound CCCCCCOC1=C(C=CC(=C1)C(=O)C2=CC=C(C=C2)O)O CWPKKBWXSJQVOM-UHFFFAOYSA-N 0.000 description 2
- RXEVVYAIYHOCGD-UHFFFAOYSA-N (4-hydroxyphenyl)-(4-hydroxy-3-propoxyphenyl)methanone Chemical compound CCCOC1=C(C=CC(=C1)C(=O)C2=CC=C(C=C2)O)O RXEVVYAIYHOCGD-UHFFFAOYSA-N 0.000 description 2
- ZEFBTJQAIPEWER-UHFFFAOYSA-N 2-cycloheptylphenol Chemical compound OC1=CC=CC=C1C1CCCCCC1 ZEFBTJQAIPEWER-UHFFFAOYSA-N 0.000 description 2
- ZAJAQTYSTDTMCU-UHFFFAOYSA-N 3-aminobenzenesulfonic acid Chemical compound NC1=CC=CC(S(O)(=O)=O)=C1 ZAJAQTYSTDTMCU-UHFFFAOYSA-N 0.000 description 2
- VLLXOHZPGOGGGA-UHFFFAOYSA-N 3-cyclopropylphenol Chemical compound OC1=CC=CC(C2CC2)=C1 VLLXOHZPGOGGGA-UHFFFAOYSA-N 0.000 description 2
- CRIQSWIRYKZJAV-UHFFFAOYSA-N 3-hexylphenol Chemical compound CCCCCCC1=CC=CC(O)=C1 CRIQSWIRYKZJAV-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000005844 Thymol Substances 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- ITOCFWXXFHXKKY-UHFFFAOYSA-N bis(3-cyclohexyl-4-hydroxyphenyl)methanone Chemical compound C1(CCCCC1)C=1C=C(C(=O)C2=CC(=C(C=C2)O)C2CCCCC2)C=CC1O ITOCFWXXFHXKKY-UHFFFAOYSA-N 0.000 description 2
- CNHYITZHGVWWQL-UHFFFAOYSA-N bis(4-hydroxy-3-propoxyphenyl)methanone Chemical compound OC1=C(C=C(C=C1)C(=O)C1=CC(=C(C=C1)O)OCCC)OCCC CNHYITZHGVWWQL-UHFFFAOYSA-N 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229950000244 sulfanilic acid Drugs 0.000 description 2
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 229960000790 thymol Drugs 0.000 description 2
- MVRPPTGLVPEMPI-UHFFFAOYSA-N 2-cyclohexylphenol Chemical compound OC1=CC=CC=C1C1CCCCC1 MVRPPTGLVPEMPI-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940061587 calcium behenate Drugs 0.000 description 1
- SMBKCSPGKDEPFO-UHFFFAOYSA-L calcium;docosanoate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCCCCCC([O-])=O SMBKCSPGKDEPFO-UHFFFAOYSA-L 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6568—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms
- C07F9/65681—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms the ring phosphorus atom being part of a (thio)phosphinic acid or ester thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/10—Interconnection of layers at least one layer having inter-reactive properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
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- 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
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/02—2 layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
- B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
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- B32—LAYERED PRODUCTS
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- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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Abstract
The invention discloses a phosphorus-containing acrylate which has a structure shown in the following formula:
the invention also discloses a halogen-free flame-retardant unsaturated polyester composition which comprises the phosphorus-containing acrylate. The invention also discloses a preparation method and application of the phosphorus-containing acrylate, the halogen-free flame-retardant unsaturated polyester composition and a cured product thereof. The halogen-free flame-retardant unsaturated polyester composition and the condensate thereof have the advantages of simple preparation process, simple and convenient operation method, good controllability and easy implementation. The halogen-free flame-retardant unsaturated polyester composition and the condensate thereof have excellent flame retardant property while maintaining good thermodynamic property, and have good application prospect and wide application range.
Description
Technical Field
The invention relates to an unsaturated polyester material, in particular to a phosphorus-containing acrylate, a halogen-free flame-retardant unsaturated polyester composition, a polyester product, a preparation method and application thereof, and belongs to the technical field of composite materials.
Background
The unsaturated polyester resin is a linear polyester prepared by reacting a mixed acid formed by mixing unsaturated dibasic acid with partially saturated dibasic acid with dihydric alcohol or polyhydric alcohol, and is crosslinked and cured by using an olefin monomer to form the thermosetting resin with a body structure. Unsaturated polyester resins have a very long history of development, and have been industrially produced in the united states in 1942, and we have also started the industrial production of unsaturated polyesters in 1958. Unsaturated polyester resin has very important status in national production and life, and is widely applied to various industries.
However, like other conventional thermosetting resins, the polymer materials based on unsaturated polyester resins are flammable and tend to cause immeasurable loss of life and property of people in the event of fire during use. Therefore, the flame retardant treatment by adding a proper amount of flame retardant to the unsaturated polyester resin system is very urgent. The traditional flame-retardant modification method is mainly to use a halogen-containing flame retardant as an additive or a copolymer to physically or chemically modify matrix resin, so that the purpose of good flame-retardant performance of the material is achieved. However, these halogen-containing polymers release corrosive and toxic gases during combustion, which can cause significant harm to both the human body and the environment. Therefore, research into halogen-free flame retardants has become more important in recent years, and among them, phosphorus-based flame retardants are receiving the most attention. However, how to use phosphorus flame retardant to prepare a polymer material of unsaturated polyester resin with good flame retardant property and no harm to human body and environment is still a problem to be solved by researchers in the field.
Disclosure of Invention
The invention mainly aims to provide a phosphorus-containing acrylate and a preparation method thereof, thereby overcoming the defects of the prior art.
The invention also aims to provide a halogen-free flame-retardant unsaturated polyester composition, a condensate thereof and a preparation method thereof, wherein the halogen-free flame-retardant unsaturated polyester resin composition and the condensate thereof have flame retardant property and high thermodynamic property.
The invention also aims to provide application of the phosphorus-containing acrylate halogen-free flame-retardant unsaturated polyester composition.
Another object of the present invention is to provide a method for processing a polyester article.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a phosphorus-containing acrylate which has a structure as shown in a formula (2):
（2）
wherein R is1、R2、R3、R4、R5、R6Are independently selected from hydrogen atoms, alkyl of C1-C6, alkoxy of C1-C6, phenyl, phenoxy or cycloalkyl of C3-C7;
x is
Or
(ii) a Y is
Or
；
Z is selected from
、
、
Or
。
The invention also provides a preparation method of the phosphorus-containing acrylate, which is characterized by comprising the following steps:
carrying out condensation reaction on a first mixed reaction system containing an organic phosphorus compound shown as a formula (4), a compound shown as a formula (5), a compound shown as a formula (6) and an acid catalyst at 100-130 ℃ for 12-36 h to obtain a compound shown as a formula (3);
（3）
wherein R is1To R6Are independently selected from hydrogen atoms, alkyl of C1-C6, alkoxy of C1-C6, phenyl, phenoxy or cycloalkyl of C3-C7, R7is-OH or NH2；
And (3) reacting the second mixed reaction system containing the compound shown in the formula (3), acryloyl chloride or methacryloyl chloride and an acid binding agent at-30 ℃ for 6-24 h to obtain the phosphorus-containing acrylate, namely the compound shown in the formula (2).
The embodiment of the invention also provides a halogen-free flame-retardant unsaturated polyester composition, which comprises the following components in percentage by weight: resin A, resin B and an initiator; the resin A comprises an unsaturated polyester resin, and the resin B comprises the phosphorus-containing acrylate.
The embodiment of the invention also provides a preparation method of the halogen-free flame-retardant unsaturated polyester condensate, which comprises the following steps: and carrying out gradient curing on the halogen-free flame-retardant unsaturated polyester composition at the temperature of 80-180 ℃.
In some embodiments, the unsaturated polyester resin has a structure as shown in formula (1):
（1）
wherein G, P is respectively derived from divalent alkyl or aromatic group in dihydric alcohol and saturated dibasic acid, x and y represent polymerization degree, 2 < x < 5, and 2 < y < 5. The dihydric alcohol and the saturated dibasic acid can be dihydric alcohol and saturated dibasic acid which are commonly used in commercial unsaturated polyester.
The embodiment of the invention also provides a halogen-free flame-retardant unsaturated polyester cured product prepared by the method, the glass transition temperature of the cured product is 102-151 ℃, the tensile strength of the cured product is 98-164 MPa, and the flame retardant property of the cured product is V0 grade.
The embodiment of the invention also provides the application of the halogen-free flame-retardant unsaturated polyester composition and a condensate thereof.
The embodiment of the invention also provides a processing method of the polyester product, which comprises the following steps: and preparing the halogen-free flame-retardant unsaturated polyester composition into a required polyester product by adopting any one of extrusion, injection and spinning.
The embodiment of the invention also provides a device with a heat-resistant flame-retardant structure, wherein the heat-resistant flame-retardant structure comprises the halogen-free flame-retardant unsaturated polyester cured product.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the halogen-free flame-retardant unsaturated polyester composition and the cured product thereof, the phosphorus-containing additive resin is introduced by adopting a copolymerization method, so that no negative influence is caused on the thermodynamic performance of the cured product no matter how much the phosphorus-containing additive resin is added, and the thermodynamic performance and the flame retardant performance of the cured resin can be improved;
(2) the invention provides a preparation method of a halogen-free flame-retardant unsaturated polyester composition and a condensate thereof, which mainly prepares a DOPO compound containing an unsaturated monomer by a chemical modification method, and copolymerizes the DOPO compound with unsaturated polyester resin to achieve the purpose of simultaneously improving the thermodynamic property and the flame retardant property of an unsaturated polyester system.
(3) The halogen-free flame-retardant unsaturated polyester composition and the condensate thereof have the advantages of simple preparation process, simple and convenient operation method, good controllability and easy implementation, and the obtained halogen-free flame-retardant unsaturated polyester condensate has excellent flame retardant property while maintaining good thermodynamic property, thereby having good application prospect and wide application range.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 shows resin A (i.e., unsaturated polyester resin) in example 1 of the present invention: stress-strain plot of cured resin under resin B (i.e., phosphorous acrylate) =80: 20;
FIG. 2 shows resin A (i.e., unsaturated polyester resin) in example 2 of the present invention: stress-strain graph of cured resin of resin B (i.e., phosphorous acrylate) =70: 30.
Detailed Description
Aiming at the problems that the addition of a flame retardant into a traditional unsaturated polyester resin easily affects the mechanical property of a cured product and the traditional additive type has precipitation and uneven blending, the inventor of the invention provides a technical scheme of the invention through long-term research and a great deal of practice, and the technical scheme of the invention is clearly and completely described below. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The phosphorus flame retardant has excellent flame retardance, and can promote the polymer to be dehydrated in advance in the combustion process, so that the temperature of the surrounding environment is reduced and is lower than the combustion temperature for flame retardance; in addition, phosphoric acid can form polyphosphoric acid compound at high temperature to cover the surface of the polymer to form a protective layer, and oxygen is prevented from entering the protective layer. The phosphorus-containing compound 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) attracts attention, and the flame-retardant compound based on the structure has very high flame-retardant performance, is easy to chemically modify and can obtain a flame-retardant monomer with good reaction activity.
The invention provides a preparation method of a halogen-free flame-retardant unsaturated polyester composition by utilizing the excellent flame retardant property of an environment-friendly DOPO-based compound, the DOPO-based compound containing an unsaturated monomer is prepared by a chemical modification method, and is copolymerized with unsaturated polyester, so that the purposes of simultaneously improving the thermodynamic property and the flame retardant property of an unsaturated polyester system are achieved, and the unsaturated polyester resin has the flame retardant property and high thermodynamic property.
One aspect of the embodiments of the present invention provides a class of phosphorus-containing acrylates having a structure as shown in formula (2):
the embodiment of the invention provides a phosphorus-containing acrylate which has a structure as shown in a formula (2):
（2）
wherein R is1、R2、R3、R4、R5、R6Are independently selected from hydrogen atoms, alkyl of C1-C6, alkoxy of C1-C6, phenyl, phenoxy or cycloalkyl of C3-C7;
x is
Or
(ii) a Y is
Or
；
Z is selected from
、
、
Or
。
Another aspect of an embodiment of the present invention provides a method for preparing a phosphorous acrylate, including:
carrying out condensation reaction on a first mixed reaction system containing an organic phosphorus compound shown as a formula (4), a compound shown as a formula (5), a compound shown as a formula (6) and an acid catalyst at 100-130 ℃ for 12-36 h to obtain a compound shown as a formula (3);
（3）
wherein R is1To R6Are independently selected from hydrogen atoms, alkyl of C1-C6, alkoxy of C1-C6, phenyl, phenoxy or cycloalkyl of C3-C7, R7is-OH or NH2；
And (3) reacting a second mixed reaction system containing the compound shown in the formula (3), acryloyl chloride or methacryloyl chloride and an acid binding agent at-30 ℃ for 6-24 h to obtain the phosphorus-containing acrylate.
In some more specific embodiments, the phosphorous containing acrylate is prepared by the steps of:
(1) carrying out condensation reaction on a first mixed reaction system of an organic phosphorus compound shown as a formula (4), a compound shown as a formula (5), a compound shown as a formula (6) and an acid catalyst at 100-130 ℃ for 12-36 h to obtain a compound shown as a formula (3);
wherein R is1、R2、R3、R4、R5、R6And R7As previously defined.
(2) Reacting the compound shown in the formula (3) obtained in the step (1) with acryloyl chloride or methacryloyl chloride in the presence of an acid binding agent to obtain resin shown in the formula (2), namely phosphorus-containing acrylate;
（2）
wherein R is1、R2、R3、R4、R5、R6、R7X, Y and Z are as defined above.
In some embodiments, in step (1), the condensation reaction conditions are: under the protection of nitrogen, the molar mass ratio of the organic phosphorus compound shown in the formula (4), the compound shown in the formula (5) and the compound shown in the formula (6) is 1: 1: 1-6, preferably 1: 1: 3 to 5. Reacting for 12-36 h at 100-130 ℃ under the action of an acid catalyst.
Further, the compound represented by the formula (5) may be more specifically 4,4 '-dihydroxybenzophenone, 2-methyl-4, 4' -dihydroxybenzophenone, 2-propyl-4, 4 '-dihydroxybenzophenone, 3-hexyl-4, 4' -dihydroxybenzophenone, 4 '-dihydroxy-3-methoxybenzophenone, 4' -dihydroxy-3-propoxybenzophenone, 4 '-dihydroxy-3-hexyloxybenzophenone, 4' -dihydroxybenzophenone, 4 '-dihydroxy-3, 3' -dipropyloxybenzophenone, 4 '-dihydroxy-3, 3' -dihexyloxybenzophenone, 4,4 '-dihydroxy-3-phenylbenzophenone, 4' -dihydroxy-3, 3 '-dicyclohexylbenzophenone, 4' -dihydroxy-3-phenoxybenzophenone, 4 '-dihydroxy-3-cyclopropylbenzophenone, 4' -dihydroxy-3-cycloheptylbenzophenone, and the like, without being limited thereto.
Further, the compound represented by the formula (6) may be more specifically guaiacol, phenol, o-methylphenol, m-oxypropylphenol, m-hexylphenol, aniline, o-methylaniline, cyclohexylphenol, m-ethylaniline, carvacrol, thymol, m-oxyhexylphenol, o-phenylphenol, o-oxyphenol, m-cyclopropylphenol, o-cycloheptylphenol, etc., without being limited thereto.
In some embodiments, in the step (1), the mass ratio of the acidic catalyst to the organophosphorus compound represented by the formula (4) is 0.1 to 10: 100. that is, the acidic catalyst for the condensation reaction is used in an amount of 0.1 to 10% by weight based on the content of the organic phosphorus compound represented by formula (4).
In some embodiments, in step (1), the acidic catalyst may be any one or a combination of two or more of organic acid, inorganic acid, lewis acid, and the like, and is not limited thereto.
Further, in the step (1), the organic acid may be acetic acid, trifluoroacetic acid, methanesulfonic acid, aminobenzenesulfonic acid, pyridinesulfonic acid, sulfanilic acid, p-methylbenzenesulfonic acid, or the like; the inorganic acid can be sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, boric acid, etc.; the lewis acid may be aluminum chloride, ferric bromide, ferric chloride, boron trifluoride, etc., without being limited thereto.
In some embodiments, in step (2), the molar ratio of the compound represented by formula (3), acryloyl chloride or methacryloyl chloride, and the acid-binding agent is 1: 6-12: 6 to 12.
In some embodiments, in the step (2), the acid-binding agent may be any one or a combination of two or more of potassium carbonate, sodium acetate, triethylamine, pyridine, N-diisopropylethylamine, 4-dimethylaminopyridine, triethanolamine, and the like, but is not limited thereto.
In another aspect of the embodiments of the present invention, there is also provided a halogen-free flame retardant unsaturated polyester composition, including: unsaturated polyester resin, the aforementioned phosphorus-containing acrylate and an initiator.
Further, the halogen-free flame-retardant unsaturated polyester composition comprises the following three components:
(1) resin A: an unsaturated polyester resin;
(2) resin B: one or more phosphorus-containing acrylates;
(3) and (3) an initiator.
In some embodiments, the resin a has a structure as shown in formula (1):
in the formula (1), G, P represents respectively alkyl or aryl in dihydric alcohol and saturated dibasic acid commonly used in commercial unsaturated polyester, x and y represent polymerization degree, 2 < x < 5, and 2 < y < 5. For example, the dihydric alcohol includes propylene glycol, diethylene glycol, dipropylene glycol, and the like, and the saturated dibasic acid includes phthalic acid, isophthalic acid, adipic acid, and the like, but is not limited thereto.
The resin B has a structure shown in a formula (2):
（2）
wherein R is1、R2、R3、R4、R5、R6Are independently selected from hydrogen atoms, alkyl of C1-C6, alkoxy of C1-C6, phenyl, phenoxy or cycloalkyl of C3-C7;
x is
Or
(ii) a Y is
Or
；
Z is selected from
、
、
Or
。
In some embodiments, the mass ratio of the resin A (including unsaturated polyester resin), the resin B (including phosphorus-containing acrylate) and the initiator is 60-90: 10-40: 0.03 to 0.06.
In some embodiments, the initiator may be any one or a combination of two or more of benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, t-butyl peroxybenzoate, t-butyl peroxypivalate, methyl ethyl ketone peroxide, cyclohexanone peroxide, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, azobisisobutyronitrile, azobisisoheptonitrile, and the like, without being limited thereto.
In another aspect of the embodiments of the present invention, a preparation method of a halogen-free flame retardant unsaturated polyester composition is provided, which includes: commercial unsaturated polyester is used as resin A, and resin B is completely dissolved in matrix resin according to different proportions at a certain temperature to obtain a uniform mixture.
The embodiment of the invention also provides a preparation method of the halogen-free flame-retardant unsaturated polyester cured product, which comprises the following steps: the halogen-free flame-retardant unsaturated polyester composition is subjected to gradient curing at the temperature of 80-180 ℃.
The embodiment of the invention also provides a preparation method of the halogen-free flame-retardant unsaturated polyester cured product, which comprises the following steps: and carrying out gradient curing on the mixed reaction system containing the resin A, the resin B and the initiator within the range of 80-180 ℃.
In some embodiments, the resin a has a structure as shown in formula (1):
（1）
in the formula (1), G and P respectively represent alkyl or aryl in dihydric alcohol and saturated dibasic acid commonly used in commercial unsaturated polyester, x and y represent polymerization degree, x is more than 2 and less than 5, and y is more than 2 and less than 5; for example, the dihydric alcohol includes propylene glycol, diethylene glycol, dipropylene glycol, and the like, and the saturated dibasic acid includes phthalic acid, isophthalic acid, adipic acid, and the like, but is not limited thereto.
The resin B has a structure shown in a formula (2):
（2）
wherein R is1、R2、R3、R4、R5、R6Are independently selected from hydrogen atoms, alkyl of C1-C6, alkoxy of C1-C6, phenyl, phenoxy or cycloalkyl of C3-C7;
x is
Or
(ii) a Y is
Or
；
Z is selected from
、
、
Or
。
In some embodiments, the mass ratio of the resin A, the resin B and the initiator is 60-90: 10-40: 0.03 to 0.06.
In some embodiments, the initiator may be any one or a combination of two or more of benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, t-butyl peroxybenzoate, t-butyl peroxypivalate, methyl ethyl ketone peroxide, cyclohexanone peroxide, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, azobisisobutyronitrile, azobisisoheptonitrile, and the like, without being limited thereto.
Further, another aspect of the embodiment of the present invention provides the halogen-free flame retardant unsaturated polyester cured product prepared by the method, wherein the glass transition temperature of the cured product is 102 to 151 ℃, the tensile strength of the cured product is 98 to 164MPa, and the flame retardant property of the cured product is grade V0.
The invention also provides the application of the halogen-free flame-retardant unsaturated polyester composition and the condensate thereof in the fields of composite materials and the like.
Another aspect of an embodiment of the present invention also provides a method for processing a polyester article, including: and preparing the halogen-free flame-retardant unsaturated polyester composition into a required polyester product by adopting any one of extrusion, injection and spinning.
In some embodiments, the halogen-free flame retardant unsaturated polyester composition may be mixed with other additives, such as reinforcing materials, lubricants, etc., and then subjected to the extrusion, injection, spinning, etc.
Further, the reinforcing material includes mineral powder, glass fiber, etc. and is not limited thereto, and the addition amount thereof may be a common addition amount well known in the art.
Furthermore, heating is carried out in the processes of extrusion, injection, spinning and the like, and the heating temperature is 180-250 ℃.
For example, embodiments of the present invention provide a method of making a polyester article, comprising: injecting the halogen-free flame-retardant unsaturated polyester composition into a polyester product by using an injection molding machine, wherein the operating parameters of the injection molding machine comprise: the temperature of the charging barrel is 200-220 ℃, and the pressure maintaining time is more than 10 s.
For example, an embodiment of the present invention provides a method for processing a polyester film, including:
feeding the halogen-free flame-retardant unsaturated polyester composition into a single-screw extruder, performing melt extrusion at the temperature of 200-220 ℃, and casting a molten fluid onto a rotating cooling roller to obtain a casting thick sheet with the thickness of 1500-5500 mu m;
preheating the casting thick sheet to 110-160 ℃, longitudinally stretching for 3-4 times, preheating to 110-160 ℃ again, transversely stretching for 3-4.5 times, and then carrying out heat setting at 200-220 ℃ to obtain the polyester film.
For another example, an embodiment of the present invention further provides a multilayer composite film, which includes a first structural layer and a second structural layer sequentially stacked, wherein the first structural layer and the second structural layer are bonded together, and the first structural layer is a film formed from the halogen-free flame retardant unsaturated polyester composition. The second structural layer can be formed by inorganic materials, organic materials or composite materials thereof. The multilayer composite film may be applied to a garment material, a protective film for surfaces of flammable goods, and the like, without being limited thereto.
In another aspect of the embodiments of the present invention, there is also provided a device having a heat-resistant flame-retardant structure, where the heat-resistant flame-retardant structure includes the aforementioned halogen-free flame-retardant unsaturated polyester cured product.
In conclusion, in the halogen-free flame-retardant unsaturated polyester composition and the cured product thereof provided by the invention, the introduction of the phosphorus-containing additive resin does not cause negative influence on the performance of the matrix resin, but can simultaneously improve the thermodynamic property and the flame retardant property of the cured resin. In addition, the halogen-free flame-retardant unsaturated polyester composition and the condensate thereof have the advantages of simple preparation process, low pollution, low toxicity and simple post-treatment, and the obtained resin has excellent processing performance, and the prepared casting body also has excellent flame retardant property and mechanical property.
The technical solutions of the present invention will be described in further detail below with reference to several preferred embodiments and accompanying drawings, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. It is to be noted that the following examples are intended to facilitate the understanding of the present invention, and do not set forth any limitation thereto. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. The test methods in the following examples, which are not specified under specific conditions, are generally carried out under conventional conditions.
In the following examples, the flame retardancy of the cured halogen-free flame-retardant unsaturated polyester resin was measured by a vertical burning test apparatus, in which V0 was the highest grade in the vertical burning test.
The resin A, a commercially available unsaturated polyester, in the following examples was obtained from commercial sources and had a molecular weight in the range of 2000 to 3000.
Example 1
Synthesis of resin B:
dissolving 1 part of 4,4' -dihydroxybenzophenone, 1 part of DOPO and a catalyst methanesulfonic acid (1 wt% of the DOPO content) in 4 parts of guaiacol at 120 ℃, and reacting at the temperature for 36 hours to obtain a phosphorus-containing monomer; then, 1 part of the phosphorus-containing monomer and 6 parts of triethylamine were dissolved in an appropriate amount of DMSO. After cooling the system to 0 ℃, slowly dripping 6 parts of acryloyl chloride into the system by using a constant pressure dropping funnel, and continuously stirring and reacting for 15 hours after finishing the dripping, so as to obtain the resin B (4, 4' -dihydroxybenzophenone/DOPO/guaiacol).
Resin B
Resin A
Resin A (G: ethylene glycol; P: terephthalic acid) and resin B (4, 4' -dihydroxybenzophenone/DOPO/guaiacol) were mixed in the following ratio of 80:20 mass ratio was stirred and mixed at 50 c, and 0.06 part of benzoyl peroxide as a radical initiator was added to the mixture. Finally, the obtained resin solution is subjected to gradient temperature rise solidification in a vacuum oven, and the procedure is as follows: pre-curing at 80 deg.C for 2-4h, heating to 120 deg.C, curing for 2-4h, and finally curing at 180 deg.C for 2-4 h.
The glass transition temperature of the obtained cast body is 120 ℃, the tensile strength is 133MPa (see figure 1), and the flame retardant property is V0 grade.
Example 2
Synthesis of resin B:
dissolving 1 part of 4,4' -dihydroxybenzophenone, 1 part of DOPO and a catalyst acetic acid (0.5 wt% of the DOPO content) in 2 parts of phenol at 130 ℃ and reacting at the temperature for 24 hours to obtain a phosphorus-containing monomer; then 1 part of the phosphorus-containing monomer, 10 parts of potassium carbonate were dissolved and dispersed in an appropriate amount of DMSO. After the system is cooled to-20 ℃, 10 parts of acryloyl chloride is slowly dripped into the system by using a constant pressure dropping funnel, and the stirring reaction is continued for 20 hours after the completion of the dripping reaction, so that the resin B (4, 4' -dihydroxy benzophenone/DOPO/phenol) is obtained.
Resin B
Resin A
Resin A (G: ethylene glycol; P: terephthalic acid) and resin B (4, 4' -dihydroxybenzophenone/DOPO/phenol) were mixed in a ratio of 70:30 mass ratio was stirred and mixed at 55 c, and 0.03 part of t-butyl hydroperoxide as a radical initiator was added to the mixture. Finally, the obtained resin solution is subjected to gradient temperature rise solidification in a vacuum oven, and the procedure is as follows: pre-curing at 80 deg.C for 2-4h, heating to 120 deg.C, curing for 2-4h, and finally curing at 180 deg.C for 2-4 h.
The glass transition temperature of the obtained cast body is 131 ℃, the tensile strength is 144MPa (see figure 2), and the flame retardant property is V0 grade.
Example 3
Synthesis of resin B:
dissolving 1 part of 2-methyl-4, 4' -dihydroxy benzophenone, 1 part of DOPO and catalyst sulfuric acid (7.5 wt% of DOPO content) in 3 parts of aniline at 130 ℃, reacting for 12 hours at the temperature, filtering while hot, and cleaning to obtain a phosphorus-containing monomer; then 1 part of the phosphorus-containing monomer, 12 parts of pyridine were dissolved in an appropriate amount of DMSO. After the system is cooled to 30 ℃, 12 parts of acryloyl chloride is slowly dripped into the system by using a constant pressure dropping funnel, and after the reaction is finished, the stirring reaction is continued for 6 hours to obtain the resin B (2-methyl-4, 4' -dihydroxy benzophenone/DOPO/aniline).
Resin B
Resin A
The resin A (G: ethylene glycol; P: phthalic acid) and the resin B ((2-methyl-4, 4' -dihydroxybenzophenone/DOPO/aniline) are stirred and mixed at the temperature of 60 ℃ according to the mass ratio of 60: 40, 0.04 part of free radical initiator di-tert-butyl peroxide is added into the mixture, and finally, the obtained resin solution is subjected to gradient temperature rise curing in a vacuum oven, wherein the procedure comprises the steps of precuring at the temperature of 80 ℃ for 2-4h, then heating to the temperature of 120 ℃ for curing for 2-4h, and finally curing at the temperature of 180 ℃ for 2-4 h.
The glass transition temperature of the obtained cast body is 151 ℃, the tensile strength is 164MPa, and the flame retardant property is V0 grade.
Example 4
Synthesis of resin B:
dissolving 1 part of 4,4' -dihydroxy-3-methoxybenzophenone, 1 part of DOPO and a catalyst aminobenzenesulfonic acid (2.5 wt% of DOPO content) in 6 parts of m-hexylphenol at 120 ℃ and reacting at the temperature for 12 hours to obtain a phosphorus-containing monomer; then a mixture of 1 part of the phosphorus-containing monomer, 10 parts of pyridine and triethylamine was dissolved in an appropriate amount of DMSO. After the system is cooled to 20 ℃, 10 parts of methacryloyl chloride is slowly dripped into the system by using a constant pressure dropping funnel, and the stirring reaction is continued for 8 hours after the completion of the dripping reaction, so that the resin B (4, 4' -dihydroxy-3-methoxybenzophenone/DOPO/m-hexylphenol) is obtained.
Resin B
Resin A
Resin A (G: propylene glycol; P: phthalic acid) and resin B (4, 4' -dihydroxy-3-methoxybenzophenone/DOPO/m-hexylphenol) were mixed in the following ratio of 70:30 mass ratio was stirred and mixed at 55 c, and 0.06 part of dicumyl peroxide as a radical initiator was added to the mixture. Finally, the obtained resin solution is subjected to gradient temperature rise solidification in a vacuum oven, and the procedure is as follows: pre-curing at 80 deg.C for 2-4h, heating to 120 deg.C, curing for 2-4h, and finally curing at 180 deg.C for 2-4 h.
The glass transition temperature of the obtained cast body is 112 ℃, the tensile strength is 106MPa, and the flame retardant property is V0 grade.
Example 5
Synthesis of resin B:
dissolving 1 part of 4,4' -dihydroxybenzophenone, 1 part of DOPO and a catalyst of ferric chloride (4.5 wt% of the DOPO content) in 2 parts of o-methylphenol at 130 ℃, and reacting for 12 hours at the temperature to obtain a phosphorus-containing monomer; a mixture of 1 part of this phosphorus-containing monomer, 12 parts of triethanolamine and 4-dimethylaminopyridine is then dissolved in an appropriate amount of DMSO. After cooling the system to 10 ℃, slowly dripping 12 parts of methacryloyl chloride into the system by using a constant pressure dropping funnel, continuously stirring for reaction for 12 hours after the reaction is finished, and finally removing the solvent to obtain the resin B (4, 4' -dihydroxybenzophenone/DOPO/o-methylphenol).
Resin B
Resin A
Resin A (G: ethylene glycol; P: phthalic acid) and resin B (4, 4' -dihydroxybenzophenone/DOPO/o-methylphenol) were mixed in the following ratio of 90: 10 at 50 c, and 0.03 parts of azobisisobutyronitrile, a radical initiator, was added to the mixture. Finally, the obtained resin solution is subjected to gradient temperature rise solidification in a vacuum oven, and the procedure is as follows: pre-curing at 80 deg.C for 2-4h, heating to 120 deg.C, curing for 2-4h, and finally curing at 180 deg.C for 2-4 h.
The glass transition temperature of the obtained cast body is 106 ℃, the tensile strength is 109MPa, and the flame retardant property is V0 grade.
Example 6
Synthesis of resin B:
dissolving 1 part of 4,4' -dihydroxy-3-methoxybenzophenone, 1 part of DOPO and a catalyst pyridine sulfonic acid (10 wt% of DOPO content) in 6 parts of carvacrol at 100 ℃, and reacting at the temperature for 36 hours to obtain a phosphorus-containing monomer; then a mixture of 1 part of the phosphorus-containing monomer, 8 parts of pyridine and triethylamine was dissolved in an appropriate amount of DMSO. After cooling the system to-10 ℃, slowly dripping 10 parts of methacryloyl chloride into the system by using a constant pressure dropping funnel, and continuously stirring for reacting for 24 hours to obtain the resin B (4, 4' -dihydroxy-3-methoxybenzophenone/DOPO/carvacrol).
Resin B
Resin A
The resin A (G: monoethylene glycol; P: phthalic acid) and the resin B ((4, 4' -dihydroxy-3-methoxybenzophenone/DOPO/carvacrol) are stirred and mixed at 60 ℃ according to the mass ratio of 60: 40, and a mixture of 0.05 part of a free radical initiator dicumyl peroxide and azobisisobutyronitrile is added into the mixture, finally, the obtained resin solution is subjected to gradient temperature rise curing in a vacuum oven, wherein the procedure is that the resin solution is pre-cured at 80 ℃ for 2-4h, then is heated to 120 ℃ for curing for 2-4h, and finally is cured at 180 ℃ for 2-4 h.
The glass transition temperature of the obtained casting body is 120 ℃, the tensile strength is 126MPa, and the flame retardant property is V0 grade.
Example 7
Synthesis of resin B:
dissolving 1 part of 4,4' -dihydroxybenzophenone, 1 part of DOPO and a catalyst of aluminum trichloride (0.1 wt% of the DOPO content) in 5 parts of thymol at 130 ℃ and reacting at the temperature for 12 hours to obtain a phosphorus-containing monomer; then 1 part of this phosphorus-containing monomer, 10 parts of sodium acetate mixture were dissolved and dispersed in an appropriate amount of DMSO. After cooling the system to 15 ℃, slowly dripping 12 parts of methacryloyl chloride into the system by using a constant pressure dropping funnel, continuously stirring and reacting for 18h after finishing, and finally removing the solvent to obtain the resin B (4, 4' -dihydroxybenzophenone/DOPO/vanillyl phenol).
Resin B
Resin A
Resin A (G: monoethylene glycol; P: terephthalic acid) and resin B (4, 4' -dihydroxybenzophenone/DOPO/vanilla) were mixed in the following ratio 80:20 at 60 c and 0.04 part of the free radical initiator cyclohexanone peroxide + diisopropyl peroxydicarbonate is added to the mixture. Finally, the obtained resin solution is subjected to gradient temperature rise solidification in a vacuum oven, and the procedure is as follows: pre-curing at 80 deg.C for 2-4h, heating to 120 deg.C, curing for 2-4h, and finally curing at 180 deg.C for 2-4 h.
The glass transition temperature of the obtained casting is 106 ℃, the tensile strength is 98MPa, and the flame retardant property is V0 grade.
Example 8
Synthesis of resin B:
dissolving 1 part of 4,4 '-dihydroxy-3, 3' -dipropoxybenzophenone, 1 part of DOPO and a catalyst boron trifluoride (10 wt% of DOPO content) in 1 part of m-oxypropylphenol at 120 ℃ and reacting at this temperature for 20 hours to give a phosphorus-containing monomer; then 1 part of the phosphorus-containing monomer, 10 parts of N, N-diisopropylethylamine were dissolved in an appropriate amount of DMSO. After the system is cooled to-20 ℃, 10 parts of methacryloyl chloride is slowly dripped into the system by using a constant pressure dropping funnel, and the stirring reaction is continued for 10 hours after the completion of the dripping reaction, so that the resin B (4, 4 '-dihydroxy-3, 3' -dipropoxybenzophenone/DOPO/m-oxypropylphenol) is obtained.
Resin B
Resin A
Resin A (G: monoethylene glycol; P: isophthalic acid) and resin B (4, 4 '-dihydroxy-3, 3' -dipropoxybenzophenone/DOPO/m-oxypropylphenol) were mixed in the following ratio of 60: 40 are mixed with stirring at 55 c and 0.06 part of the free radical initiator lauroyl peroxide + cumene hydroperoxide is added to the mixture. Finally, the obtained resin solution is subjected to gradient temperature rise solidification in a vacuum oven, and the procedure is as follows: pre-curing at 80 deg.C for 2-4h, heating to 120 deg.C, curing for 2-4h, and finally curing at 180 deg.C for 2-4 h.
The glass transition temperature of the obtained casting is 116 ℃, the tensile strength is 111MPa, and the flame retardant property is V0 grade.
Example 9
Synthesis of resin B:
dissolving 1 part of 4,4' -2-methyl dihydroxy benzophenone, 1 part of DOPO and a catalyst boric acid (0.5 wt% of the DOPO content) in 5 parts of aniline at 130 ℃, reacting for 12 hours at the temperature, filtering while hot, and cleaning to obtain a phosphorus-containing monomer; then 1 part of the phosphorus-containing monomer, 12 parts of pyridine were dissolved in an appropriate amount of DMSO. After the system is cooled to-15 ℃, 10 parts of methacryloyl chloride is slowly dripped into the system by using a constant pressure dropping funnel, and the stirring reaction is continued for 18 hours after the completion of the dripping reaction, so that the resin B (2-methyl-4, 4' -dihydroxy benzophenone/DOPO/aniline) is obtained.
Resin B
Resin A
The resin A (G: monoethylene glycol; P: isophthalic acid) and the resin B ((2-methyl-4, 4' -dihydroxybenzophenone/DOPO/aniline) are stirred and mixed at the temperature of 60 ℃ according to the mass ratio of 80:20, and 0.03 part of free radical initiator tert-butyl peroxybenzoate + tert-butyl peroxypivalate is added into the mixture, finally, the obtained resin solution is subjected to gradient temperature rise curing in a vacuum oven, wherein the procedure is that the resin solution is pre-cured at the temperature of 80 ℃ for 2-4h, then is heated to the temperature of 120 ℃ for curing for 2-4h, and finally is cured at the temperature of 180 ℃ for 2-4 h.
The glass transition temperature of the obtained cast body is 109 ℃, the tensile strength is 112MPa, and the flame retardant property is V0 grade.
Example 10
Synthesis of additive resin B:
dissolving 1 part of 4,4' -dihydroxybenzophenone, 1 part of DOPO and a catalyst of ferric bromide (2 wt% of the DOPO content) in 1 part of m-ethylaniline at 130 ℃, and reacting for 12 hours at the temperature to obtain a phosphorus-containing monomer; then 1 part of this phosphorus-containing monomer, 10 parts of N, N-diisopropylethylamine were dissolved and dispersed in an appropriate amount of DMSO. After the system is cooled to 5 ℃, 12 parts of acryloyl chloride is slowly dripped into the system by using a constant pressure dropping funnel, and after the reaction is finished, the stirring reaction is continued for 10 hours to obtain resin B (4, 4' -dihydroxy benzophenone/DOPO/m-ethylaniline).
Resin B
Resin A
Resin A (G: monoethylene glycol; P: isophthalic acid) and resin B (4, 4' -dihydroxybenzophenone/DOPO/m-ethylaniline) were mixed in the following ratio of 60: 40 at 55 c, and 0.04 part of a radical initiator of methyl ethyl ketone peroxide + azobisisoheptonitrile was added to the mixture. Finally, the obtained resin solution is subjected to gradient temperature rise solidification in a vacuum oven, and the procedure is as follows: pre-curing at 80 deg.C for 2-4h, heating to 120 deg.C, curing for 2-4h, and finally curing at 180 deg.C for 2-4 h.
The glass transition temperature of the obtained cast body is 133 ℃, the tensile strength is 135MPa, and the flame retardant property is V0 grade.
Example 11
Synthesis of resin B:
dissolving 1 part of 4,4' -dihydroxy-3-phenylbenzophenone, 1 part of DOPO and a catalyst boron trifluoride (10 wt% of DOPO content) in 1 part of phenol at 120 ℃ and reacting at this temperature for 15 hours to give a phosphorus-containing monomer; then, 1 part of the phosphorus-containing monomer and 10 parts of 4-dimethylaminopyridine were dissolved in an appropriate amount of DMSO. After the system is cooled to-12 ℃, 10 parts of methacryloyl chloride is slowly dripped into the system by using a constant pressure dropping funnel, and the stirring reaction is continued for 15 hours after the completion of the dripping reaction, so that the resin B (4, 4' -dihydroxy-3-phenylbenzophenone/DOPO/phenol) is obtained.
Resin B
Resin A
Resin A (G: monoethylene glycol; P: isophthalic acid) and resin B (4, 4 '-dihydroxy-3, 3' -dipropoxybenzophenone/DOPO/phenol) were mixed in the following ratio of 70:30 at 55 c, and 0.06 part of a radical initiator azobisisobutyronitrile + azobisisoheptonitrile is added to the mixture. Finally, the obtained resin solution is subjected to gradient temperature rise solidification in a vacuum oven, and the procedure is as follows: pre-curing at 80 deg.C for 2-4h, heating to 120 deg.C, curing for 2-4h, and finally curing at 180 deg.C for 2-4 h.
The glass transition temperature of the obtained casting body is 123 ℃, the tensile strength is 119MPa, and the flame retardant property is V0 grade.
Example 12
Synthesis of resin B:
dissolving 1 part of 4,4 '-dihydroxy-3, 3' -dicyclohexylbenzophenone, 1 part of DOPO and a catalyst of iron bromide (4.5 wt% of the DOPO content) in 5 parts of guaiacol at 120 ℃ and reacting for 15 hours at the temperature to obtain a phosphorus-containing monomer; then, 1 part of the phosphorus-containing monomer and 8 parts of pyridine were dissolved in an appropriate amount of DMSO. After cooling the system to-30 ℃, slowly dripping 10 parts of methacryloyl chloride into the system by using a constant pressure dropping funnel, and continuously stirring for reacting for 6 hours to obtain the resin B (4, 4 '-dihydroxy-3, 3' -dicyclohexyl benzophenone/DOPO/guaiacol).
Resin B
Resin A
Resin A (G: propylene glycol; P: phthalic acid) and resin B (4, 4 '-dihydroxy-3, 3' -dicyclohexylbenzophenone/DOPO/guaiacol) were mixed in the following ratio of 60: 40 are mixed with stirring at 55 c and 0.05 part of cyclohexanone peroxide, a radical initiator, is added to the mixture. Finally, the obtained resin solution is subjected to gradient temperature rise solidification in a vacuum oven, and the procedure is as follows: pre-curing at 80 deg.C for 2-4h, heating to 120 deg.C, curing for 2-4h, and finally curing at 180 deg.C for 2-4 h.
The glass transition temperature of the obtained casting body is 120 ℃, the tensile strength is 118MPa, and the flame retardant property is V0 grade.
Example 13
Synthesis of resin B:
dissolving 1 part of 2-propyl-4, 4' -dihydroxybenzophenone, 1 part of DOPO and a catalyst trifluoroacetic acid (1 wt% of the DOPO content) in 4 parts of guaiacol at 120 ℃, and reacting at the temperature for 36 hours to obtain a phosphorus-containing monomer; then, 1 part of the phosphorus-containing monomer and 6 parts of triethylamine were dissolved in an appropriate amount of DMSO. After the system is cooled to 0 ℃, 6 parts of acryloyl chloride is slowly dripped into the system by using a constant pressure dropping funnel, and the stirring reaction is continued for 15 hours after the completion of the dripping reaction, so that the resin B (2-propyl-4, 4' -dihydroxy benzophenone/DOPO/guaiacol) is obtained.
Resin B
Resin A
Resin A (G: ethylene glycol; P: terephthalic acid) and resin B (2-propyl-4, 4' -dihydroxybenzophenone/DOPO/guaiacol) were mixed in a ratio of 70:30 parts by mass are stirred and mixed at 50 c and 0.06 part of the free radical initiator dicyclohexyl peroxydicarbonate is added to the mixture. Finally, the obtained resin solution is subjected to gradient temperature rise solidification in a vacuum oven, and the procedure is as follows: pre-curing at 80 deg.C for 2-4h, heating to 120 deg.C, curing for 2-4h, and finally curing at 180 deg.C for 2-4 h.
The glass transition temperature of the obtained cast body is 131 ℃, the tensile strength is 138MPa, and the flame retardant property is V0 grade.
Example 14
Synthesis of resin B:
dissolving 1 part of 3-hexyl-4, 4' -dihydroxy benzophenone, 1 part of DOPO and a catalyst p-aminobenzenesulfonic acid (2 wt percent of the DOPO content) in 4 parts of m-oxyhexylphenol at 120 ℃, and reacting for 36 hours at the temperature to obtain a phosphorus-containing monomer; then, 1 part of the phosphorus-containing monomer and 6 parts of triethylamine were dissolved in an appropriate amount of DMSO. After the system is cooled to 0 ℃, 6 parts of acryloyl chloride is slowly dripped into the system by using a constant pressure dropping funnel, and after the reaction is finished, the reaction is continuously stirred for 15 hours to obtain a resin B (3-hexyl-4, 4' -dihydroxy benzophenone/DOPO/m-oxyhexyl phenol).
Resin B
Resin A
Resin A (G: ethylene glycol; P: terephthalic acid) and resin B (3-hexyl-4, 4' -dihydroxybenzophenone/DOPO/m-oxyhexylphenol) were mixed in a ratio of 70:30 parts by mass are stirred and mixed at 50 c and 0.06 part of the free radical initiator dicyclohexyl peroxydicarbonate is added to the mixture. Finally, the obtained resin solution is subjected to gradient temperature rise solidification in a vacuum oven, and the procedure is as follows: pre-curing at 80 deg.C for 2-4h, heating to 120 deg.C, curing for 2-4h, and finally curing at 180 deg.C for 2-4 h.
The glass transition temperature of the obtained casting body is 120 ℃, the tensile strength is 119MPa, and the flame retardant property is V0 grade.
Example 15
Synthesis of resin B:
dissolving 1 part of 4,4' -dihydroxy-3-propoxybenzophenone, 1 part of DOPO and a catalyst p-toluenesulfonic acid (2.5 wt% of DOPO content) in 5 parts of guaiacol at 120 ℃, and reacting at the temperature for 15 hours to obtain a phosphorus-containing monomer; then, 1 part of the phosphorus-containing monomer and 8 parts of pyridine were dissolved in an appropriate amount of DMSO. After cooling the system to-30 ℃, slowly dripping 10 parts of methacryloyl chloride into the system by using a constant pressure dropping funnel, and continuously stirring for reacting for 6 hours to obtain the resin B (4, 4' -dihydroxy-3-propoxybenzophenone/DOPO/guaiacol).
Resin B
Resin A
Resin A (G: propylene glycol; P: phthalic acid) and resin B (4, 4' -dihydroxy-3-propoxybenzophenone/DOPO/guaiacol) were mixed in the following ratio of 60: 40 are mixed with stirring at 55 c and 0.05 part of cyclohexanone peroxide, a radical initiator, is added to the mixture. Finally, the obtained resin solution is subjected to gradient temperature rise solidification in a vacuum oven, and the procedure is as follows: pre-curing at 80 deg.C for 2-4h, heating to 120 deg.C, curing for 2-4h, and finally curing at 180 deg.C for 2-4 h.
The glass transition temperature of the obtained cast body is 115 ℃, the tensile strength is 110MPa, and the flame retardant property is V0 grade.
Example 16
Synthesis of resin B:
dissolving 1 part of 4,4' -dihydroxy-3-hexyloxybenzophenone, 1 part of DOPO and a catalyst hydrochloric acid (5.5 wt% of the DOPO content) in 6 parts of o-phenylphenol at 130 ℃ and reacting at the temperature for 14 hours to obtain a phosphorus-containing monomer; a mixture of 1 part of this phosphorus-containing monomer, 12 parts of triethanolamine and 4-dimethylaminopyridine is then dissolved in an appropriate amount of DMSO. After the system is cooled to 10 ℃, 12 parts of methacryloyl chloride is slowly dripped into the system by using a constant pressure dropping funnel, the stirring reaction is continued for 12 hours after the completion, and finally the solvent is removed to obtain the resin B (4, 4' -dihydroxy-3-hexyloxybenzophenone/DOPO/o-phenylphenol).
Resin B
Resin A
Resin A (G: ethylene glycol; P: phthalic acid) and resin B (4, 4' -dihydroxy-3-hexyloxybenzophenone/DOPO/orthophenylphenol) were mixed in the following ratio of 90: 10 at 50 c, and 0.03 parts of azobisisobutyronitrile, a radical initiator, was added to the mixture. Finally, the obtained resin solution is subjected to gradient temperature rise solidification in a vacuum oven, and the procedure is as follows: pre-curing at 80 deg.C for 2-4h, heating to 120 deg.C, curing for 2-4h, and finally curing at 180 deg.C for 2-4 h.
The glass transition temperature of the obtained cast body is 117 ℃, the tensile strength is 115MPa, and the flame retardant property is V0 grade.
Example 17
Synthesis of resin B:
dissolving 1 part of 4,4' -dihydroxy-3-phenoxybenzophenone, 1 part of DOPO and a catalyst nitric acid (8 wt% of the DOPO content) in 1 part of o-phenylphenol at 120 ℃, and reacting for 15 hours at the temperature to obtain a phosphorus-containing monomer; then, 1 part of the phosphorus-containing monomer and 10 parts of 4-dimethylaminopyridine were dissolved in an appropriate amount of DMSO. After the system is cooled to-12 ℃, 10 parts of methacryloyl chloride is slowly dripped into the system by using a constant pressure dropping funnel, and the stirring reaction is continued for 15 hours after the completion of the dripping reaction, so that the resin B (4, 4' -dihydroxy-3-phenoxybenzophenone/DOPO/o-phenylphenol) is obtained.
Resin B
Resin A
Mixing resin A (G: monoethylene glycol; P: isophthalic acid) and resin B (4, 4' -dihydroxy-3-phenoxybenzophenone DOPO/o-phenylphenol) according to a weight ratio of 80:20 at 55 c, and 0.06 part of azobisisobutyronitrile + azobisisoheptonitrile, a radical initiator, was added to the mixture. Finally, the obtained resin solution is subjected to gradient temperature rise solidification in a vacuum oven, and the procedure is as follows: pre-curing at 80 deg.C for 2-4h, heating to 120 deg.C, curing for 2-4h, and finally curing at 180 deg.C for 2-4 h.
The glass transition temperature of the obtained casting body is 129 ℃, the tensile strength is 128MPa, and the flame retardant property is V0 grade.
Example 18
Synthesis of additive resin B:
dissolving 1 part of 4,4' -dihydroxy-3-cyclopropyl benzophenone, 1 part of DOPO and a catalyst of ferric bromide (2 wt percent of the DOPO content) in 1 part of m-cyclopropyl phenol at the temperature of 130 ℃, and reacting for 12 hours at the temperature to obtain a phosphorus-containing monomer; then 1 part of this phosphorus-containing monomer, 10 parts of N, N-diisopropylethylamine were dissolved and dispersed in an appropriate amount of DMSO. After the system is cooled to 5 ℃, 12 parts of acryloyl chloride is slowly dripped into the system by using a constant pressure dropping funnel, and after the reaction is finished, the reaction is continuously stirred for 10 hours to obtain the resin B (4, 4' -dihydroxy-3-cyclopropyl benzophenone/DOPO/m-cyclopropyl phenol).
Resin B
Resin A
Resin A (G: monoethylene glycol; P: isophthalic acid) and resin B (4, 4' -dihydroxy-3-cyclopropylbenzophenone/DOPO/m-cyclopropylphenol) were mixed in the following ratio of 60: 40 at 55 c, and 0.04 part of a radical initiator of methyl ethyl ketone peroxide + azobisisoheptonitrile was added to the mixture. Finally, the obtained resin solution is subjected to gradient temperature rise solidification in a vacuum oven, and the procedure is as follows: pre-curing at 80 deg.C for 2-4h, heating to 120 deg.C, curing for 2-4h, and finally curing at 180 deg.C for 2-4 h.
The glass transition temperature of the obtained casting is 131 ℃, the tensile strength is 132MPa, and the flame retardant property is V0 grade.
Example 19
Synthesis of resin B:
dissolving 1 part of 4,4' -dihydroxy-3-cycloheptylbenzophenone, 1 part of DOPO and a catalyst sulfuric acid (7.5 wt% of the DOPO content) in 3 parts of o-cycloheptylphenol at 130 ℃, reacting for 12 hours at the temperature, filtering while hot, and cleaning to obtain a phosphorus-containing monomer; then 1 part of the phosphorus-containing monomer, 12 parts of pyridine were dissolved in an appropriate amount of DMSO. After the system is cooled to 30 ℃, 12 parts of acryloyl chloride is slowly dripped into the system by using a constant pressure dropping funnel, and the stirring reaction is continued for 6 hours after the reaction is finished, so that the resin B (4, 4' -dihydroxy-3-cycloheptylbenzophenone DOPO/o-cycloheptylphenol) is obtained.
Resin B
Resin A
Resin A (G: ethylene glycol; P: phthalic acid) and resin B (4, 4' -dihydroxy-3-cycloheptylbenzophenone/DOPO/o-cycloheptylphenol) were mixed in the following ratio of 60: 40 parts by mass were stirred and mixed at 60 c, and 0.04 parts of a radical initiator, di-tert-butyl peroxide, was added to the mixture. Finally, the obtained resin solution is subjected to gradient temperature rise solidification in a vacuum oven, and the procedure is as follows: pre-curing at 80 deg.C for 2-4h, heating to 120 deg.C, curing for 2-4h, and finally curing at 180 deg.C for 2-4 h.
The glass transition temperature of the obtained casting is 147 ℃, the tensile strength is 152MPa, and the flame retardant property is V0 grade.
Example 20
Synthesis of resin B:
dissolving 1 part of 4,4 '-dihydroxy-3, 3' -dihexobenzophenone, 1 part of DOPO and a catalyst pyridine sulfonic acid (10 wt% of DOPO content) in 6 parts of carvacrol at 100 ℃, and reacting for 36 hours at the temperature to obtain a phosphorus-containing monomer; then a mixture of 1 part of the phosphorus-containing monomer, 8 parts of pyridine and triethylamine was dissolved in an appropriate amount of DMSO. After cooling the system to-10 ℃, slowly dripping 10 parts of methacryloyl chloride into the system by using a constant pressure dropping funnel, and continuously stirring for reacting for 24 hours to obtain the resin B (4, 4 '-dihydroxy-3, 3' -dihexobenzophenone/DOPO/carvacrol).
Resin B
Resin A
The resin A (G: monoethylene glycol; P: phthalic acid) and the resin B ((4, 4 '-dihydroxy-3, 3' -dihexobenzophenone/DOPO/carvacrol) are stirred and mixed at the mass ratio of 60: 40 at the temperature of 60 ℃, and 0.05 part of a mixture of a free radical initiator dicumyl peroxide and azobisisobutyronitrile is added into the mixture, finally, the obtained resin solution is subjected to gradient temperature rise curing in a vacuum oven, wherein the gradient temperature rise curing is carried out for 2-4h at the temperature of 80 ℃, the gradient temperature rise curing is carried out for 2-4h at the temperature of 120 ℃, and the gradient temperature rise curing is carried out for 2-4h at the temperature of 180 ℃.
The glass transition temperature of the obtained casting body is 111 ℃, the tensile strength is 113MPa, and the flame retardant property is V0 grade.
Comparative example 1
This comparative example differs from example 1 in that: resin B in example 1 was replaced with a common halogen-containing polymer as a flame retardant. The product obtained in this comparative example has a glass transition temperature of 90 ℃, a tensile strength of 95MPa and a flame retardancy test rating V0.
Comparative example 2
This comparative example differs from example 1 in that: resin B in example 1 was replaced with DOPO as a flame retardant. The product obtained in this comparative example has a glass transition temperature of 90 ℃, a tensile strength of 91MPa and a flame retardancy test rating V0.
Example 21: the resin solution obtained in example 1 was injected into a standard sample using an injection molding machine with the following parameters: the cylinder temperature is 200-220 ℃, the dwell time is 10s, and the standard sample is tested according to ASTM D638-08 and GB/T1843-2008 respectively, and the results show that the standard sample has good tensile property, elongation at break and notch impact strength.
Example 22: the resin solution obtained in example 2 was mixed with calcium behenate in the following ratio of 1: 0.07 percent of the mass ratio is mixed to prepare spinning melt, and then spinning is carried out, wherein the spinning technological parameters are as follows: the pressure after filtration during spinning was 128kg/cm2(ii) a The extrusion temperature is 180-220 ℃; the cooling temperature is 20 ℃; the winding speed is 3500 m/min; the swell ratio of the spinning melt was 1.24. The polyester fiber yarn prepared by the method has higher tensile strength and elongation at break.
Example 23: feeding the resin solution obtained in the embodiment 1 into a single-screw extruder, carrying out melt extrusion at 200-220 ℃, casting a molten fluid on a rotating cooling roller to obtain a casting thick sheet with the thickness of 1500-5500 microns, preheating the casting thick sheet to 125-140 ℃, longitudinally stretching the casting thick sheet by 3-4 times, then preheating the casting thick sheet to 125-140 ℃, transversely stretching the casting thick sheet by 3-4.5 times, and carrying out heat setting at 200-220 ℃ to obtain the polyester film.
The polyester film can be applied in various fields. For example, the flame-retardant and heat-resistant composite fabric can be combined with fabric and lining materials through adhesives to form clothes with a composite laminated structure, and the flame-retardant and heat-resistant composite fabric can be used for manufacturing various protective clothes with flame-retardant and heat-resistant performances.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.
Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.
It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.
Claims (13)
1. A halogen-free flame-retardant unsaturated polyester composition is characterized by comprising: resin A, resin B and an initiator; the resin A is unsaturated polyester resin, the resin B is phosphorus-containing acrylate,
the unsaturated polyester resin has a structure shown in a formula (1):
（1）
wherein G, P is divalent alkyl or aryl derived from dihydric alcohol and saturated dibasic acid, x and y represent polymerization degree, x is more than 2 and less than 5, and y is more than 2 and less than 5;
the phosphorus-containing acrylate has a structure shown as a formula (2):
（2）
wherein R is1、R2、R3、R4、R5、R6Are independently selected from hydrogen atoms, alkyl of C1-C6, alkoxy of C1-C6, phenyl, phenoxy or cycloalkyl of C3-C7;
and the glass transition temperature of a cured product formed by curing the halogen-free flame-retardant unsaturated polyester composition is 102-151 ℃, the tensile strength is 98-164 MPa, and the flame retardant property is V0 grade.
2. The halogen-free flame-retardant unsaturated polyester composition according to claim 1, wherein the phosphorus-containing acrylate is prepared by a method comprising:
carrying out condensation reaction on a first mixed reaction system containing an organic phosphorus compound shown as a formula (4), a compound shown as a formula (5), a compound shown as a formula (6) and an acid catalyst at 100-130 ℃ for 12-36 h to obtain a compound shown as a formula (3);
（3）
wherein R is1To R6Are independently selected from hydrogen atoms, alkyl of C1-C6, alkoxy of C1-C6, phenyl, phenoxy or cycloalkyl of C3-C7, R7is-OH or NH2；
And (2) reacting a second mixed reaction system containing a compound shown as a formula (3), acryloyl chloride or methacryloyl chloride and an acid-binding agent at the temperature of-30 ℃ for 6-24 hours to obtain the phosphorus-containing acrylate, wherein the acid-binding agent is selected from any one or a combination of more than two of potassium carbonate, sodium acetate, triethylamine, pyridine, N-diisopropylethylamine, 4-dimethylaminopyridine and triethanolamine.
3. The halogen-free flame-retardant unsaturated polyester composition according to claim 2, wherein: the molar ratio of the organophosphorus compound represented by the formula (4), the compound represented by the formula (5) to the compound represented by the formula (6) is 1: 1: 1 to 6.
4. The halogen-free flame-retardant unsaturated polyester composition according to claim 2, wherein: the mass ratio of the acidic catalyst to the organic phosphorus compound represented by the formula (4) is 0.1-10: 100.
5. the halogen-free flame-retardant unsaturated polyester composition according to claim 2, wherein: the acidic catalyst is selected from any one or combination of more than two of organic acid, inorganic acid and Lewis acid.
6. The halogen-free flame-retardant unsaturated polyester composition according to claim 2, wherein: the mol ratio of the compound shown in the formula (3), acryloyl chloride or methacryloyl chloride to the acid binding agent is 1: 6-12: 6 to 12.
7. The halogen-free flame-retardant unsaturated polyester composition according to claim 1, wherein: the mass ratio of the resin A to the resin B to the initiator is 60-90: 10-40: 0.03 to 0.06.
8. The halogen-free flame-retardant unsaturated polyester composition according to claim 1, wherein: the initiator is selected from any one or the combination of more than two of benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxypivalate, methyl ethyl ketone peroxide, cyclohexanone peroxide, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, azobisisobutyronitrile and azobisisoheptonitrile.
9. A preparation method of a halogen-free flame-retardant unsaturated polyester condensate is characterized by comprising the following steps: subjecting the halogen-free flame-retardant unsaturated polyester composition according to any one of claims 1 to 8 to gradient curing at 80 to 180 ℃.
10. The cured halogen-free flame-retardant unsaturated polyester prepared by the method according to claim 9, wherein the cured halogen-free flame-retardant unsaturated polyester has a glass transition temperature of 102 to 151 ℃, a tensile strength of 98 to 164MPa, and a flame retardancy of V0 grade.
11. A method of processing a polyester article, comprising: the halogen-free flame-retardant unsaturated polyester composition according to any one of claims 1 to 8 is formed into a desired polyester product by at least any one of extrusion, injection and spinning.
12. A method for processing a polyester film, comprising:
feeding the halogen-free flame-retardant unsaturated polyester composition according to any one of claims 1 to 8 into a single-screw extruder, melt-extruding at 200 to 220 ℃, and casting the molten fluid onto a rotating cooling drum to obtain a cast slab having a thickness of 1500 to 5500 μm;
preheating the casting thick sheet to 110-160 ℃, longitudinally stretching for 3-4 times, preheating to 110-160 ℃ again, transversely stretching for 3-4.5 times, and then carrying out heat setting at 200-220 ℃ to obtain the polyester film.
13. A multilayer composite film comprising a first structural layer and a second structural layer laminated in this order, wherein the first structural layer and the second structural layer are bonded to each other, and the first structural layer is a film formed from the halogen-free flame-retardant unsaturated polyester composition according to any one of claims 1 to 8.
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