CN106046688A - Phosphonitrile fire retardant-containing carbon fiber-reinforced resin composite material and preparation method thereof - Google Patents
Phosphonitrile fire retardant-containing carbon fiber-reinforced resin composite material and preparation method thereof Download PDFInfo
- Publication number
- CN106046688A CN106046688A CN201610633224.5A CN201610633224A CN106046688A CN 106046688 A CN106046688 A CN 106046688A CN 201610633224 A CN201610633224 A CN 201610633224A CN 106046688 A CN106046688 A CN 106046688A
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- China
- Prior art keywords
- substituted
- unsubstituted
- group
- fire retardant
- resin composite
- Prior art date
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Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 62
- ZSTLPJLUQNQBDQ-UHFFFAOYSA-N azanylidyne(dihydroxy)-$l^{5}-phosphane Chemical compound OP(O)#N ZSTLPJLUQNQBDQ-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000000463 material Substances 0.000 title claims abstract description 41
- 239000000805 composite resin Substances 0.000 title claims abstract description 29
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000003822 epoxy resin Substances 0.000 claims abstract description 27
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 27
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 13
- 239000007822 coupling agent Substances 0.000 claims abstract description 13
- 239000004014 plasticizer Substances 0.000 claims abstract description 13
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 12
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 32
- -1 alkyl sulfide Chemical compound 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 24
- 229910052736 halogen Inorganic materials 0.000 claims description 21
- 150000002367 halogens Chemical class 0.000 claims description 20
- 125000001072 heteroaryl group Chemical group 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 125000001118 alkylidene group Chemical group 0.000 claims description 13
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000000000 cycloalkoxy group Chemical group 0.000 claims description 12
- 150000002148 esters Chemical class 0.000 claims description 12
- 125000004171 alkoxy aryl group Chemical group 0.000 claims description 10
- 125000004104 aryloxy group Chemical group 0.000 claims description 10
- 239000002134 carbon nanofiber Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 10
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 10
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 125000005114 heteroarylalkoxy group Chemical group 0.000 claims description 9
- 125000001424 substituent group Chemical group 0.000 claims description 9
- 125000004437 phosphorous atom Chemical group 0.000 claims description 8
- RVOVWQHDIUDZOR-UHFFFAOYSA-N OP(O)(=O)OP(=O)(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)C(CO)(CO)CO Chemical compound OP(O)(=O)OP(=O)(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)C(CO)(CO)CO RVOVWQHDIUDZOR-UHFFFAOYSA-N 0.000 claims description 7
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 7
- 125000004647 alkyl sulfenyl group Chemical group 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 125000005587 carbonate group Chemical group 0.000 claims description 7
- 125000003262 carboxylic acid ester group Chemical group [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 claims description 7
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 6
- 230000000269 nucleophilic effect Effects 0.000 claims description 6
- 229920002627 poly(phosphazenes) Polymers 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- JBTXGEJRJCNRLU-UHFFFAOYSA-N [2-(dihydroxyphosphanyloxymethyl)-3-hydroxy-2-(hydroxymethyl)propyl] dihydrogen phosphite Chemical compound OP(O)OCC(CO)(CO)COP(O)O JBTXGEJRJCNRLU-UHFFFAOYSA-N 0.000 claims description 4
- 125000005248 alkyl aryloxy group Chemical group 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- 125000005326 heteroaryloxy alkyl group Chemical group 0.000 claims description 4
- 125000000962 organic group Chemical group 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid group Chemical group C(C=1C(C(=O)O)=CC=CC1)(=O)O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 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 claims description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 150000002009 diols Chemical class 0.000 claims description 2
- DIORMHZUUKOISG-UHFFFAOYSA-N sulfoformic acid Chemical compound OC(=O)S(O)(=O)=O DIORMHZUUKOISG-UHFFFAOYSA-N 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- 229930185605 Bisphenol Natural products 0.000 claims 2
- 239000004593 Epoxy Substances 0.000 claims 1
- GFTGHOJGGLNVMC-UHFFFAOYSA-N N=NC=NN.N=NC=NN.C(C=1C(C(=O)O)=CC=CC1)(=O)O Chemical compound N=NC=NN.N=NC=NN.C(C=1C(C(=O)O)=CC=CC1)(=O)O GFTGHOJGGLNVMC-UHFFFAOYSA-N 0.000 claims 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims 1
- DUWWHGPELOTTOE-UHFFFAOYSA-N n-(5-chloro-2,4-dimethoxyphenyl)-3-oxobutanamide Chemical compound COC1=CC(OC)=C(NC(=O)CC(C)=O)C=C1Cl DUWWHGPELOTTOE-UHFFFAOYSA-N 0.000 claims 1
- 235000019260 propionic acid Nutrition 0.000 claims 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- 229920000049 Carbon (fiber) Polymers 0.000 abstract 1
- 235000006708 antioxidants Nutrition 0.000 abstract 1
- 239000004917 carbon fiber Substances 0.000 abstract 1
- 239000002585 base Substances 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000003153 chemical reaction reagent Substances 0.000 description 17
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- UXJHQBVRZUANLK-UHFFFAOYSA-N azanylidyne(dichloro)-$l^{5}-phosphane Chemical compound ClP(Cl)#N UXJHQBVRZUANLK-UHFFFAOYSA-N 0.000 description 13
- 229940106691 bisphenol a Drugs 0.000 description 13
- 239000002131 composite material Substances 0.000 description 13
- 239000001257 hydrogen Substances 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 8
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical group CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 125000004429 atom Chemical group 0.000 description 7
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 238000000053 physical method Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 235000019253 formic acid Nutrition 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 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 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- ZYUVGYBAPZYKSA-UHFFFAOYSA-N 5-(3-hydroxybutan-2-yl)-4-methylbenzene-1,3-diol Chemical compound CC(O)C(C)C1=CC(O)=CC(O)=C1C ZYUVGYBAPZYKSA-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 229910021295 PNCl2 Inorganic materials 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 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 2
- 150000001721 carbon Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- XCJXQCUJXDUNDN-UHFFFAOYSA-N chlordene Chemical group C12C=CCC2C2(Cl)C(Cl)=C(Cl)C1(Cl)C2(Cl)Cl XCJXQCUJXDUNDN-UHFFFAOYSA-N 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- NHADDZMCASKINP-HTRCEHHLSA-N decarboxydihydrocitrinin Natural products C1=C(O)C(C)=C2[C@H](C)[C@@H](C)OCC2=C1O NHADDZMCASKINP-HTRCEHHLSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- RMBAVIFYHOYIFM-UHFFFAOYSA-M sodium methanethiolate Chemical compound [Na+].[S-]C RMBAVIFYHOYIFM-UHFFFAOYSA-M 0.000 description 2
- 125000000547 substituted alkyl group Chemical group 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- WLRMANUAADYWEA-NWASOUNVSA-N (S)-timolol maleate Chemical compound OC(=O)\C=C/C(O)=O.CC(C)(C)NC[C@H](O)COC1=NSN=C1N1CCOCC1 WLRMANUAADYWEA-NWASOUNVSA-N 0.000 description 1
- PEJQKHLWXHKKGS-UHFFFAOYSA-N 2,2,4,4,6,6,8,8-octachloro-1,3,5,7-tetraza-2$l^{5},4$l^{5},6$l^{5},8$l^{5}-tetraphosphacycloocta-1,3,5,7-tetraene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 PEJQKHLWXHKKGS-UHFFFAOYSA-N 0.000 description 1
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 1
- CAPNUXMLPONECZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-2-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=C(O)C(C(C)(C)C)=C1 CAPNUXMLPONECZ-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- 206010000369 Accident Diseases 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- IEBJZLRZRKTGFN-UHFFFAOYSA-N N=NC=NN.N=NC=NN.C1=CC=CC=C1 Chemical compound N=NC=NN.N=NC=NN.C1=CC=CC=C1 IEBJZLRZRKTGFN-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 1
- UYAGPULHTNCMOT-UHFFFAOYSA-N [B].FB(F)F Chemical compound [B].FB(F)F UYAGPULHTNCMOT-UHFFFAOYSA-N 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- BDKZHNJTLHOSDW-UHFFFAOYSA-N [Na].CC(O)=O Chemical compound [Na].CC(O)=O BDKZHNJTLHOSDW-UHFFFAOYSA-N 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000005213 alkyl heteroaryl group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- SMYKVLBUSSNXMV-UHFFFAOYSA-K aluminum;trihydroxide;hydrate Chemical compound O.[OH-].[OH-].[OH-].[Al+3] SMYKVLBUSSNXMV-UHFFFAOYSA-K 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 125000002102 aryl alkyloxo group Chemical group 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000021523 carboxylation Effects 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000004446 heteroarylalkyl group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- GPRDLRZMTVQCHM-UHFFFAOYSA-L magnesium;dihydroxide;hydrate Chemical compound O.[OH-].[OH-].[Mg+2] GPRDLRZMTVQCHM-UHFFFAOYSA-L 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 125000004043 oxo group Chemical group O=* 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 229950007908 piconol Drugs 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- ZJLMKPKYJBQJNH-UHFFFAOYSA-N propane-1,3-dithiol Chemical compound SCCCS ZJLMKPKYJBQJNH-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
-
- 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
- C07F9/6581—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 and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
- C07F9/65812—Cyclic phosphazenes [P=N-]n, n>=3
- C07F9/65815—Cyclic phosphazenes [P=N-]n, n>=3 n = 3
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/5399—Phosphorus bound to nitrogen
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
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- Fireproofing Substances (AREA)
Abstract
The invention provides a phosphonitrile fire retardant-containing carbon fiber-reinforced resin composite material and a preparation method thereof. The phosphonitrile fire retardant-containing carbon fiber-reinforced resin composite material is prepared from 5-15 parts by weight of nanometer carbon fibers, 2-10 parts by weight of a halogen-free phosphonitrile fire retardant, 50-70 parts by weight of epoxy resin, 1-5 parts by weight of a coupling agent, 1-3 parts by weight of an anti-oxidant and 0.01-0.2 parts by weight of a plasticizer. The halogen-free phosphonitrile fire retardant has a structure shown in the formula. Through use of the halogen-free phosphonitrile fire retardant, the resin composite material has excellent fire retardance. Through cooperation of all the components, the resin composite material has good tensile strength and good fracture percentage elongation.
Description
Technical field
The present invention relates to the technical field of fire retardant matter, particularly relate to a kind of fibre reinforced tree containing phosphonitrile fire retardant
Resin composite material and preparation method thereof.
Background technology
Along with economic develops rapidly, carbon fibre composite is widely used in industry-by-industry field, by
In the frequent generation of electrical fire accident, the fire-retardant problem of material gradually causes the attention of countries in the world；Discharge during material combustion
Go out a large amount of smog and poisonous, corrosive gas is the risk factor in fire, hamper people's safe escape and fire extinguishing work
Make, make lives and properties suffer heavy losses.
Traditional technology typically uses interpolation aluminium hydroxide hydrate, magnesium hydroxide hydrate etc. in material system to contain
The inorganic fire-retarded material such as the metal hydroxides of water of crystallization, and in material system, add brominated bisphenol A, bmminated bisphenol-A type
The method of the organic fire-resisting material that the content of halogen such as epoxy resin are higher, make product reach required fire resistance or etc.
Level.In order to improve the anti-flammability of these organic chemicalss containing halogen, the most usually add such as antimony oxide in system
Deng inorganic fire-retarded material disagreeableness to environment.
Halogen-containing fire retardant matter can produce the noxious substance without degradability or difficult degradation (as dioxin has when burning
Machine halogen chemical substance), pollute environment, affect the mankind and animal health.
Because adding organophosphorus ester and/or phosphorus nitrogen expansion type flame-retardant system in the material of prior art, cause material mechanical
The shortcomings such as performance declines to a great extent, and flame retardant rating is low, and temperature resistant grade is low.
Summary of the invention
In view of this, one aspect of the present invention provides a kind of carbon fiber-reinforced resin composite materials containing phosphonitrile fire retardant,
This composite has good flame-retardance, thermostability, good mechanical performance.
A kind of carbon fiber-reinforced resin composite materials containing phosphonitrile fire retardant, described resin composite materials comprises following weight
The component of amount part:
In composite of the present invention, the consumption of carbon nano-fiber is 5-15 weight portion, such as 5 weight portions, 6 weight
Part, 7 weight portions, 8 weight portions, 9 weight portions, 10 weight portions, 11 weight portions, 12 weight portions, 13 weight portions, 14 weight portions or 15 weights
Amount part.
In composite of the present invention, the consumption of Halogen phosphonitrile fire retardant is 2-10 weight portion, such as 2 weight portions, 3
Weight portion, 4 weight portions, 5 weight portions, 6 weight portions, 7 weight portions, 8 weight portions, 9 weight portions or 10 weight portions.
Consumption in composite epoxy resin of the present invention is 50-70 weight portion, such as 50 weight portions, 52 weight
Part, 55 weight portions, 58 weight portions, 60 weight portions, 63 weight portions, 65 weight portions, 68 weight portions or 70 weight portions.
In composite of the present invention, the consumption of coupling agent is 1-5 weight portion, such as 1 weight portion, 1.2 weight portions,
1.4 weight portions, 1.6 weight portions, 1.8 weight portions, 2 weight portions, 2.3 weight portions, 2.5 weight portions, 2.8 weight portions, 3 weight portions,
3.5 weight portions, 4 weight portions, 4.5 weight portions or 5 weight portions.
In composite of the present invention, the consumption of antioxidant is 1-3 weight portion, such as 1 weight portion, 1.2 weight portions,
1.4 weight portions, 1.6 weight portions, 1.8 weight portions, 2 weight portions, 2.3 weight portions, 2.5 weight portions, 2.8 weight portions or 3 weight portions.
In composite of the present invention, plasticizer consumption is 0.01-0.2 weight portion, such as 0.01 weight portion, 0.03
Weight portion, 0.05 weight portion, 0.08 weight portion, 0.1 weight portion, 0.13 weight portion, 0.15 weight portion, 0.18 weight portion or 0.2
Weight portion.
In the present invention, described Halogen phosphonitrile fire retardant has a structure shown in formula I:
In formula I, R1And R2Independently be any inertia nucleophilic group meeting its chemical environment, R3And R4Change for meeting it
Learn any organic group of environment, X1And X2Independently be-O-Ar-O-,-S-R5-S-、-NH-R6-NH-、-NH-R7-O-、-S-R11NH-、-O-R12COO-or-S-R13Any one in COO-, R5、R6、R7、R8、R9、R10、R11、R12
And R13For meeting any organic group of its chemical environment, Y1And Y2Independently be any nucleophilic group meeting its chemical environment
Group；M is ring three phosphonitrile base M1, ring more than four phosphonitrile base M2Or non-annularity polyphosphazene base M3In any one or at least two
Combination, m, n are the integer more than or equal to zero；A, b, c, d are the integer more than or equal to zero, and a+b+c+d+2 is equal to phosphorus on M group
2 times of atom number.
In the present invention, described meet the atom that its chemical environment refers to be adjacent and be connected, obtain stable change
Learn connecting key.
Preferably, R1And R2Independently be substituted or unsubstituted alkoxyl, substituted or unsubstituted cycloalkyloxy, replacement
Or unsubstituted aryloxy group, substituted or unsubstituted alkoxy aryl, substituted or unsubstituted heteroarylalkoxy, replacement or not
Substituted alkyl sulfenyl, substituted or unsubstituted artyl sulfo, substituted or unsubstituted carboxylic acid ester groups, substituted or unsubstituted carbon
Any one in perester radical, substituted or unsubstituted sulfonate group or substituted or unsubstituted phosphonate group；Described alkoxyl,
Cycloalkyloxy, aryloxy group, alkoxy aryl, heteroarylalkoxy, alkyl sulfenyl, artyl sulfo, carbonate group, sulfonate group or
The substituent group of phosphonate group independently be straight or branched alkyl, alkoxyl, cycloalkyloxy, aryl, aryloxy group, arylalkoxy
Any one in base, heteroaryl, alkyl sulfenyl, artyl sulfo, carboxylic acid ester groups, carbonate group, sulfonate group or phosphonate group
Or the combination of at least two, described substituent group does not contains reactive end-capping group；Such as, described substituent group for do not contain OH ,-
CN、-NH2、-SH、-COOH、-CHO、-CONH2Isoreactivity group；Illustrate with instantiation, when substituent group is carboxylic acid ester groups,
Can not be that one end is still with the formic acid ester group of carboxyl.
Specifically, R1And R2CH can be independently be3O-、CH3CH2O-、CH3S-、CH3CH2CH2S-、CH3COO-or PhO-(Ph
Represent phenyl) in any one.
R in the present invention1And R2Can be that identical group can also be for different groups.
Preferably, R3And R4Independently be substituted or unsubstituted straight or branched alkylidene, substituted or unsubstituted Asia
Cycloalkyl, substituted or unsubstituted arlydene, substituted or unsubstituted inferior heteroaryl, substituted or unsubstituted arlydene
Alkylidene, substituted or unsubstituted alkylenearylene, substituted or unsubstituted alkylidene inferior heteroaryl or substituted or
Any one in unsubstituted inferior heteroaryl alkylidene.
Specifically, R3And R4-CH can be independently be2-、-CH2CH2CH2-、 In any one.
Preferably, R5、R6、R7、R8、R11、R12And R13Independently be substituted or unsubstituted straight or branched alkylidene, take
Generation or unsubstituted cycloalkylidene, substituted or unsubstituted arlydene, substituted or unsubstituted inferior heteroaryl, substituted
Or unsubstituted arylidene alkylene, substituted or unsubstituted alkylenearylene, substituted or unsubstituted alkylidene are sub-
Any one in heteroaryl or substituted or unsubstituted inferior heteroaryl alkylidene.
Specifically, R5、R6、R7、R8、R11、R12And R13-CH can be independently be2-、-CH2CH2CH2-、In appoint
Meaning one.
Preferably, R9And R10Independently be substituted or unsubstituted straight or branched alkyl, substituted or unsubstituted ring
Alkyl, substituted or unsubstituted alkoxyl, substituted or unsubstituted cycloalkyloxy, substituted or unsubstituted aryl, take
Generation or unsubstituted heteroaryl, substituted or unsubstituted substituted or unsubstituted aryloxy group, substituted or unsubstituted aryl
Alkoxyl, substituted or unsubstituted alkyl-aryloxy, substituted or unsubstituted heteroarylalkoxy, substituted or unsubstituted alcoxyl
Base heteroaryl, substituted or unsubstituted heteroaryl oxyalkyl, substituted or unsubstituted miscellaneous alkyl aryl, substituted or unsubstituted alkane
Base aryl, substituted or unsubstituted aryl alkyl, substituted or unsubstituted miscellaneous alkyl aryl, substituted or unsubstituted alkyl sulfide
Base, substituted or unsubstituted artyl sulfo, substituted or unsubstituted carboxylic acid ester groups, substituted or unsubstituted carbonate group, replacement
Or any one in unsubstituted sulfonate group or substituted or unsubstituted phosphonate group.
Specifically, R9And R10-CH can be independently be3、-OCH3、-CN、-COOH、-CHO、-CONH2Or any one in Ph-
Kind.
Preferably, Y1And Y2Independently be substituted or unsubstituted alkoxyl, substituted or unsubstituted cycloalkyloxy, replacement
Or unsubstituted aryloxy group, substituted or unsubstituted alkoxy aryl, substituted or unsubstituted heteroarylalkoxy, replacement or not
Substituted alkyl sulfenyl, substituted or unsubstituted artyl sulfo, substituted or unsubstituted carboxylic acid ester groups, substituted or unsubstituted carbon
Any one in perester radical, substituted or unsubstituted sulfonate group or substituted or unsubstituted phosphonate group.
Specifically, Y1And Y2-OCH can be independently be3、PhO-、CH3S-, PhS-or CH3Any one in COO-.
In the present invention, substituted or unsubstituted straight chained alkyl or branched alkyl be preferably substituted or unsubstituted C1～
C12 (such as C1, C2, C3, C4, C5, C6, C7, C8, C9, C10 or C11) straight chained alkyl or branched alkyl, further preferred C1～
C8 straight chained alkyl or branched alkyl, be methyl when carbon number is 1, when carbon number is 2, is ethyl.
Substituted or unsubstituted cycloalkyl be preferably substituted or unsubstituted C3～C12 (such as C4, C5, C6, C7, C8,
C9, C10 or C11) cycloalkyl.
Substituted or unsubstituted alkoxyl be preferably substituted or unsubstituted C1～C12 (such as C2, C3, C4, C5, C6,
C7, C8, C9, C10 or C11) alkoxyl.
Substituted or unsubstituted cycloalkyloxy be preferably substituted or unsubstituted C3～C12 (such as C4, C5, C6, C7,
C8, C9, C10 or C11) cycloalkyloxy.
Substituted or unsubstituted aryl be preferably phenyl, benzyl, naphthyl, Deng.
Substituted or unsubstituted heteroaryl is five yuan or six membered heteroaryl, the most substituted or unsubstituted furan
Mutter base or pyridine radicals.
Substituted or unsubstituted aryl alkyl is preferably C7-C13 (such as C8, C9, C10, C11 or C12) aryl alkyl.
Substituted or unsubstituted alkylaryl is preferably C7-C13 (such as C8, C9, C10, C11 or C12) alkylaryl.
Substituted or unsubstituted alkoxy aryl is preferably C7-C13 (such as C8, C9, C10, C11 or C12) alkoxy aromatic
Base.
Substituted or unsubstituted heteroaryl alkyl is preferably C7-C13 (such as C8, C9, C10, C11 or C12) heteroaryl alkane
Base.
Substituted or unsubstituted miscellaneous alkyl aryl is preferably C7-C13 (such as C8, C9, C10, C11 or C12) alkyl heteroaryl
Base.
Substituted or unsubstituted straight-chain alkyl-sub-be preferably C1-C12 (such as C2, C3, C4, C5, C6, C7, C8, C9,
C10 or C11) straight-chain alkyl-sub-.
Substituted or unsubstituted branched alkylidene be preferably C1-C12 (such as C2, C3, C4, C5, C6, C7, C8, C9,
C10 or C11) branched alkylidene.
Substituted or unsubstituted arlydene is preferably the arlydene of C6-C13 (such as C7, C8, C9, C10, C11 or C12).
Substituted or unsubstituted inferior heteroaryl is preferably C5-C13's (such as C6, C7, C8, C9, C10, C11 or C12)
Inferior heteroaryl.
Substituted or unsubstituted alkylenearylene is preferably C7-C13 (such as C8, C9, C10, C11 or C12) alkylene
Base arlydene.
Substituted or unsubstituted arylidene alkylene is preferably C7-C13 (such as C8, C9, C10, C11 or C12) alkylene
Base arlydene.
Substituted or unsubstituted alkylidene inferior heteroaryl is preferably C6-C13 (such as C7, C8, C9, C10, C11 or C12)
Alkylidene inferior heteroaryl.
Substituted or unsubstituted inferior heteroaryl alkylidene is preferably C6-C13 (such as C7, C8, C9, C10, C11 or C12)
Inferior heteroaryl alkylidene.
Substituted or unsubstituted alkoxyl heteroaryl is preferably C7-C13 (such as C8, C9, C10, C11 or C12) alkoxyl
Heteroaryl.
Substituted or unsubstituted heteroarylalkoxy is preferably C7-C13 (such as C8, C9, C10, C11 or C12) heteroaryl
Alkoxyl.
Substituted or unsubstituted heteroaryl oxyalkyl is preferably C7-C13 (such as C8, C9, C10, C11 or C12) heteroaryl
Oxyalkyl.
Substituted or unsubstituted alkoxy aryl is C7-C12 (such as C8, C9, C10 or C11) aralkoxy.
Substituted or unsubstituted alkyl-aryloxy is preferably C7-C12 (such as C8, C9, C10 or C11) alkyl-aryloxy.
Substituted or unsubstituted alkyl sulfenyl is preferably C1-C8 (such as C1, C2, C3, C4, C5, C6, C7 or C8) alkyl sulfide
Base.
Substituted or unsubstituted artyl sulfo is preferably C7-C12 (such as C8, C9, C10 or C11) artyl sulfo.
Term used in the present invention " substituted " refers to that any one or more hydrogen atoms on specified atom are selected from
The substituent group of designated groups replaces, and condition is that described specified atom is less than normal valency, and substituted result is to produce to stablize
Compound.When substituent group is oxo group or ketone group (i.e.=O), then 2 hydrogen atoms on atom are replaced.Ketone replaces
Base does not exists on aromatic rings." stable compound " refers to enough separate from reactant mixture con vigore to effectively
Purity is also configured to compounds effective.
In the present invention, M is ring three phosphonitrile base M1, ring more than four phosphonitrile base M2, non-annularity polyphosphazene base M3In one or
The combination of at least two.
Preferably, M comprises at least 50wt%M1, at most 30wt%M2And at most 45wt%M3。
In the present invention, M1Content is at least 50wt%, i.e. M1Content can be 50wt～100wt%, M1Become for main body
Point.Work as M1When content is 100wt%, then do not contain M2And M3.The typical but non-limiting M of the present invention1Content can be
50wt%, 51wt%, 55wt%, 58wt%, 60wt%, 65wt%, 70wt%, 74wt%, 75wt%, 80wt%, 85wt%,
90wt%, 92wt%, 95wt%, 98wt% or 100wt%.
In the present invention, M2Content is at most 30wt%, i.e. refers to, M2Content can be 0～30wt%.Work as M2Content is
During 0wt%, i.e. refer to, do not contain M2.The typical but non-limiting M of the present invention2Content can be 0wt%, 2wt%, 5wt%,
8wt%, 11wt%, 14wt%, 16wt%, 17wt%, 19wt%, 20wt%, 22wt%, 25wt%, 27wt%, 28wt% or
29wt%.
In the present invention, M3Content is at most 45wt%, i.e. refers to, M3Content can be 0～45wt%.Work as M3Content is
During 0wt%, i.e. refer to, do not contain M3.The typical but non-limiting M of the present invention3Content can be 0wt%, 2wt%, 5wt%,
8wt%, 10wt%, 12wt%, 14wt%, 16wt%, 18wt%, 20wt%, 23wt%, 25wt%, 27wt%, 28wt%,
30wt%, 32wt%, 35wt%, 38wt%, 40wt%, 43wt% or 45wt%.
In the present invention, M1、M2And M3Mass percent sum is 100%.
Preferably, M1Structure is:
M2Structure is:
Wherein, x is more than or equal to 4；
M3Structure is:
Wherein, y is more than or equal to 3.
Note, M1、M2In the expression of structural formula, occurred symbolIt it is only the one to " ring-type " structure
Signal.
In the structural formula I of the present invention, m, n are the integer more than or equal to zero, and m, n can be zero simultaneously, it is also possible to different
Time be zero, such as m can be but be not limited to 0,1,2,3,4,5,6,7,8,9 or 10, n can be but be not limited to 0,1,2,3,4,5,
6,7,8,9 or 10.
A, b, c, d are the integer more than or equal to zero, and can not be zero both c, d simultaneously, i.e. ensure that M institute band group at least contains
There is a group with reactivity (such as-SH or-OH).
In the structural formula of the present invention, the group being connected with M is all to be connected with the phosphorus atoms in M.And at formula I of the present invention
Middle a+b+c+d+2, equal on M group 2 times of number of phosphorus atoms, i.e. ensures that on M, phosphorus atoms reaches the saturated shape that quantivalence is pentavalent
State.
The phosphonitrile fire retardant that the present invention provides is a kind of halogen-free flameproof thing, all groups in its chemical formula or group
Substituent group does not all contain halogen.
Preferably, Halogen phosphonitrile fire retardant of the present invention is to have a kind of in the compound of following structure or at least two
Combination:
Wherein M is ring three phosphonitrile base.
The Halogen phosphonitrile flame retardant of the formula I of the present invention is by phosphonitrile chloride and nucleopilic reagent generation nucleophilic substitution system
For obtain.
Phosphonitrile chloride refers to that M-Cla+b+c+d+2, nucleopilic reagent refer to R1、R2、-S-R3-SH、-O-R4-OH、X1、X2、Y1
And Y2Corresponding affinity reagent, such as, works as R1During for methoxyl group, it is possible to achieve with phosphonitrile chloride generation nucleophilic displacement of fluorine by first
The affinity reagent that epoxide is connected on the phosphorus atoms of M can be methanol or Feldalat NM；Work as R2For methylsulfany (CH3S-) time, permissible
The affinity reagent realizing being connected on the phosphorus atoms of M by methylsulfany with phosphonitrile chloride generation nucleophilic substitution can be first
Mercaptan or sodium methyl mercaptide；As-S-R3-SH is-S-CH2CH2During-SH, it is possible to achieve with phosphonitrile chloride generation nucleophilic substitution
By-S-CH2CH2The affinity reagent that-SH is connected on the phosphorus atoms of M can be HS-CH2CH2-SH；As-O-R4-OH beTime, it is possible to achieve will with phosphonitrile chloride generation nucleophilic substitutionIt is connected to the phosphorus of M
Affinity reagent on atom can beSame method can realize X1、X2、Y1And Y2Connection, X1And X2
Corresponding nucleopilic reagent be at least contain two can with M generation nucleophilic substitution and by X1And X2It is connected on the phosphorus atoms of M
The nucleopilic reagent of active reactive group.
The phosphonitrile fire retardant of formula I at least contains a group-SH or-OH with reactivity.In c, d, which person is
Zero, then show that the reactant participating in necleophilic reaction does not contains its corresponding reactant.
In described nucleophilic substitution, the chlorine in phosphonitrile chloride is replaced.Necleophilic reaction can use known in this field
Method complete, such as refer to " progress of polyphosphazene, Zhang Hongwei etc., material Leader the 7th phase of volume 24 in 2010 ".
The instantiation of catalyst used in necleophilic reaction has metal chlorides such as zinc chloride, magnesium chloride, aluminum chloride or borontrifluoride
Boron and the lewis base such as complex or sodium hydroxide thereof.These catalyst can be used in mixed way with one or more, in the present invention
There is no particularly regulation.Here the compound that during " phosphonitrile chloride " refers to formula (I), M group is connected with Cl.As for phosphonitrile
Chloride can use known solvent, catalyst to synthesize in known reaction scheme, it is possible to use phosphorus pentachloride and chlorination
Ammonium is synthesized after phosphonitrilic chloride compound according to known methods, processes through physical method and purifies or do not purify directly system
Make, its PCl5+NH4Cl→1/n(NPCl2) n+4HCl, this product is mainly trimer (PNCl2)3(that is chlordene ring
Three phosphonitriles) and the tetramer (PNCl2)4, product is again by obtaining pure chlordene ring by slowly distilling in 60 DEG C of vacuum
Three phosphonitriles.Chloro ring more than four phosphonitrile and chloro non-annularity polyphosphazene can also be prepared by prior art.
In above-mentioned preparation method, nucleopilic reagent necessarily comprises the nucleopilic reagent containing at least two active reactive group
(i.e.-S-R3-SH、-O-R4-OH、X1、X2Corresponding affinity reagent, R3、R4、X1、X2Limit ibid), to obtain structure shown in formula I
Halogen phosphonitrile flame-retardant compound in the attachment structure ensureing of group structure shown in formula I at least contains a reactivity envelope
End group group.The example of the nucleopilic reagent of at least two active reactive group can include but not limited to hydroquinone, resorcinol,
Naphthalenediol, benzene mixed diphenol, 1,4-naphthols, bisphenol-A, bisphenol S, Bisphenol F, 1,4-phenyl two mercaptan, 1,2-dithioglycol, 1,3-
Dimercaptopropane, p-phthalic acid etc..
In addition to the above-mentioned nucleopilic reagent containing at least two active reactive group, also can use containing an active reaction base
Other nucleopilic reagents of group, such as monohydric alcohol (such as, methanol, ethanol) or its sodium salt, phenol, unary carboxylation's (such as, acetic acid
Sodium), monoamine (such as, methylamine, ethamine), unitary mercaptan (such as, methanthiol, ethyl mercaptan) etc..
In the nucleopilic reagent reaction with phosphonitrile chloride, the nucleophilic containing an active reactive group can be first used to try
Agent is reacted with phosphonitrile chloride, and part replaces the chlorine in phosphonitrile chloride, the most again with described containing at least two active reaction
The nucleopilic reagent of group reacts with phosphonitrile chloride, to obtain the Halogen phosphonitrile fire retardant of structure shown in formula I.
Of the present invention containing in the raw material of the carbon fiber-reinforced resin composite materials of phosphonitrile fire retardant, described asphalt mixtures modified by epoxy resin
Fat is liquid bisphenol A type epoxy resin, liquid bisphenol F type epoxy resin, solid-state bisphenol A type epoxy resin, solid-state bisphenol-f type ring
One in epoxy resins, bisphenol-s epoxy resin, acyclic isoprenoid type epoxy resin or biphenyl type epoxy resin or at least two
Combination.
Preferably, described coupling agent is silane coupler and/or titanate coupling agent.
Preferably, described antioxidant is double (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphate, four-" 3-(3,5-
Di-tert-butyl-hydroxy phenyl) propanoic acid) quaternary amyl alcohol ester, β (3,5-di-tert-butyl-hydroxy phenyl) propanoic acid octadecyl, (2,
4,6-di-tert-butyl-phenyl-2-butyl-2-ethyl)-1,3 one diol phosphite, 2,2 ' one ethylenebis (the tertiary fourth of 4,6-bis-
Base phenyl) one or at least two in fluorophosphite or two (2,4-bis-p-isopropyl phenyl) pentaerythritol bis-phosphite
The combination planted.
Preferably, described plasticizer is phthalic acid two (2-ethyl hexyl) ester, dioctyl phthalate or O-phthalic
Any one or the combination of at least two in dimethyl phthalate.
Further aspect of the present invention provides the preparation of the described carbon fiber-reinforced resin composite materials containing phosphonitrile fire retardant
Method, this preparation method the composite obtained has good flame-retardance, thermostability, good mechanical performance.
A kind of method preparing composite described above, described method is: by fire-retardant to carbon nano-fiber, Halogen phosphonitrile
After agent, epoxy resin, coupling agent, antioxidant and plasticizer mixing, then plasticate, more mixing obtaining described hinders containing phosphonitrile
The carbon fiber-reinforced resin composite materials of combustion agent.
Preferably, the temperature plasticated is 120～150 DEG C, such as 125 DEG C, 130 DEG C, 135 DEG C, 138 DEG C, 140 DEG C, 143
DEG C, 145 DEG C or 148 DEG C, the time plasticated is 5～10min, such as 5.5min, 6min, 7min, 8min or 9min.That plasticates sets
For using mill or mixing roll, the operation that this area can be used conventional is implemented to plasticate.
Preferably, mixing temperature is 150～200 DEG C, such as 155 DEG C, 158 DEG C, 160 DEG C, 163 DEG C, 165 DEG C, 170
DEG C, 175 DEG C, 178 DEG C, 180 DEG C, 183 DEG C, 185 DEG C, 187 DEG C, 190 DEG C, 193 DEG C, 195 DEG C or 198 DEG C, the mixing time is excellent
Elect 15～30min as, such as 15min, 18min, 20min, 23min, 25min, 28min or 29min.This area can be used conventional
Operation implement mixing.
Above-mentioned term " ××× base or group " refers to slough in ××× molecular structure of compounds one or more hydrogen atom
Or remaining part after other atom or atomic group.
Compared with prior art, the method have the advantages that
Halogen phosphonitrile fire retardant shown in contained I in the resin composite materials of the present invention, this Halogen phosphonitrile fire retardant
Adding the anti-flammability making resin composite materials have excellence, each composition cooperates so that resin composite materials has good
Hot strength and elongation at break.The hot strength of the resin composite materials that the present invention prepares is up to 31.5-39MPa, disconnected
Splitting percentage elongation and be up to 392-438%, flammability reaches A level, and ageing properties also makes moderate progress, and thermostability is good.
Detailed description of the invention
Technical scheme is further illustrated below in conjunction with embodiment.
Embodiment 1
In the present embodiment, Halogen phosphonitrile fire retardant has a structure that
Hexachlorocyclotriph,sphazene 1mol, acetone 250ml, double is put in three mouthfuls of 2000ml glass reactors with agitating device
Phenol A 3mol, sodium methyl mercaptide 3mol, stir and lead to nitrogen, is warmed up to 60 DEG C, instills 20% sodium hydroxide with 60min
Solution 620g, keeps 60 DEG C of temperature, stirring reaction 15 hours.After reaction, with the moisture in physical method removal system, after
Filter off except the insoluble matter in system, distill solvent in system, obtain the Halogen phosphonitrile fire retardant containing above-mentioned substance.
The phosphonitrile fire retardant obtained is carried out proton nmr spectra sign, and result is as follows:
1H NMR(CDCl3, 500MHz): 6.6-7.0 (m, 24H, hydrogen on phenyl ring), 5.0 (s, 3H, phenolic hydroxyl group hydrogen), 2.0 (m,
9H,SCH 3) 1.6 (m, 18H, methyl hydrogen on bisphenol-A group).
The position of infrared spectrum characteristic peak: the characteristic absorption peak 1217cm of P=N key in phosphazene backbone-1, P-in phosphazene backbone
N 874cm-1, the absworption peak 2995cm of methyl ether-1, P-O-C key absworption peak 1035cm-1, in bisphenol-A group, the skeleton of phenyl ring shakes
Dynamic absworption peak 1611cm-1、1509cm-1、1446cm-1, phenolic hydroxyl group absworption peak 3610cm-1、1260cm-1。
According to weight portion by 5 parts of above-mentioned fire retardants, 10 parts of carbon nano-fibers, 65 parts of liquid bisphenol A type epoxy resin, 2 parts
Titanate coupling agent, 1 part of antioxidant double (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphate, 0.1 part of plasticizer benzene two
Formic acid two (2-ethyl hexyl) ester is sufficiently mixed by batch mixer, then, is inserted by mixing raw material in mill at 150 DEG C
Plasticate 10min, mixing 30min at 170 DEG C.
Embodiment 2
In the present embodiment, Halogen phosphonitrile fire retardant has a structure that
Hexachlorocyclotriph,sphazene 1mol, acetone 250ml, second is put in three mouthfuls of 2000ml glass reactors with agitating device
Two mercaptan 3mol, 2-piconol 3mol, stirs and leads to nitrogen, be warmed up to 60 DEG C, instill 20% hydrogen-oxygen with 60min
Changing sodium solution 620g, keeps 60 DEG C of temperature, stirring is reacted 15 hours, after reaction, with the moisture in physical method removal system,
Refilter the insoluble matter in removal system, distill solvent in system, obtain the flame-retardant compound containing above-mentioned substance.
The flame-retardant compound obtained is carried out proton nmr spectra sign, and result is as follows:
1H NMR(CDCl3, 500MHz): δ 7.4-7.7 (m, 6H, the hydrogen on pyridine ring 3 and 5), 8.1 (s, 3H, pyridines
Hydrogen on 4, ring), 8.7 (s, 3H, the hydrogen on pyridine ring 6), 2.8 (m, 12H, HS-CH 2CH 2S-),1.5(s,3H,HS-
CH2CH2S-)。
The position of infrared spectrum characteristic peak: the characteristic absorption peak 1217cm of P=N key in phosphazene backbone-1, P-in phosphazene backbone
N 874cm-1, the absworption peak 2995cm of methyl ether-1, P-O-C key absworption peak 1035cm-1, CH2The absworption peak 2980cm of-S-1,-SH
Absworption peak 2560cm-1, pyridine ring skeleton absworption peak 1600～1500cm-1。
According to weight portion by 10 parts of above-mentioned fire retardants, 15 parts of carbon nano-fibers, 70 parts of bisphenol-s epoxy resins, 1 part of silane
Coupling agent, 2 parts of antioxidants double (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphate, 0.2 part of plasticizer phthalic acid
Dioctyl ester is sufficiently mixed by batch mixer, then, mixing raw material is inserted the 10min that plasticates at 120 DEG C in mill, then
Mixing 20min at 150 DEG C.
Embodiment 3
In the present embodiment, Halogen phosphonitrile fire retardant has a structure that
Hexachlorocyclotriph,sphazene 1mol, acetone 250ml, benzene is put in three mouthfuls of 2000ml glass reactors with agitating device
Thiophenol 3mol, Feldalat NM 2mol, ethylene glycol 1mol, stir and lead to nitrogen, is warmed up to 60 DEG C, instills 20% with 60min
Sodium hydroxide solution 620g, keeps 60 DEG C of temperature, stirring reaction 15 hours, then adds hexachlorocyclotriph,sphazene 1mol, continue
React 2 hours, add hydroquinone 2mol, Feldalat NM 3mol afterwards, continue reaction 6 hours.After reaction, remove with physical method
Moisture in system, refilters the insoluble matter in removal system, distills solvent in system, obtains the resistance containing above-mentioned substance
Retardant compound.
The flame-retardant compound obtained is carried out proton nmr spectra sign, and result is as follows:
1H NMR(CDCl3,500MHz):δ7.0-7.2(m,15H,Hydrogen on phenyl ring in group), 6.6 (m,
8H,Hydrogen on phenyl ring in group), 5.0 (m, 2H,Hydrogen on hydroxyl in group), 3.7 (d,
4H,O-CH 2CH 2O-),3.4(t,15H,O-CH 3)。
The position of infrared spectrum characteristic peak: the characteristic absorption peak 1217cm of P=N key in phosphazene backbone-1, P-in phosphazene backbone
N 874cm-1, the absworption peak 2995cm of methyl ether-1, P-O-C key absworption peak 1035cm-1, CH2The absworption peak 2983cm of-O-1, phenol
Hydroxyl group absorption peak 3610cm-1、1260cm-1。
According to weight portion by 5 parts of above-mentioned fire retardants, 2 parts of carbon nano-fibers, 60 parts of liquid bisphenol A type epoxy resin, 5 parts of titaniums
Acid esters coupling agent, 3 parts of antioxidant two (2,4-bis-p-isopropyl phenyl) pentaerythritol bis-phosphites, 0.15 part of plasticizer benzene
Dioctyl phthalate two (2-ethyl hexyl) ester is sufficiently mixed by batch mixer, then, is inserted by mixing raw material in mill at 145 DEG C
Under plasticate 8min, mixing 22min at 185 DEG C.
Embodiment 4
In the present embodiment, Halogen phosphonitrile fire retardant has a structure that
Hexachlorocyclotriph,sphazene 1mol, acetone 250ml, second is put in three mouthfuls of 2000ml glass reactors with agitating device
Two mercaptan 5mol and hydroquinone 1mol, stir and lead to nitrogen, are warmed up to 60 DEG C, instill 20% hydrogen-oxygen with 60min
Change sodium solution 620g, keep 60 DEG C of temperature, stirring reaction 15 hours, then add hexachlorocyclotriph,sphazene 1mol, continue reaction 5
Hour, add bisphenol-A 1mol, Feldalat NM 4mol afterwards, continue reaction 10 hours.After reaction, with in physical method removal system
Moisture, refilter the insoluble matter in removal system, distill solvent in system, obtain the fire-retardant chemical combination containing above-mentioned substance
Thing.
The flame-retardant compound obtained is carried out proton nmr spectra sign, and result is as follows:
1H NMR(CDCl3, 500MHz): δ 6.5-7.0 (m, 12H, hydrogen on phenyl ring), 5.0 (s, 1H, phenolic hydroxyl group hydrogen), 3.4
(t,12H,O-CH 3), 2.8 (m, 20H, HS-CH 2CH 2S-), 1.7 (s, 30H, methyl hydrogen on bisphenol-A), 1.5 (s, 5H,HS-
CH2CH2S-)。
The position of infrared spectrum characteristic peak: the characteristic absorption peak 1217cm of P=N key in phosphazene backbone-1, P-in phosphazene backbone
N 874cm-1, the absworption peak 2995cm of methyl ether-1, P-O-C key absworption peak 1035cm-1, CH2The absworption peak 2983cm of-O-1, double
The skeletal vibration absworption peak 1611cm of phenyl ring in phenol A group-1、1509cm-1、1446cm-1, phenolic hydroxyl group absworption peak 3610cm-1、
1260cm-1。
According to weight portion by 10 parts of above-mentioned fire retardants, 4 parts of carbon nano-fibers, 50 parts of liquid bisphenol A type epoxy resin, 1 part
Silane coupler, 1 part of antioxidant double (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphate, 0.01 part of plasticizer neighbour's benzene two
Formic acid dimethyl ester is sufficiently mixed by batch mixer, then, is inserted in mill by mixing raw material and plasticates at 150 DEG C
5min, mixing 15min at 200 DEG C.
Comparative example 1
In this example, using commercially available hexaphenoxycyclotriphosphazene as fire retardant, prepare according to the same manner as in Example 1
Composite, i.e. according to weight portion by 5 parts of above-mentioned fire retardants, 10 parts of carbon nano-fibers, 65 parts of liquid bisphenol A type epoxy resin, 2
Part titanate coupling agent, 1 part of antioxidant double (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphate, 0.1 part of plasticizer benzene
Dioctyl phthalate two (2-ethyl hexyl) ester is sufficiently mixed by batch mixer, then, is inserted by mixing raw material in mill at 150 DEG C
Under plasticate 10min, mixing 30min at 170 DEG C.
Comparative example 2
In this example, using commercially available hexachlorocyclotriph,sphazene as fire retardant, prepare compound according to the same manner as in Example 1
Material, i.e. according to weight portion by 5 parts of above-mentioned fire retardants, 10 parts of carbon nano-fibers, 65 parts of liquid bisphenol A type epoxy resin, 2 parts of titaniums
Acid esters coupling agent, 1 part of antioxidant double (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphate, 0.1 part of plasticizer benzene diformazan
Acid two (2-ethyl hexyl) ester is sufficiently mixed by batch mixer, then, is inserted in mill by mixing raw material and moulds at 150 DEG C
Refining 10min, mixing 30min at 170 DEG C.
Comparative example 3
In this example, using commercially available aluminium hydroxide as fire retardant, prepare composite wood according to the same manner as in Example 3
Material, i.e. according to weight portion by 5 parts of above-mentioned fire retardants, 2 parts of carbon nano-fibers, 60 parts of liquid bisphenol A type epoxy resin, 5 parts of metatitanic acids
Ester coupling agent, 3 parts of antioxidant two (2,4-bis-p-isopropyl phenyl) pentaerythritol bis-phosphites, 0.15 part of plasticizer benzene two
Formic acid two (2-ethyl hexyl) ester is sufficiently mixed by batch mixer, then, is inserted by mixing raw material in mill at 145 DEG C
Plasticate 8min, mixing 22min at 185 DEG C.
The composite of above-mentioned all embodiments and comparative example is done test as shown in the table, and result is (mirror in this table
It is well known to those skilled in the art in concrete method of testing, at this, method is no longer described in detail).
Table-1
The test data of above table, show that the present invention has good hot strength and elongation at break, excellent resistance
Combustion property.
Applicant state, the present invention by above-described embodiment illustrate the present invention carbon fiber-reinforced resin composite materials and
Its preparation method, but the invention is not limited in above-described embodiment, i.e. do not mean that the present invention has to rely on above-described embodiment
Can implement.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention, raw material each to product of the present invention
Equivalence is replaced and the interpolation of auxiliary element, concrete way choice etc., all fall within protection scope of the present invention and open scope it
In.
Claims (10)
1. the carbon fiber-reinforced resin composite materials containing phosphonitrile fire retardant, it is characterised in that described resin composite materials
Prepared by the component of following weight portion:
Carbon fiber-reinforced resin composite materials containing phosphonitrile fire retardant the most according to claim 1, it is characterised in that institute
State Halogen phosphonitrile fire retardant and there is structure shown in formula I:
In formula I, R1And R2Independently be any inertia nucleophilic group meeting its chemical environment, R3And R4For meeting its chemical environment
Any organic group, X1And X2Independently be-O-Ar-O-,-S-R5-S-、-NH-R6-NH-、-NH-R7-O-、-S-R11NH-、-O-R12COO-or-S-R13Any one in COO-, R5、R6、R7、R8、R9、R10、R11、R12
And R13For meeting any organic group of its chemical environment, Y1And Y2Independently be any nucleophilic group meeting its chemical environment
Group；M is ring three phosphonitrile base M1, ring more than four phosphonitrile base M2Or non-annularity polyphosphazene base M3In any one or at least two
Combination, m, n are the integer more than or equal to zero；A, b, c, d are the integer more than or equal to zero, and both c, d can not be zero simultaneously, and a+
B+c+d+2 is equal on M group 2 times of number of phosphorus atoms.
Carbon fiber-reinforced resin composite materials containing phosphonitrile fire retardant the most according to claim 2, it is characterised in that R1
And R2Independently be substituted or unsubstituted alkoxyl, substituted or unsubstituted cycloalkyloxy, substituted or unsubstituted aryloxy group,
Substituted or unsubstituted alkoxy aryl, substituted or unsubstituted heteroarylalkoxy, substituted or unsubstituted alkyl sulfenyl, take
Generation or unsubstituted artyl sulfo, substituted or unsubstituted carboxylic acid ester groups, substituted or unsubstituted carbonate group, replacement or do not take
Any one in the sulfonate group in generation or substituted or unsubstituted phosphonate group；Described alkoxyl, cycloalkyloxy, aryloxy group,
Alkoxy aryl, heteroarylalkoxy, alkyl sulfenyl, artyl sulfo, carbonate group, sulfonate group or the substituent group of phosphonate group
Independently be straight or branched alkyl, alkoxyl, cycloalkyloxy, aryl, aryloxy group, alkoxy aryl, heteroaryl, alkyl sulfide
Any one or the combination of at least two in base, artyl sulfo, carboxylic acid ester groups, carbonate group, sulfonate group or phosphonate group,
Described substituent group does not contains reactive end-capping group；
Preferably, R3And R4Independently be substituted or unsubstituted straight or branched alkylidene, substituted or unsubstituted sub-cycloalkanes
Base, substituted or unsubstituted arlydene, substituted or unsubstituted inferior heteroaryl, substituted or unsubstituted arlydene alkylene
Base, substituted or unsubstituted alkylenearylene, substituted or unsubstituted alkylidene inferior heteroaryl or substituted or do not take
Any one in the inferior heteroaryl alkylidene in generation；
Preferably, R5、R6、R7、R8、R11、R12And R13Independently be substituted or unsubstituted straight or branched alkylidene, substituted
Or it is unsubstituted cycloalkylidene, substituted or unsubstituted arlydene, substituted or unsubstituted inferior heteroaryl, substituted or not
Substituted arylidene alkylene, substituted or unsubstituted alkylenearylene, substituted or unsubstituted alkylidene Asia heteroaryl
Any one in base or substituted or unsubstituted inferior heteroaryl alkylidene；
Preferably, R9And R10Independently be substituted or unsubstituted straight or branched alkyl, substituted or unsubstituted cycloalkyl,
Substituted or unsubstituted alkoxyl, substituted or unsubstituted cycloalkyloxy, substituted or unsubstituted aryl, substituted or
Unsubstituted heteroaryl, substituted or unsubstituted substituted or unsubstituted aryloxy group, substituted or unsubstituted alkoxy aryl,
Substituted or unsubstituted alkyl-aryloxy, substituted or unsubstituted heteroarylalkoxy, substituted or unsubstituted alkoxyl heteroaryl
Base, substituted or unsubstituted heteroaryl oxyalkyl, substituted or unsubstituted miscellaneous alkyl aryl, substituted or unsubstituted alkyl virtue
Base, substituted or unsubstituted aryl alkyl, substituted or unsubstituted miscellaneous alkyl aryl, substituted or unsubstituted alkyl sulfenyl, take
Generation or unsubstituted artyl sulfo, substituted or unsubstituted carboxylic acid ester groups, substituted or unsubstituted carbonate group, replacement or do not take
Any one in the sulfonate group in generation or substituted or unsubstituted phosphonate group；
Preferably, Y1And Y2Independently be substituted or unsubstituted alkoxyl, substituted or unsubstituted cycloalkyloxy, replacement or not
Substituted aryloxy group, substituted or unsubstituted alkoxy aryl, substituted or unsubstituted heteroarylalkoxy, replacement or unsubstituted
Alkyl sulfenyl, substituted or unsubstituted artyl sulfo, substituted or unsubstituted carboxylic acid ester groups, substituted or unsubstituted carbonic ester
Any one in base, substituted or unsubstituted sulfonate group or substituted or unsubstituted phosphonate group；
Preferably, M1Structure is:
M2Structure is:
Wherein, x is more than or equal to 4；
M3Structure is:
Wherein, y is more than or equal to 3；
Preferably, M comprises at least 50wt%M1, at most 30wt%M2And at most 45wt%M3。
4. according to the carbon fiber-reinforced resin composite materials containing phosphonitrile fire retardant according to any one of claim 1-3, its
Being characterised by, described Halogen phosphonitrile fire retardant is to have a kind of in the compound of following structure or the combination of at least two:
Wherein M is ring three phosphonitrile base.
5. according to the carbon fiber-reinforced resin composite materials containing phosphonitrile fire retardant according to any one of claim 1-4, its
Being characterised by, described epoxy resin is liquid bisphenol A type epoxy resin, liquid bisphenol F type epoxy resin, solid-state bisphenol A-type ring
Epoxy resins, solid-state bisphenol f type epoxy resin, bisphenol-s epoxy resin, acyclic isoprenoid type epoxy resin or biphenyl type epoxy tree
The combination of a kind of or at least two in fat.
6. according to the carbon fiber-reinforced resin composite materials containing phosphonitrile fire retardant according to any one of claim 1-5, its
Being characterised by, described coupling agent is silane coupler and/or titanate coupling agent.
7. according to the carbon fiber-reinforced resin composite materials containing phosphonitrile fire retardant according to any one of claim 1-6, its
Being characterised by, described antioxidant is double (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphate, four-" 3-(3,5-bis-tertiary fourths
Base-4-hydroxy phenyl) propanoic acid) quaternary amyl alcohol ester, β (3,5-di-tert-butyl-hydroxy phenyl) propanoic acid octadecyl, (2,4,6-bis-
Tert-butyl-phenyl-2-butyl-2-ethyl)-1,3 one diol phosphite, 2,2 ' one ethylenebis (4,6-di-tert-butyls
Base) fluorophosphite, a kind of or at least two in two (2,4-bis-p-isopropyl phenyl) pentaerythritol bis-phosphite
Combination.
8. according to the carbon fiber-reinforced resin composite materials containing phosphonitrile fire retardant according to any one of claim 1-7, its
Being characterised by, described plasticizer is phthalic acid two (2-ethyl hexyl) ester, dioctyl phthalate or phthalic acid diformazan
Any one or the combination of at least two in ester.
9. prepare the carbon fiber-reinforced resin composite materials containing phosphonitrile fire retardant as according to any one of claim 1-8 for one kind
Method, it is characterised in that described method is: by carbon nano-fiber, phosphonitrile fire retardant, epoxy resin, coupling agent, antioxidant and
After plasticizer mixing, then plasticate, more mixing obtain the described carbon fiber-reinforced resin composite wood containing phosphonitrile fire retardant
Material.
Method the most according to claim 9, it is characterised in that described in the temperature plasticated be 120～150 DEG C, plasticate time
Between be 5～10min；
Preferably, described mixing temperature is 150～200 DEG C, and the mixing time is 15～30min.
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| CN108864168B (en) * | 2017-05-12 | 2020-10-20 | 苏州科技大学 | Preparation method and application of thiophenylmethyl pentaerythritol silicate |
| US11985841B2 (en) | 2020-12-07 | 2024-05-14 | Oti Lumionics Inc. | Patterning a conductive deposited layer using a nucleation inhibiting coating and an underlying metallic coating |
| CN113773506A (en) * | 2021-10-14 | 2021-12-10 | 中国电建集团中南勘测设计研究院有限公司 | Poly tetrabromo bisphenol A phosphazene flame retardant and resin matrix composite material |
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