CN109337050A - A kind of aromatic heterocyclic polymer resin of high intensity UV resistant high transparent and fire-retardant and preparation method thereof and application in fiber or film - Google Patents
A kind of aromatic heterocyclic polymer resin of high intensity UV resistant high transparent and fire-retardant and preparation method thereof and application in fiber or film Download PDFInfo
- Publication number
- CN109337050A CN109337050A CN201811148663.2A CN201811148663A CN109337050A CN 109337050 A CN109337050 A CN 109337050A CN 201811148663 A CN201811148663 A CN 201811148663A CN 109337050 A CN109337050 A CN 109337050A
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- China
- Prior art keywords
- aromatic heterocyclic
- acid
- polymer resin
- fluorine
- heterocyclic polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 125000006615 aromatic heterocyclic group Chemical group 0.000 title claims abstract description 62
- 239000002952 polymeric resin Substances 0.000 title claims abstract description 62
- 229920003002 synthetic resin Polymers 0.000 title claims abstract description 62
- 239000003063 flame retardant Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000835 fiber Substances 0.000 title claims abstract description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 239
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims abstract description 167
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 90
- 239000011737 fluorine Substances 0.000 claims abstract description 90
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 88
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 claims abstract description 42
- DYWGEVDXJIYDCC-UHFFFAOYSA-N phthalic acid;hydrobromide Chemical compound Br.OC(=O)C1=CC=CC=C1C(O)=O DYWGEVDXJIYDCC-UHFFFAOYSA-N 0.000 claims abstract description 32
- QPBGNSFASPVGTP-UHFFFAOYSA-N 2-bromoterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(Br)=C1 QPBGNSFASPVGTP-UHFFFAOYSA-N 0.000 claims abstract description 28
- FUSNOPLQVRUIIM-UHFFFAOYSA-N 4-amino-2-(4,4-dimethyl-2-oxoimidazolidin-1-yl)-n-[3-(trifluoromethyl)phenyl]pyrimidine-5-carboxamide Chemical compound O=C1NC(C)(C)CN1C(N=C1N)=NC=C1C(=O)NC1=CC=CC(C(F)(F)F)=C1 FUSNOPLQVRUIIM-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000012493 hydrazine sulfate Substances 0.000 claims abstract description 28
- 229910000377 hydrazine sulfate Inorganic materials 0.000 claims abstract description 28
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 18
- 239000001301 oxygen Substances 0.000 claims abstract description 18
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 15
- ZFCNECLRCWFTLI-UHFFFAOYSA-N 3-(3-carboxyphenoxy)benzoic acid Chemical compound OC(=O)C1=CC=CC(OC=2C=C(C=CC=2)C(O)=O)=C1 ZFCNECLRCWFTLI-UHFFFAOYSA-N 0.000 claims abstract description 12
- WVDRSXGPQWNUBN-UHFFFAOYSA-N 4-(4-carboxyphenoxy)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C=C1 WVDRSXGPQWNUBN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000003252 repetitive effect Effects 0.000 claims description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 21
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 11
- 239000005864 Sulphur Chemical group 0.000 claims description 11
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 claims description 10
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052794 bromium Inorganic materials 0.000 claims description 10
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 125000001072 heteroaryl group Chemical group 0.000 claims description 8
- 239000011256 inorganic filler Substances 0.000 claims description 8
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 8
- KHZYMPDILLAIQY-UHFFFAOYSA-N 3-(3-carboxyphenyl)benzoic acid Chemical compound OC(=O)C1=CC=CC(C=2C=C(C=CC=2)C(O)=O)=C1 KHZYMPDILLAIQY-UHFFFAOYSA-N 0.000 claims description 7
- -1 polytetrafluoroethylene Polymers 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 150000004767 nitrides Chemical class 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical class O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims description 4
- MPPQGYCZBNURDG-UHFFFAOYSA-N 2-propionyl-6-dimethylaminonaphthalene Chemical compound C1=C(N(C)C)C=CC2=CC(C(=O)CC)=CC=C21 MPPQGYCZBNURDG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052580 B4C Inorganic materials 0.000 claims description 3
- 229910052582 BN Inorganic materials 0.000 claims description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 3
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229920006231 aramid fiber Polymers 0.000 claims description 3
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- 239000001506 calcium phosphate Substances 0.000 claims description 3
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 3
- 235000011010 calcium phosphates Nutrition 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 238000003763 carbonization Methods 0.000 claims description 3
- 235000019700 dicalcium phosphate Nutrition 0.000 claims description 3
- MHJAJDCZWVHCPF-UHFFFAOYSA-L dimagnesium phosphate Chemical compound [Mg+2].OP([O-])([O-])=O MHJAJDCZWVHCPF-UHFFFAOYSA-L 0.000 claims description 3
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- 230000017525 heat dissipation Effects 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000001095 magnesium carbonate Substances 0.000 claims description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 claims description 3
- 239000004137 magnesium phosphate Substances 0.000 claims description 3
- 229910000157 magnesium phosphate Inorganic materials 0.000 claims description 3
- 229960002261 magnesium phosphate Drugs 0.000 claims description 3
- 235000010994 magnesium phosphates Nutrition 0.000 claims description 3
- 239000000391 magnesium silicate Substances 0.000 claims description 3
- 229910052919 magnesium silicate Inorganic materials 0.000 claims description 3
- 235000019792 magnesium silicate Nutrition 0.000 claims description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 3
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical group [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical group [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical group N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 3
- 239000010456 wollastonite Substances 0.000 claims description 3
- 229910052882 wollastonite Inorganic materials 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 2
- 150000002221 fluorine Chemical class 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 239000011667 zinc carbonate Substances 0.000 claims description 2
- 235000004416 zinc carbonate Nutrition 0.000 claims description 2
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- 239000010439 graphite Substances 0.000 claims 1
- 229910002804 graphite Inorganic materials 0.000 claims 1
- ZADYMNAVLSWLEQ-UHFFFAOYSA-N magnesium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[Mg+2].[Si+4] ZADYMNAVLSWLEQ-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 11
- 239000011347 resin Substances 0.000 abstract description 11
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 239000000178 monomer Substances 0.000 description 89
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 32
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 16
- 235000019253 formic acid Nutrition 0.000 description 16
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 11
- ZSDJVGXBJDDOCD-UHFFFAOYSA-N benzene dioctyl benzene-1,2-dicarboxylate Chemical compound C(C=1C(C(=O)OCCCCCCCC)=CC=CC1)(=O)OCCCCCCCC.C1=CC=CC=C1 ZSDJVGXBJDDOCD-UHFFFAOYSA-N 0.000 description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 5
- 125000005842 heteroatom Chemical group 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 229920002313 fluoropolymer Polymers 0.000 description 3
- 239000004811 fluoropolymer Substances 0.000 description 3
- 238000005087 graphitization Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- KSRLHLUUZHITAF-UHFFFAOYSA-N C(C=1C(C(=O)OCCCCCCCC)=CC=CC1)(=O)OCCCCCCCC.C1(=CC=CC=C1)SC1=CC=CC=C1 Chemical compound C(C=1C(C(=O)OCCCCCCCC)=CC=CC1)(=O)OCCCCCCCC.C1(=CC=CC=C1)SC1=CC=CC=C1 KSRLHLUUZHITAF-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- UOFDVLCOMURSTA-UHFFFAOYSA-N 2-(2-carboxyphenoxy)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1OC1=CC=CC=C1C(O)=O UOFDVLCOMURSTA-UHFFFAOYSA-N 0.000 description 1
- HSSYVKMJJLDTKZ-UHFFFAOYSA-N 3-phenylphthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(O)=O HSSYVKMJJLDTKZ-UHFFFAOYSA-N 0.000 description 1
- 241001465805 Nymphalidae Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000012648 alternating copolymerization Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
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Abstract
The present invention relates to resin technology fields, aromatic heterocyclic polymer resin more particularly to a kind of high-intensitive UV resistant high transparent and fire-retardant and preparation method thereof and application in fiber or film, the aromatic heterocyclic polymer resin of the high intensity UV resistant high transparent and fire-retardant the preparation method comprises the following steps: when R is oxygen, with terephthalic acid (TPA) and/or phthalic acid, azobenzene -4, 4 '-dioctyl phthalate and/or azobenzene -3, 3 '-dioctyl phthalate, fluorine-containing terephthalic acid (TPA) and/or fluorine-containing phthalic acid, containing bromo terephthalic acid and/or contain phthalate bromine, 4, 4'- oxydibenzoic acid and/or 3, 3'- oxydibenzoic acid, hydrazine sulfate is reaction raw materials, polycondensation reaction is carried out in oleum, obtain the aromatic heterocyclic polymer resin.Aromatic heterocyclic polymer resin intensity with higher, transparency, limit oxygen index and excellent UV resistant performance of the invention, excellent fireproof performance, heating conduction is excellent, excellent combination property.
Description
Technical field
The present invention relates to resin technology fields, and in particular to a kind of heteroaromatic of high intensity UV resistant high transparent and fire-retardant is poly-
Polymer resin and preparation method thereof and application in fiber or film.
Background technique
In heterocyclic compound cyclic organic compounds, constitute there are also other atomic time outside the atom carbon atom of ring, it is this kind of
Cyclic organic compounds are called heterocyclic compound, and non-carbon is known as hetero atom.The most common hetero atom is oxygen and sulphur, on heterocycle
Can have a hetero atom, can also there are two or more hetero atom, hetero atom can be a kind of atom, be also possible to two kinds
Different atoms.As cycloalkane, heterocycle can also be divided into alicyclic heterocyclic and heteroaromatic two major classes.In general, heteroaromatic
Ring system has a degree of stability and armaticity, and in general chemical reaction, ring is not easily broken.Part heteroaromatic can gather
Synthetic macromolecule resin has extensive potential using value due to its unique excellent performance.
Summary of the invention
In order to overcome shortcoming and defect existing in the prior art, the purpose of the present invention is to provide a kind of resistance to purples of high intensity
The aromatic heterocyclic polymer resin of outside line high transparent and fire-retardant, the aromatic heterocyclic polymer resin intensity with higher, transparency, the limit
Oxygen index (OI) and excellent UV resistant performance, excellent fireproof performance, heating conduction is excellent, can increase carbon element content, can use
It is graphitized heat sink material in preparation, also there is good dimensional stability, heat resistance, resistance to oxidation, electrical isolation, solvent resistance, spy
The performances such as different electric conductivity and electroluminescent, excellent combination property.
It is another object of the present invention to provide a kind of aromatic heterocyclic polymers of high-intensitive UV resistant high transparent and fire-retardant
The preparation method of resin, the preparation method step is simple, convenient operation and control, and quality is stablized, high production efficiency, production cost
It is low, it can large-scale industrial production.
Another purpose of the invention is that providing a kind of aromatic heterocyclic polymer of high-intensitive UV resistant high transparent and fire-retardant
The application of resin.
The purpose of the invention is achieved by the following technical solution: a kind of heteroaromatic of high intensity UV resistant high transparent and fire-retardant
Fluoropolymer resin, the aromatic heterocyclic polymer resin includes with Am-Bn-Cx-Dy-EzThe polymer chain of expression, wherein A, B, C, D
It is the repetitive unit for constituting polymer chain backbone with E, and repetitive unit A, B, C, D and E are arranged with random order, m, n, x, y
It is positive integer with z；
The structural formula of the repetitive unit A are as follows:
The structural formula of the repetitive unit B are as follows:
The structural formula of the repetitive unit C are as follows:Wherein, R1, R2, R3 and R4 are unsubstituted or take
The fluorine in generation, and at least one in R1, R2, R3 and R4 is the fluorine replaced；
The structural formula of the repetitive unit D are as follows:Wherein, R5, R6, R7 and R8 are unsubstituted or take
The bromine in generation, and at least one in R5, R6, R7 and R8 is the bromine replaced；
The structural formula of the repetitive unit E are as follows: Wherein, R is oxygen, sulphur or is not present.
Preferably, there is random copolymer configuration, alternate copolymer configuration or block copolymer configuration in the main chain,
That is, the polymerization methods of the aromatic heterocyclic polymer resin can be random copolymerization, alternating copolymerization or block copolymerization.
Preferably, the aromatic heterocyclic polymer resin is modified using inorganic filler.
Preferably, the inorganic filler is mica, carbon black, white carbon black, talcum powder, wollastonite, nitride, carbide, oxygen
At least one of compound, sulfate, carbonate, silicate, fluosilicate and phosphate.
Preferably, the nitride is silicon nitride and/or boron nitride；The carbide is silicon carbide and/or boron carbide；Institute
Stating oxide is at least one of calcium oxide, zinc oxide, magnesia, iron oxide, silica and titanium dioxide.
Preferably, the silica is nano silica, and the titanium dioxide is nano-titanium dioxide.
Preferably, the sulfate be calcium sulfate, magnesium sulfate, zinc sulfate, barium sulfate, ferric sulfate, in ferrous sulfate extremely
Few one kind；The silicate is at least one of sodium metasilicate, alumina silicate and magnesium silicate；The carbonate is calcium carbonate, carbonic acid
At least one of magnesium and zinc carbonate；The fluosilicate is at least one of prodan, potassium fluosilicate and magnesium fluosilicate；
The phosphate is at least one of calcium phosphate, calcium monohydrogen phosphate, magnesium phosphate and magnesium monohydrogen phosphate.
Preferably, the aromatic heterocyclic polymer resin is modified using modifying agent, and the modifying agent is glass microballoon, crystalline substance
At least one of the short fine, silicone of palpus, carbon fiber, glass fibre, Fanglun slurry cake, aramid fiber and polytetrafluoroethylene (PTFE).
Another object of the present invention is achieved through the following technical solutions: a kind of high intensity UV resistant high transparent and fire-retardant
The preparation method of aromatic heterocyclic polymer resin, in the absence of R is, with terephthalic acid (TPA) and/or phthalic acid, azobenzene-
It is 4,4 '-dioctyl phthalate and/or azobenzene -3,3 '-dioctyl phthalate, fluorine-containing terephthalic acid (TPA) and/or fluorine-containing phthalic acid, brominated to benzene
Dioctyl phthalate and/or be that reaction is former containing phthalate bromine, 4,4'- biphenyl dicarboxylic acid and/or 3,3'- biphenyl dicarboxylic acid, hydrazine sulfate
Material, polycondensation reaction is carried out in oleum, obtains the aromatic heterocyclic polymer resin.
Specifically, polymerized monomer (terephthalic acid (TPA) and/or phthalic acid, 4,4 '-dioctyl phthalate of azobenzene-and/or azo
Benzene -3,3 '-dioctyl phthalate, fluorine-containing terephthalic acid (TPA) and/or fluorine-containing phthalic acid contain bromo terephthalic acid and/or brominated adjacent benzene
Dioctyl phthalate, 4,4'- biphenyl dicarboxylic acid and/or 3,3'- biphenyl dicarboxylic acid), the molar ratio of hydrazine sulfate and oleum be 1:
(1.01-5.0): (5-15), wherein oleum molal quantity is with SO in oleum3Molal quantity meter.
Wherein, polymerized monomer (terephthalic acid (TPA) and/or phthalic acid), polymerized monomer (4,4 '-dioctyl phthalate of azobenzene-
And/or azobenzene -3,3 '-dioctyl phthalate), polymerized monomer (fluorine-containing terephthalic acid (TPA) and/or fluorine-containing phthalic acid), polymerized monomer
(containing bromo terephthalic acid and/or containing phthalate bromine) and polymerized monomer (4,4 '-biphenyl dicarboxylic acids and/or 3,3 '-biphenyl two
Formic acid) molar ratio be (0.01-0.99): (0.99-0.01): (0.99-0.01): (0.99-0.01): (0.99-0.01).For
Saving cost, it is preferred that polymerized monomer (terephthalic acid (TPA) and/or phthalic acid), polymerized monomer (azobenzene -4,4 '-two
Formic acid and/or azobenzene -3,3 '-dioctyl phthalate), polymerized monomer (fluorine-containing terephthalic acid (TPA) and/or fluorine-containing phthalic acid), polymerization
Monomer (containing bromo terephthalic acid and/or containing phthalate bromine) and polymerized monomer (4,4 '-biphenyl dicarboxylic acids and/or 3,3 '-connection
Phthalic acid) molar ratio be (0.60-0.96): (0.10-0.01): (0.10-0.01): (0.10-0.01): (0.10-
0.01)。
Further, the molar ratio of terephthalic acid (TPA) and phthalic acid is (0-1): (1-0), 4,4 '-diformazan of azobenzene-
The molar ratio of acid and 3,3 '-dioctyl phthalate of azobenzene-is (0-1): (1-0), fluorine-containing terephthalic acid (TPA) and fluorine-containing phthalic acid
Molar ratio is (0-1): (1-0), and molar ratio containing bromo terephthalic acid and containing phthalate bromine is (0-1): (1-0), 4,4 '-
The molar ratio of biphenyl dicarboxylic acid and 3,3 '-biphenyl dicarboxylic acids is (0-1): (1-0).
A kind of preparation method of the aromatic heterocyclic polymer resin of high intensity UV resistant high transparent and fire-retardant, when R is oxygen, with
It is terephthalic acid (TPA) and/or phthalic acid, azobenzene -4,4 '-dioctyl phthalate and/or azobenzene -3,3 '-dioctyl phthalate, fluorine-containing to benzene
Dioctyl phthalate and/or fluorine-containing phthalic acid contain bromo terephthalic acid and/or contain phthalate bromine, 4,4'- oxydibenzoic acid
And/or 3,3'- oxydibenzoic acid, hydrazine sulfate are reaction raw materials, and polycondensation reaction is carried out in oleum, it is miscellaneous to obtain the virtue
Cyclopolymer resin.
Specifically, polymerized monomer (terephthalic acid (TPA) and/or phthalic acid, 4,4 '-dioctyl phthalate of azobenzene-and/or azo
Benzene -3,3 '-dioctyl phthalate, fluorine-containing terephthalic acid (TPA) and/or fluorine-containing phthalic acid contain bromo terephthalic acid and/or brominated adjacent benzene
Dioctyl phthalate, 4,4'- oxydibenzoic acid and/or 3,3'- oxydibenzoic acid), the molar ratio of hydrazine sulfate and oleum be 1:
(1.01-5.0): (5-15), wherein oleum molal quantity is with SO in oleum3Molal quantity meter.
Wherein, polymerized monomer (terephthalic acid (TPA) and/or phthalic acid), polymerized monomer (4,4 '-dioctyl phthalate of azobenzene-
And/or azobenzene -3,3 '-dioctyl phthalate), polymerized monomer (fluorine-containing terephthalic acid (TPA) and/or fluorine-containing phthalic acid), polymerized monomer
(containing bromo terephthalic acid and/or containing phthalate bromine) and polymerized monomer (4,4 '-oxydibenzoic acids and/or 3,3 '-hexichol
Ether dioctyl phthalate) molar ratio be (0.01-0.99): (0.99-0.01): (0.99-0.01): (0.99-0.01): (0.99-
0.01).In order to save cost, it is preferred that polymerized monomer (terephthalic acid (TPA) and/or phthalic acid), polymerized monomer (azo
Benzene -4,4 '-dioctyl phthalate and/or azobenzene -3,3 '-dioctyl phthalate), polymerized monomer (fluorine-containing terephthalic acid (TPA) and/or fluorine-containing adjacent benzene two
Formic acid), polymerized monomer (containing bromo terephthalic acid and/or contain phthalate bromine) with polymerized monomer (4,4 '-oxydibenzoic acids
And/or 3,3 '-oxydibenzoic acids) molar ratio be (0.60-0.96): (0.10-0.01): (0.10-0.01): (0.10-
0.01): (0.10-0.01).
Further, the molar ratio of terephthalic acid (TPA) and phthalic acid is (0-1): (1-0), 4,4 '-diformazan of azobenzene-
The molar ratio of acid and 3,3 '-dioctyl phthalate of azobenzene-is (0-1): (1-0), fluorine-containing terephthalic acid (TPA) and fluorine-containing phthalic acid
Molar ratio is (0-1): (1-0), and molar ratio containing bromo terephthalic acid and containing phthalate bromine is (0-1): (1-0), 4,4 '-
The molar ratio of oxydibenzoic acid and 3,3 '-oxydibenzoic acids is (0-1): (1-0).
A kind of preparation method of the aromatic heterocyclic polymer resin of high intensity UV resistant high transparent and fire-retardant, when R is sulphur, with
It is terephthalic acid (TPA) and/or phthalic acid, azobenzene -4,4 '-dioctyl phthalate and/or azobenzene -3,3 '-dioctyl phthalate, fluorine-containing to benzene
Dioctyl phthalate and/or fluorine-containing phthalic acid contain bromo terephthalic acid and/or contain phthalate bromine, 4,4'- diphenyl sulfide diformazan
Acid and/or 3,3'- diphenyl sulfide dioctyl phthalate, hydrazine sulfate are reaction raw materials, and polycondensation reaction is carried out in oleum, are obtained described
Aromatic heterocyclic polymer resin.
Specifically, polymerized monomer (terephthalic acid (TPA) and/or phthalic acid, 4,4 '-dioctyl phthalate of azobenzene-and/or azo
Benzene -3,3 '-dioctyl phthalate, fluorine-containing terephthalic acid (TPA) and/or fluorine-containing phthalic acid contain bromo terephthalic acid and/or brominated adjacent benzene
Dioctyl phthalate, 4,4'- diphenyl sulfide dioctyl phthalate and/or 3,3'- diphenyl sulfide dioctyl phthalate), the molar ratio of hydrazine sulfate and oleum
For 1:(1.01-5.0): (5-15), wherein oleum molal quantity is with SO in oleum3Molal quantity meter.
Wherein, polymerized monomer (terephthalic acid (TPA) and/or phthalic acid), polymerized monomer (4,4 '-dioctyl phthalate of azobenzene-
And/or azobenzene -3,3 '-dioctyl phthalate), polymerized monomer (fluorine-containing terephthalic acid (TPA) and/or fluorine-containing phthalic acid), polymerized monomer
(containing bromo terephthalic acid and/or containing phthalate bromine) and polymerized monomer (4,4 '-diphenyl sulfide dioctyl phthalate and/or 3,3 '-two
Diphenyl sulfide dioctyl phthalate) molar ratio be (0.01-0.99): (0.99-0.01): (0.99-0.01): (0.99-0.01): (0.99-
0.01).In order to save cost, it is preferred that polymerized monomer (terephthalic acid (TPA) and/or phthalic acid), polymerized monomer (azo
Benzene -4,4 '-dioctyl phthalate and/or azobenzene -3,3 '-dioctyl phthalate), polymerized monomer (fluorine-containing terephthalic acid (TPA) and/or fluorine-containing adjacent benzene two
Formic acid), polymerized monomer (containing bromo terephthalic acid and/or contain phthalate bromine) with polymerized monomer (4,4 '-diphenyl sulfide diformazans
Acid and/or 3,3 '-diphenyl sulfide dioctyl phthalate) molar ratio be (0.60-0.96): (0.10-0.01): (0.10-0.01):
(0.10-0.01): (0.10-0.01).
Further, the molar ratio of terephthalic acid (TPA) and phthalic acid is (0-1): (1-0), 4,4 '-diformazan of azobenzene-
The molar ratio of acid and 3,3 '-dioctyl phthalate of azobenzene-is (0-1): (1-0), fluorine-containing terephthalic acid (TPA) and fluorine-containing phthalic acid
Molar ratio is (0-1): (1-0), and molar ratio containing bromo terephthalic acid and containing phthalate bromine is (0-1): (1-0), 4,4 '-
The molar ratio of diphenyl sulfide dioctyl phthalate and 3,3 '-diphenyl sulfide dioctyl phthalate is (0-1): (1-0).
Applicants have found that when using terephthalic acid (TPA) as monomer polymerization, although obtained aromatic heterocyclic polymer resin
Intensity is higher, but shrinking percentage is slightly bigger than normal, and when phthalic acid is added polymerizeing together as monomer, obtained heteroaromatic polymerization
On the basis of keeping higher-strength, shrinking percentage can be improved object tree.
An also purpose of the invention is achieved through the following technical solutions: a kind of high intensity UV resistant high transparent and fire-retardant
The application of aromatic heterocyclic polymer resin, the aromatic heterocyclic polymer resin are applied to fiber or film.
Preferably, the film is applied to high temperature gummed tape, FPC substrate, COF substrate, FCCL substrate, carbonization film base material, stone
Inkization heat dissipation film base material, high temperature dwell cuticula, LED light bar, OLED Flexible Displays substrate, conductive film base material, high-temperature insulation film or hand
Cover plate.
The beneficial effects of the present invention are: aromatic heterocyclic polymer resin intensity with higher of the invention, transparency, pole
Limited oxygen index and excellent UV resistant performance, excellent fireproof performance, heating conduction is excellent, can increase carbon element content, can
Be used to prepare graphitization heat sink material, also have good dimensional stability, heat resistance, resistance to oxidation, electrical isolation, solvent resistance,
The performances such as special electric conductivity and electroluminescent, excellent combination property.
Preparation method step of the invention is simple, convenient operation and control, and quality is stablized, and high production efficiency, production cost is low,
It can large-scale industrial production.
Application of the aromatic heterocyclic polymer resin of high-intensitive UV resistant high transparent and fire-retardant of the invention in fiber or film.
Specific embodiment
For the ease of the understanding of those skilled in the art, below with reference to embodiment, the present invention is further illustrated, real
The content that the mode of applying refers to not is limitation of the invention.
Embodiment 1
A kind of aromatic heterocyclic polymer resin of high intensity UV resistant high transparent and fire-retardant, the aromatic heterocyclic polymer resin packet
It includes with Am-Bn-Cx-Dy-EzThe polymer chain of expression, wherein A, B, C, D and E are the repetitive unit for constituting polymer chain backbone,
And repetitive unit A, B, C, D and E are arranged with random order, m, n, x, y and z are positive integer；
The structural formula of the repetitive unit A are as follows:
The structural formula of the repetitive unit B are as follows:
The structural formula of the repetitive unit C are as follows:Wherein, R1, R2, R3 and R4 are not take
Generation or the fluorine replaced, and at least one in R1, R2, R3 and R4 is the fluorine replaced；
The structural formula of the repetitive unit D are as follows:Wherein, R5, R6, R7 and R8 are not take
Generation or the bromine replaced, and at least one in R5, R6, R7 and R8 is the bromine replaced；
The structural formula of the repetitive unit E are as follows:Wherein, R be oxygen,
Sulphur is not present.
The aromatic heterocyclic polymer resin is modified using inorganic filler.
The inorganic filler is in mica, carbon black, white carbon black, talcum powder, wollastonite, nitride, carbide and oxide
At least one.
The nitride is silicon nitride and/or boron nitride；The carbide is silicon carbide and/or boron carbide；The oxidation
Object is at least one of calcium oxide, zinc oxide, magnesia, iron oxide, silica and titanium dioxide.
The silica is nano silica, and the titanium dioxide is nano-titanium dioxide.
A kind of preparation method of the aromatic heterocyclic polymer resin of high intensity UV resistant high transparent and fire-retardant, when R be there is no
When, with terephthalic acid (TPA), 4,4 '-dioctyl phthalate of azobenzene-, fluorine-containing terephthalic acid (TPA), contain bromo terephthalic acid, 4,4'- biphenyl two
Formic acid, hydrazine sulfate are reaction raw materials, and polycondensation reaction is carried out in oleum, obtains the aromatic heterocyclic polymer resin.Polymerization
(terephthalic acid (TPA), fluorine-containing terephthalic acid (TPA), contains bromo terephthalic acid, 4,4'- biphenyl two at azobenzene -4,4 '-dioctyl phthalate to monomer
Formic acid), the molar ratio of hydrazine sulfate and oleum be 1:(1.01,2.0,3.0,4.0 or 5.0): (5,8,10,12 or 15),
Middle oleum molal quantity is with SO in oleum3Molal quantity meter.
Wherein, polymerized monomer (terephthalic acid (TPA)), polymerized monomer (4,4 '-dioctyl phthalate of azobenzene -), polymerized monomer are (fluorine-containing
Terephthalic acid (TPA)), the molar ratio of polymerized monomer (contain bromo terephthalic acid) and polymerized monomer (4,4 '-biphenyl dicarboxylic acid) be
(0.01,0.25,0.50,0.75 or 0.99): (0.99,0.75,0.50,0.25 or 0.01): (0.99,0.75,0.50,0.25
Or 0.01): (0.99,0.75,0.50,0.25 or 0.01): (0.99,0.75,0.50,0.25 or 0.01).
When R is oxygen, with terephthalic acid (TPA), 4,4 '-dioctyl phthalate of azobenzene-, fluorine-containing terephthalic acid (TPA), brominated terephthaldehyde
Acid, 4,4'- oxydibenzoic acid, hydrazine sulfate are reaction raw materials, and polycondensation reaction is carried out in oleum, obtains the heteroaromatic
Fluoropolymer resin.Polymerized monomer (terephthalic acid (TPA), azobenzene -4,4 '-dioctyl phthalate, fluorine-containing terephthalic acid (TPA), brominated terephthaldehyde
Acid, 4,4'- oxydibenzoic acid), the molar ratio of hydrazine sulfate and oleum be 1:(1.01,2.0,3.0,4.0 or 5.0): (5,
8,10,12 or 15), wherein oleum molal quantity is with SO in oleum3Molal quantity meter.
Wherein, polymerized monomer (terephthalic acid (TPA)), polymerized monomer (4,4 '-dioctyl phthalate of azobenzene -), polymerized monomer are (fluorine-containing
Terephthalic acid (TPA)), the molar ratio of polymerized monomer (contain bromo terephthalic acid) and polymerized monomer (4,4 '-oxydibenzoic acid) be
(0.01,0.25,0.50,0.75 or 0.99): (0.99,0.75,0.50,0.25 or 0.01): (0.99,0.75,0.50,0.25
Or 0.01): (0.99,0.75,0.50,0.25 or 0.01): (0.99,0.75,0.50,0.25 or 0.01).
When R is sulphur, with terephthalic acid (TPA), 4,4 '-dioctyl phthalate of azobenzene-, fluorine-containing terephthalic acid (TPA), brominated terephthaldehyde
Acid, 4,4'- diphenyl sulfide dioctyl phthalate, hydrazine sulfate are reaction raw materials, and polycondensation reaction is carried out in oleum, it is miscellaneous to obtain the virtue
Cyclopolymer resin.Polymerized monomer is (terephthalic acid (TPA), azobenzene -4,4 '-dioctyl phthalate, fluorine-containing terephthalic acid (TPA), brominated to benzene two
Formic acid, 4,4'- diphenyl sulfide dioctyl phthalate), the molar ratio of hydrazine sulfate and oleum be 1:(1.01,2.0,3.0,4.0 or
5.0): (5,8,10,12 or 15), wherein oleum molal quantity is with SO in oleum3Molal quantity meter.
Wherein, polymerized monomer (terephthalic acid (TPA)), polymerized monomer (4,4 '-dioctyl phthalate of azobenzene -), polymerized monomer are (fluorine-containing
Terephthalic acid (TPA)), the molar ratio of polymerized monomer (contain bromo terephthalic acid) and polymerized monomer (4,4 '-diphenyl sulfide dioctyl phthalate) be
(0.01,0.25,0.50,0.75 or 0.99): (0.99,0.75,0.50,0.25 or 0.01): (0.99,0.75,0.50,0.25
Or 0.01): (0.99,0.75,0.50,0.25 or 0.01): (0.99,0.75,0.50,0.25 or 0.01).
Embodiment 2
A kind of aromatic heterocyclic polymer resin of high intensity UV resistant high transparent and fire-retardant, the aromatic heterocyclic polymer resin packet
It includes with Am-Bn-Cx-Dy-EzThe polymer chain of expression, wherein A, B, C, D and E are the repetitive unit for constituting polymer chain backbone,
And repetitive unit A, B, C, D and E are arranged with random order, m, n, x, y and z are positive integer；
The structural formula of the repetitive unit A are as follows:
The structural formula of the repetitive unit B are as follows:
The structural formula of the repetitive unit C are as follows:Wherein, R1, R2, R3 and R4 are not take
Generation or the fluorine replaced, and at least one in R1, R2, R3 and R4 is the fluorine replaced；
The structural formula of the repetitive unit D are as follows:Wherein, R5, R6, R7 and R8 are not take
Generation or the bromine replaced, and at least one in R5, R6, R7 and R8 is the bromine replaced；
The structural formula of the repetitive unit E are as follows:Wherein, R is oxygen, sulphur
Or it is not present.
The aromatic heterocyclic polymer resin is modified using inorganic filler.
The inorganic filler is at least one of sulfate, carbonate, silicate, fluosilicate and phosphate.
The sulfate is at least one of calcium sulfate, magnesium sulfate, zinc sulfate, barium sulfate, ferric sulfate, ferrous sulfate；
The silicate is at least one of sodium metasilicate, alumina silicate and magnesium silicate；The carbonate is calcium carbonate, magnesium carbonate and carbonic acid
At least one of zinc；The fluosilicate is at least one of prodan, potassium fluosilicate and magnesium fluosilicate；The phosphoric acid
Salt is at least one of calcium phosphate, calcium monohydrogen phosphate, magnesium phosphate and magnesium monohydrogen phosphate.
A kind of preparation method of the aromatic heterocyclic polymer resin of high intensity UV resistant high transparent and fire-retardant, when R be there is no
When, with phthalic acid, 3,3 '-dioctyl phthalate of azobenzene-, fluorine-containing phthalic acid, contain phthalate bromine, 3,3'- biphenyl two
Formic acid, hydrazine sulfate are reaction raw materials, and polycondensation reaction is carried out in oleum, obtains the aromatic heterocyclic polymer resin.Polymerization
(phthalic acid, fluorine-containing phthalic acid, contains phthalate bromine, 3,3'- biphenyl two at azobenzene -3,3 '-dioctyl phthalate to monomer
Formic acid), the molar ratio of hydrazine sulfate and oleum be 1:(1.01,2.0,3.0,4.0 or 5.0): (5,8,10,12 or 15),
Middle oleum molal quantity is with SO in oleum3Molal quantity meter.
Wherein, polymerized monomer (phthalic acid), polymerized monomer (3,3 '-dioctyl phthalate of azobenzene -), polymerized monomer are (fluorine-containing
Phthalic acid), the molar ratio of polymerized monomer (contain phthalate bromine) and polymerized monomer (3,3 '-biphenyl dicarboxylic acid) be
(0.01,0.25,0.50,0.75 or 0.99): (0.99,0.75,0.50,0.25 or 0.01): (0.99,0.75,0.50,0.25
Or 0.01): (0.99,0.75,0.50,0.25 or 0.01): (0.99,0.75,0.50,0.25 or 0.01).
When R is oxygen, with phthalic acid, 3,3 '-dioctyl phthalate of azobenzene-, fluorine-containing phthalic acid, brominated O-phthalic
Acid, 3,3'- oxydibenzoic acid, hydrazine sulfate are reaction raw materials, and polycondensation reaction is carried out in oleum, obtains the heteroaromatic
Fluoropolymer resin.Polymerized monomer (phthalic acid, azobenzene -3,3 '-dioctyl phthalate, fluorine-containing phthalic acid, brominated O-phthalic
Acid, 3,3'- oxydibenzoic acid), the molar ratio of hydrazine sulfate and oleum be 1:(1.01,2.0,3.0,4.0 or 5.0): (5,
8,10,12 or 15), wherein oleum molal quantity is with SO in oleum3Molal quantity meter.
Wherein, polymerized monomer (phthalic acid), polymerized monomer (3,3 '-dioctyl phthalate of azobenzene -), polymerized monomer are (fluorine-containing
Phthalic acid), the molar ratio of polymerized monomer (contain phthalate bromine) and polymerized monomer (3,3 '-oxydibenzoic acid) be
(0.01,0.25,0.50,0.75 or 0.99): (0.99,0.75,0.50,0.25 or 0.01): (0.99,0.75,0.50,0.25
Or 0.01): (0.99,0.75,0.50,0.25 or 0.01): (0.99,0.75,0.50,0.25 or 0.01).
When R is sulphur, with phthalic acid, 3,3 '-dioctyl phthalate of azobenzene-, fluorine-containing phthalic acid, brominated O-phthalic
Acid, 3,3'- diphenyl sulfide dioctyl phthalate, hydrazine sulfate are reaction raw materials, and polycondensation reaction is carried out in oleum, it is miscellaneous to obtain the virtue
Cyclopolymer resin.Polymerized monomer (phthalic acid, azobenzene -3,3 '-dioctyl phthalate, fluorine-containing phthalic acid, brominated adjacent benzene two
Formic acid, 3,3'- diphenyl sulfide dioctyl phthalate), the molar ratio of hydrazine sulfate and oleum be 1:(1.01,2.0,3.0,4.0 or
5.0): (5,8,10,12 or 15), wherein oleum molal quantity is with SO in oleum3Molal quantity meter.
Wherein, polymerized monomer (phthalic acid), polymerized monomer (3,3 '-dioctyl phthalate of azobenzene -), polymerized monomer are (fluorine-containing
Phthalic acid), the molar ratio of polymerized monomer (contain phthalate bromine) and polymerized monomer (3,3 '-diphenyl sulfide dioctyl phthalate) be
(0.01,0.25,0.50,0.75 or 0.99): (0.99,0.75,0.50,0.25 or 0.01): (0.99,0.75,0.50,0.25
Or 0.01): (0.99,0.75,0.50,0.25 or 0.01): (0.99,0.75,0.50,0.25 or 0.01).
Embodiment 3
A kind of aromatic heterocyclic polymer resin of high intensity UV resistant high transparent and fire-retardant, the aromatic heterocyclic polymer resin packet
It includes with Am-Bn-Cx-Dy-EzThe polymer chain of expression, wherein A, B, C, D and E are the repetitive unit for constituting polymer chain backbone,
And repetitive unit A, B, C, D and E are arranged with random order, m, n, x, y and z are positive integer；
The structural formula of the repetitive unit A are as follows:
The structural formula of the repetitive unit B are as follows:
The structural formula of the repetitive unit C are as follows:
Wherein, R1, R2, R3 and R4 are unsubstituted or substituted fluorine, and at least one in R1, R2, R3 and R4 is the fluorine replaced；
The structural formula of the repetitive unit D are as follows:
Wherein, R5, R6, R7 and R8 are unsubstituted or substituted bromine, and at least one in R5, R6, R7 and R8 is the bromine replaced；
The structural formula of the repetitive unit E are as follows: Wherein, R is oxygen, sulphur or is not present.
The aromatic heterocyclic polymer resin is modified using modifying agent, and the modifying agent is glass microballoon, whisker, carbon fiber
At least one of the short fine, silicone of dimension, glass fibre, Fanglun slurry cake, aramid fiber and polytetrafluoroethylene (PTFE).
A kind of preparation method of the aromatic heterocyclic polymer resin of high intensity UV resistant high transparent and fire-retardant, when R be there is no
When, with 3,3 '-dioctyl phthalate of terephthalic acid (TPA) and phthalic acid, 4,4 '-dioctyl phthalate of azobenzene-and azobenzene-, fluorine-containing to benzene two
Formic acid and fluorine-containing phthalic acid join containing bromo terephthalic acid and containing phthalate bromine, 4,4'- biphenyl dicarboxylic acid and 3,3'-
Phthalic acid, hydrazine sulfate are reaction raw materials, and polycondensation reaction is carried out in oleum, obtains the aromatic heterocyclic polymer resin.
Polymerized monomer is (terephthalic acid (TPA) and phthalic acid, azobenzene -4,4 '-dioctyl phthalate and azobenzene -3,3 '-dioctyl phthalate, fluorine-containing right
Phthalic acid and fluorine-containing phthalic acid contain bromo terephthalic acid and contain phthalate bromine, 4,4'- biphenyl dicarboxylic acid and 3,
3'- biphenyl dicarboxylic acid), the molar ratio of hydrazine sulfate and oleum be 1:(1.01,2.0,3.0,4.0 or 5.0): (5,8,10,12
Or 15), wherein oleum molal quantity with SO in oleum3Molal quantity meter.
Wherein, polymerized monomer (terephthalic acid (TPA) and phthalic acid), polymerized monomer (4,4 '-dioctyl phthalate of azobenzene-and idol
Pyridine -3,3 '-dioctyl phthalate), polymerized monomer (fluorine-containing terephthalic acid (TPA) and fluorine-containing phthalic acid), polymerized monomer it is (brominated to benzene
Dioctyl phthalate and contain phthalate bromine) be with the molar ratio of polymerized monomer (4,4 '-biphenyl dicarboxylic acids and 3,3 '-biphenyl dicarboxylic acids)
(0.01,0.25,0.50,0.75 or 0.99): (0.99,0.75,0.50,0.25 or 0.01): (0.99,0.75,0.50,0.25
Or 0.01): (0.99,0.75,0.50,0.25 or 0.01): (0.99,0.75,0.50,0.25 or 0.01).
The molar ratio of terephthalic acid (TPA) and phthalic acid is (0.01,0.25,0.50,0.75 or 0.99): (0.99,
0.75,0.50,0.25 or 0.01), the molar ratio of 3,3 '-dioctyl phthalate of 4,4 '-dioctyl phthalate of azobenzene-and azobenzene-be (0.01,
0.25,0.50,0.75 or 0.99): (0.99,0.75,0.50,0.25 or 0.01), fluorine-containing terephthalic acid (TPA) and fluorine-containing adjacent benzene two
The molar ratio of formic acid is (0.01,0.25,0.50,0.75 or 0.99): (0.99,0.75,0.50,0.25 or 0.01), brominated right
Phthalic acid and molar ratio containing phthalate bromine are (0.01,0.25,0.50,0.75 or 0.99): (0.99,0.75,
0.50,0.25 or 0.01), 4,4 '-biphenyl dicarboxylic acids and 3, the molar ratio of 3 '-biphenyl dicarboxylic acids be (0.01,0.25,0.50,
0.75 or 0.99): (0.99,0.75,0.50,0.25 or 0.01).
When R is oxygen, with terephthalic acid (TPA) and phthalic acid, 4,4 '-dioctyl phthalate of azobenzene-and azobenzene -3,3 '-two
Formic acid, fluorine-containing terephthalic acid (TPA) and fluorine-containing phthalic acid contain bromo terephthalic acid and contain phthalate bromine, 4,4'- hexichol
Ether dioctyl phthalate and 3,3'- oxydibenzoic acid, hydrazine sulfate are reaction raw materials, and polycondensation reaction is carried out in oleum, obtains institute
State aromatic heterocyclic polymer resin.Polymerized monomer (terephthalic acid (TPA) and phthalic acid, azobenzene -4,4 '-dioctyl phthalate and azo
Benzene -3,3 '-dioctyl phthalate, fluorine-containing terephthalic acid (TPA) and fluorine-containing phthalic acid, containing bromo terephthalic acid and containing phthalate bromine,
4,4'- oxydibenzoic acid and 3,3'- oxydibenzoic acid), the molar ratio of hydrazine sulfate and oleum be 1:(1.01,2.0,
3.0,4.0 or 5.0): (5,8,10,12 or 15), wherein oleum molal quantity is with SO in oleum3Molal quantity meter.
Wherein, polymerized monomer (terephthalic acid (TPA) and phthalic acid), polymerized monomer (4,4 '-dioctyl phthalate of azobenzene-and idol
Pyridine -3,3 '-dioctyl phthalate), polymerized monomer (fluorine-containing terephthalic acid (TPA) and fluorine-containing phthalic acid), polymerized monomer it is (brominated to benzene
Dioctyl phthalate and contain phthalate bromine) with mole of polymerized monomer (4,4 '-oxydibenzoic acids and 3,3 '-oxydibenzoic acids)
Than for (0.01,0.25,0.50,0.75 or 0.99): (0.99,0.75,0.50,0.25 or 0.01): (0.99,0.75,0.50,
0.25 or 0.01): (0.99,0.75,0.50,0.25 or 0.01): (0.99,0.75,0.50,0.25 or 0.01).
The molar ratio of terephthalic acid (TPA) and phthalic acid is (0.01,0.25,0.50,0.75 or 0.99): (0.99,
0.75,0.50,0.25 or 0.01), the molar ratio of 3,3 '-dioctyl phthalate of 4,4 '-dioctyl phthalate of azobenzene-and azobenzene-be (0.01,
0.25,0.50,0.75 or 0.99): (0.99,0.75,0.50,0.25 or 0.01), fluorine-containing terephthalic acid (TPA) and fluorine-containing adjacent benzene two
The molar ratio of formic acid is (0.01,0.25,0.50,0.75 or 0.99): (0.99,0.75,0.50,0.25 or 0.01), brominated right
Phthalic acid and molar ratio containing phthalate bromine are (0.01,0.25,0.50,0.75 or 0.99): (0.99,0.75,
0.50,0.25 or 0.01), 4,4 '-oxydibenzoic acids and 3, the molar ratio of 3 '-oxydibenzoic acids be (0.01,0.25,
0.50,0.75 or 0.99): (0.99,0.75,0.50,0.25 or 0.01).
When R is sulphur, with terephthalic acid (TPA) and phthalic acid, 4,4 '-dioctyl phthalate of azobenzene-and azobenzene -3,3 '-two
Formic acid, fluorine-containing terephthalic acid (TPA) and fluorine-containing phthalic acid contain bromo terephthalic acid and contain phthalate bromine, 4,4'- hexichol
Thioether dioctyl phthalate and 3,3'- diphenyl sulfide dioctyl phthalate, hydrazine sulfate are reaction raw materials, and polycondensation reaction is carried out in oleum, is obtained
To the aromatic heterocyclic polymer resin.Polymerized monomer (terephthalic acid (TPA) and phthalic acid, azobenzene -4,4 '-dioctyl phthalate and idol
Pyridine -3,3 '-dioctyl phthalate, fluorine-containing terephthalic acid (TPA) and fluorine-containing phthalic acid contain bromo terephthalic acid and brominated O-phthalic
Acid, 4,4'- diphenyl sulfide dioctyl phthalate and 3,3'- diphenyl sulfide dioctyl phthalate), the molar ratio of hydrazine sulfate and oleum be 1:
(1.01,2.0,3.0,4.0 or 5.0): (5,8,10,12 or 15), wherein oleum molal quantity is with SO in oleum3Mole
Number meter.
Wherein, polymerized monomer (terephthalic acid (TPA) and phthalic acid), polymerized monomer (4,4 '-dioctyl phthalate of azobenzene-and idol
Pyridine -3,3 '-dioctyl phthalate), polymerized monomer (fluorine-containing terephthalic acid (TPA) and fluorine-containing phthalic acid), polymerized monomer it is (brominated to benzene
Dioctyl phthalate and contain phthalate bromine) with polymerized monomer (4,4 '-diphenyl sulfide dioctyl phthalate and 3,3 '-diphenyl sulfide dioctyl phthalate)
Molar ratio be (0.01,0.25,0.50,0.75 or 0.99): (0.99,0.75,0.50,0.25 or 0.01): (0.99,0.75,
0.50,0.25 or 0.01): (0.99,0.75,0.50,0.25 or 0.01): (0.99,0.75,0.50,0.25 or 0.01).
The molar ratio of terephthalic acid (TPA) and phthalic acid is (0.01,0.25,0.50,0.75 or 0.99): (0.99,
0.75,0.50,0.25 or 0.01), the molar ratio of 3,3 '-dioctyl phthalate of 4,4 '-dioctyl phthalate of azobenzene-and azobenzene-be (0.01,
0.25,0.50,0.75 or 0.99): (0.99,0.75,0.50,0.25 or 0.01), fluorine-containing terephthalic acid (TPA) and fluorine-containing adjacent benzene two
The molar ratio of formic acid is (0.01,0.25,0.50,0.75 or 0.99): (0.99,0.75,0.50,0.25 or 0.01), brominated right
Phthalic acid and molar ratio containing phthalate bromine are (0.01,0.25,0.50,0.75 or 0.99): (0.99,0.75,
0.50,0.25 or 0.01), 4,4 '-diphenyl sulfide dioctyl phthalate and 3, the molar ratio of 3 '-diphenyl sulfide dioctyl phthalate be (0.01,
0.25,0.50,0.75 or 0.99): (0.99,0.75,0.50,0.25 or 0.01).
Embodiment 4
A kind of application of the aromatic heterocyclic polymer resin of high intensity UV resistant high transparent and fire-retardant, the aromatic heterocyclic polymer
Resin is applied to fiber.
Embodiment 5
A kind of application of the aromatic heterocyclic polymer resin of high intensity UV resistant high transparent and fire-retardant, the aromatic heterocyclic polymer
Resin is applied to film.
The film is applied to high temperature gummed tape, FPC substrate, COF substrate, FCCL substrate, carbonization film base material, graphitization heat dissipation
Film base material, high temperature dwell cuticula, LED light bar, OLED Flexible Displays substrate, conductive film base material, high-temperature insulation film or hand-set lid.
After tested, it can achieve using film transverse tensile strength made from aromatic heterocyclic polymer resin of the invention
85.6-89.7MPa, longitudinal tensile strength can achieve 143.5-151.3MPa, and ultraviolet light and aging test can achieve 1450-
1650h, transparency can achieve 84.5-88.6%, and limit oxygen index can achieve 37.8-41.5%, and thermal decomposition temperature can be with
Reach 453-462 DEG C, vertical thermal conductivity can achieve 32.0-51.8W/m-K, and horizontal thermal conductivity factor can achieve 1040-
1230W/m-K, intensity, transparency, limit oxygen index and excellent UV resistant performance with higher, excellent fireproof performance,
Heat-resisting and heating conduction is excellent, can increase carbon element content, can be used for preparing graphitization heat sink material.
Above-described embodiment is the preferable implementation of the present invention, and in addition to this, the present invention can be realized with other way,
Do not depart under the premise of present inventive concept it is any obviously replace it is within the scope of the present invention.
Claims (10)
1. a kind of aromatic heterocyclic polymer resin of high intensity UV resistant high transparent and fire-retardant, it is characterised in that: the heteroaromatic is poly-
Polymer resin includes with Am-Bn-Cx-Dy-EzThe polymer chain of expression, wherein A, B, C, D and E are composition polymer chain backbone
Repetitive unit, and repetitive unit A, B, C, D and E are arranged with random order, and m, n, x, y and z are positive integer；
The structural formula of the repetitive unit A are as follows:
The structural formula of the repetitive unit B are as follows:
The structural formula of the repetitive unit C are as follows:
Wherein, R1, R2, R3 and R4 are unsubstituted or substituted fluorine, and at least one in R1, R2, R3 and R4 is the fluorine replaced；
The structural formula of the repetitive unit D are as follows:
Wherein, R5, R6, R7 and R8 are unsubstituted or substituted bromine, and at least one in R5, R6, R7 and R8 is the bromine replaced；
The structural formula of the repetitive unit E are as follows: Wherein, R is oxygen, sulphur or is not present.
2. a kind of aromatic heterocyclic polymer resin of high-intensitive UV resistant high transparent and fire-retardant according to claim 1, special
Sign is: the aromatic heterocyclic polymer resin is modified using inorganic filler.
3. a kind of aromatic heterocyclic polymer resin of high-intensitive UV resistant high transparent and fire-retardant according to claim 2, special
Sign is: the inorganic filler is mica, carbon black, white carbon black, talcum powder, wollastonite, nitride, carbide, oxide, sulfuric acid
At least one of salt, carbonate, silicate, fluosilicate and phosphate.
4. a kind of aromatic heterocyclic polymer resin of high-intensitive UV resistant high transparent and fire-retardant according to claim 3, special
Sign is: the nitride is silicon nitride and/or boron nitride；The carbide is silicon carbide and/or boron carbide；The oxide
For at least one of calcium oxide, zinc oxide, magnesia, iron oxide, silica and titanium dioxide.
5. a kind of aromatic heterocyclic polymer resin of high-intensitive UV resistant high transparent and fire-retardant according to claim 4, special
Sign is: the silica is nano silica, and the titanium dioxide is nano-titanium dioxide.
6. a kind of aromatic heterocyclic polymer resin of high-intensitive UV resistant high transparent and fire-retardant according to claim 3, special
Sign is: the sulfate is at least one of calcium sulfate, magnesium sulfate, zinc sulfate, barium sulfate, ferric sulfate, ferrous sulfate；Institute
Stating silicate is at least one of sodium metasilicate, alumina silicate and magnesium silicate；The carbonate is calcium carbonate, magnesium carbonate and zinc carbonate
At least one of；The fluosilicate is at least one of prodan, potassium fluosilicate and magnesium fluosilicate；The phosphate
For at least one of calcium phosphate, calcium monohydrogen phosphate, magnesium phosphate and magnesium monohydrogen phosphate.
7. a kind of aromatic heterocyclic polymer resin of high-intensitive UV resistant high transparent and fire-retardant according to claim 1, special
Sign is: the aromatic heterocyclic polymer resin is modified using modifying agent, and the modifying agent is glass microballoon, whisker, carbon fiber
At least one of the short fine, silicone of dimension, glass fibre, Fanglun slurry cake, aramid fiber and polytetrafluoroethylene (PTFE).
8. such as a kind of described in any item aromatic heterocyclic polymer resins of high-intensitive UV resistant high transparent and fire-retardant of claim 1-7
Preparation method, it is characterised in that: in the absence of R is, with terephthalic acid (TPA) and/or phthalic acid, azobenzene -4,4 ' -
Dioctyl phthalate and/or azobenzene -3,3 '-dioctyl phthalate, fluorine-containing terephthalic acid (TPA) and/or fluorine-containing phthalic acid, brominated terephthaldehyde
Acid and/or contain phthalate bromine, 4,4'- biphenyl dicarboxylic acid and/or 3,3'- biphenyl dicarboxylic acid, hydrazine sulfate be reaction raw materials,
Polycondensation reaction is carried out in oleum, obtains the aromatic heterocyclic polymer resin；
When R is oxygen, with terephthalic acid (TPA) and/or phthalic acid, 4,4 '-dioctyl phthalate of azobenzene-and/or azobenzene -3,3 ' -
Dioctyl phthalate, fluorine-containing terephthalic acid (TPA) and/or fluorine-containing phthalic acid contain bromo terephthalic acid and/or contain phthalate bromine, 4,
4'- oxydibenzoic acid and/or 3,3'- oxydibenzoic acid, hydrazine sulfate are reaction raw materials, and it is anti-that polycondensation is carried out in oleum
It answers, obtains the aromatic heterocyclic polymer resin；
When R is sulphur, with terephthalic acid (TPA) and/or phthalic acid, 4,4 '-dioctyl phthalate of azobenzene-and/or azobenzene -3,3 ' -
Dioctyl phthalate, fluorine-containing terephthalic acid (TPA) and/or fluorine-containing phthalic acid contain bromo terephthalic acid and/or contain phthalate bromine, 4,
4'- diphenyl sulfide dioctyl phthalate and/or 3,3'- diphenyl sulfide dioctyl phthalate, hydrazine sulfate are reaction raw materials, are contracted in oleum
Poly- reaction, obtains the aromatic heterocyclic polymer resin.
9. such as a kind of described in any item aromatic heterocyclic polymer resins of high-intensitive UV resistant high transparent and fire-retardant of claim 1-7
Application, it is characterised in that: the aromatic heterocyclic polymer resin be applied to fiber or film.
10. a kind of aromatic heterocyclic polymer resin of high-intensitive UV resistant high transparent and fire-retardant according to claim 9 is answered
With, it is characterised in that: the film is applied to high temperature gummed tape, FPC substrate, COF substrate, FCCL substrate, carbonization film base material, graphite
Change heat dissipation film base material, high temperature dwell cuticula, LED light bar, OLED Flexible Displays substrate, conductive film base material, high-temperature insulation film or mobile phone
Cover board.
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| CN104817687A (en) * | 2015-05-22 | 2015-08-05 | 江苏宝德新材料有限公司 | High-purity aromatic polyoxadiazole solution and fiber prepared from high-purity aromatic polyoxadiazole solution |
| CN104831400A (en) * | 2015-05-22 | 2015-08-12 | 江苏宝德新材料有限公司 | Low-viscosity aromatic polyoxdiazole solution and fiber prepared from same |
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2018
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| WO2007133409A2 (en) * | 2006-05-01 | 2007-11-22 | E. I. Du Pont De Nemours And Company | Two step preparation of random polyoxadiazole copolymer and articles resulting therefrom |
| CN101437871A (en) * | 2006-05-01 | 2009-05-20 | 纳幕尔杜邦公司 | Two step preparation of random polyoxadiazole copolymer and articles resulting therefrom |
| CN104093787A (en) * | 2012-01-12 | 2014-10-08 | 韩华石油化学株式会社 | Resin composition for emi shielding, comprising carbon hydride composite |
| CN104817687A (en) * | 2015-05-22 | 2015-08-05 | 江苏宝德新材料有限公司 | High-purity aromatic polyoxadiazole solution and fiber prepared from high-purity aromatic polyoxadiazole solution |
| CN104831400A (en) * | 2015-05-22 | 2015-08-12 | 江苏宝德新材料有限公司 | Low-viscosity aromatic polyoxdiazole solution and fiber prepared from same |
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Application publication date: 20190215 |