CN107337695A - Phosphazene compound, plastic packaging material and composite metal substrate with azacyclo- - Google Patents
Phosphazene compound, plastic packaging material and composite metal substrate with azacyclo- Download PDFInfo
- Publication number
- CN107337695A CN107337695A CN201610290368.5A CN201610290368A CN107337695A CN 107337695 A CN107337695 A CN 107337695A CN 201610290368 A CN201610290368 A CN 201610290368A CN 107337695 A CN107337695 A CN 107337695A
- Authority
- CN
- China
- Prior art keywords
- unsubstituted
- substituted
- azacyclo
- group
- base
- 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.)
- Pending
Links
- -1 Phosphazene compound Chemical class 0.000 title claims abstract description 53
- 239000000758 substrate Substances 0.000 title claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 14
- 239000002184 metal Substances 0.000 title claims abstract description 14
- 239000002131 composite material Substances 0.000 title claims abstract description 12
- 239000004033 plastic Substances 0.000 title claims abstract description 7
- 239000005022 packaging material Substances 0.000 title claims abstract description 6
- 239000003822 epoxy resin Substances 0.000 claims abstract description 34
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 25
- ZSTLPJLUQNQBDQ-UHFFFAOYSA-N azanylidyne(dihydroxy)-$l^{5}-phosphane Chemical compound OP(O)#N ZSTLPJLUQNQBDQ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 11
- 125000004437 phosphorous atom Chemical group 0.000 claims abstract description 8
- 230000000269 nucleophilic effect Effects 0.000 claims abstract description 7
- 229920002627 poly(phosphazenes) Polymers 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 25
- 238000006467 substitution reaction Methods 0.000 claims description 18
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 14
- 125000004171 alkoxy aryl group Chemical group 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 10
- 125000000000 cycloalkoxy group Chemical group 0.000 claims description 10
- 125000001072 heteroaryl group Chemical group 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 125000004104 aryloxy group Chemical group 0.000 claims description 9
- 125000005587 carbonate group Chemical group 0.000 claims description 9
- 125000005114 heteroarylalkoxy group Chemical group 0.000 claims description 9
- 239000004411 aluminium Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- UXJHQBVRZUANLK-UHFFFAOYSA-N azanylidyne(dichloro)-$l^{5}-phosphane Chemical compound ClP(Cl)#N UXJHQBVRZUANLK-UHFFFAOYSA-N 0.000 claims description 8
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 7
- 125000003710 aryl alkyl 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
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 6
- 125000005248 alkyl aryloxy group Chemical group 0.000 claims description 5
- 125000005326 heteroaryloxy alkyl group Chemical group 0.000 claims description 5
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 4
- 239000011188 CEM-1 Substances 0.000 claims description 4
- 239000011190 CEM-3 Substances 0.000 claims description 4
- 101100257127 Caenorhabditis elegans sma-2 gene Proteins 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 125000004446 heteroarylalkyl group Chemical group 0.000 claims description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 claims description 3
- WCZVZNOTHYJIEI-UHFFFAOYSA-N cinnoline Chemical compound N1=NC=CC2=CC=CC=C21 WCZVZNOTHYJIEI-UHFFFAOYSA-N 0.000 claims description 3
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000838 Al alloy Inorganic materials 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 2
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 239000011152 fibreglass Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 125000002757 morpholinyl group Chemical group 0.000 claims description 2
- 125000004193 piperazinyl group Chemical group 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 125000003373 pyrazinyl group Chemical group 0.000 claims description 2
- 125000005493 quinolyl group Chemical group 0.000 claims description 2
- 238000002386 leaching Methods 0.000 claims 1
- 125000003226 pyrazolyl group Chemical group 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002585 base Substances 0.000 description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000003063 flame retardant Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 6
- 150000002118 epoxides Chemical class 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 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 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- SPWIPDSCASBWFH-UHFFFAOYSA-N [P].N#CC#N Chemical compound [P].N#CC#N SPWIPDSCASBWFH-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- XCJXQCUJXDUNDN-UHFFFAOYSA-N chlordene Chemical compound C12C=CCC2C2(Cl)C(Cl)=C(Cl)C1(Cl)C2(Cl)Cl XCJXQCUJXDUNDN-UHFFFAOYSA-N 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen 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
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 150000002825 nitriles Chemical group 0.000 description 4
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000010426 asphalt Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000004843 novolac epoxy resin Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- CUMCMYMKECWGHO-UHFFFAOYSA-N 3-methyl-1,2-oxazole Chemical compound CC=1C=CON=1 CUMCMYMKECWGHO-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229940126062 Compound A Drugs 0.000 description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 2
- 229910021295 PNCl2 Inorganic materials 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- SMYKVLBUSSNXMV-UHFFFAOYSA-K aluminum;trihydroxide;hydrate Chemical compound O.[OH-].[OH-].[OH-].[Al+3] SMYKVLBUSSNXMV-UHFFFAOYSA-K 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 229940106691 bisphenol a Drugs 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- VOOLKNUJNPZAHE-UHFFFAOYSA-N formaldehyde;2-methylphenol Chemical compound O=C.CC1=CC=CC=C1O VOOLKNUJNPZAHE-UHFFFAOYSA-N 0.000 description 2
- GPRDLRZMTVQCHM-UHFFFAOYSA-L magnesium;dihydroxide;hydrate Chemical compound O.[OH-].[OH-].[Mg+2] GPRDLRZMTVQCHM-UHFFFAOYSA-L 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 2
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ASOKPJOREAFHNY-UHFFFAOYSA-N 1-Hydroxybenzotriazole Chemical compound C1=CC=C2N(O)N=NC2=C1 ASOKPJOREAFHNY-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
- DWPYQDGDWBKJQL-UHFFFAOYSA-N 2-pyridin-4-ylethanol Chemical compound OCCC1=CC=NC=C1 DWPYQDGDWBKJQL-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- CZZRETSQGNWROP-UHFFFAOYSA-N CC(C[O-]1)(c2ccccc2)[NH+]1Oc(cc1)ccc1Nc(cc1)ccc1O[NH+](C)[O-] Chemical compound CC(C[O-]1)(c2ccccc2)[NH+]1Oc(cc1)ccc1Nc(cc1)ccc1O[NH+](C)[O-] CZZRETSQGNWROP-UHFFFAOYSA-N 0.000 description 1
- SLKITKSZXUPTIK-UHFFFAOYSA-N CN(O)Oc1ccccc1 Chemical compound CN(O)Oc1ccccc1 SLKITKSZXUPTIK-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 125000005213 alkyl heteroaryl group Chemical group 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001555 benzenes Chemical group 0.000 description 1
- 239000012964 benzotriazole 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
- 230000015556 catabolic process Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical group [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 125000000842 isoxazolyl group Chemical group 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 150000002576 ketones Chemical group 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 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
- 125000001624 naphthyl group Chemical group 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-methyl phenol Natural products CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 125000002971 oxazolyl group Chemical group 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
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- RDRCCJPEJDWSRJ-UHFFFAOYSA-N pyridine;1h-pyrrole Chemical class C=1C=CNC=1.C1=CC=NC=C1 RDRCCJPEJDWSRJ-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- RMBAVIFYHOYIFM-UHFFFAOYSA-M sodium methanethiolate Chemical compound [Na+].[S-]C RMBAVIFYHOYIFM-UHFFFAOYSA-M 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 125000005415 substituted alkoxy group Chemical group 0.000 description 1
- 125000005338 substituted cycloalkoxy group Chemical group 0.000 description 1
- 125000005346 substituted cycloalkyl group Chemical group 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6581—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/09—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/02—Coating on the layer surface on fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/021—Fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/101—Glass fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/106—Carbon fibres, e.g. graphite fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
- B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/546—Flexural strength; Flexion stiffness
-
- 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
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides containing the phosphazene compound with azacyclo-, plastic packaging material and composite metal substrate, the molecular structure having containing the phosphazene compound with azacyclo- as shown in formula I, in formula I, R is the nucleophilic group with azacyclo-；Y is the arbitrary non-reacted nucleophilic group for meeting its chemical environment；A is integer more than or equal to 1, and b is the integer more than or equal to zero, and a with b sums are number of phosphorus atoms in M groups 2 times；M is the phosphonitrile base M of ring three1, the phosphonitrile base M of ring more than four2Or non-annularity polyphosphazene base M3In one kind or at least two combination.It has good anti-flammability and dielectricity, and its composition epoxy resin is applied into composite metal substrate and wiring board can make it have good heat resistance, water resistance, cohesiveness, mechanical performance and dielectric properties.
Description
Technical field
The present invention relates to the technical field of fire retardant matter, more particularly to phosphazene compound, plastic packaging with azacyclo-
Material and composite metal substrate.
Background technology
Using mobile phone, computer, video camera, electronic game machine as representative electronic product, with air-conditioning, refrigerator,
Television image, sound equipment articles for use etc. use various for the family expenses of representative, office electric equipment products and other field
Product, for safety, significant portion of product requires that it possesses different degrees of fire resistance.
In order that product reaches required fire resistance or grade, traditional technology is usually used to material bodies
Such as metal hydroxides of aluminium hydroxide hydrate, magnesium hydroxide hydrate containing the crystallization water etc. is added in system
The inorganic fire-retarded material of class and addition such as brominated bisphenol A, bmminated bisphenol-A type asphalt mixtures modified by epoxy resin into system material
The brominated amount such as fat is higher or containing the higher organic chemicals of halogen quantity, contains halogen to improve these
The anti-flammability of the organic chemicals of element, also usually add in system such as antimony oxide to environment not
Friendly inorganic chemistry fire retardant material.
Due to using halogen-containing fire retardant matter, it can produce the Toxic of no degradability or difficult degradation when burning
Matter such as dioxin organic halogen chemical contamination environment, influence the mankind and animal health.
For the purpose of environmental protection, use is phosphorous, the not halogen-containing compound such as nitrogenous is replaced containing halogenated
Compound is as fire retardant, particularly on electronics, electric, Electric Industrial, using single official with reactivity
(there was only an active reactive group in a molecule), the miscellaneous -10- phospho hetero phenanthrenes -10- of 9,10- dihydro-9-oxies is aoxidized
Thing hereinafter referred to as DOPO), more be using DOPO derivative compound be used as flame-retardant composition, add
Or do not add aluminium hydroxide hydrate, magnesium hydroxide hydrate reaches fire-retardant effect.
In electronic applications, usually used DOPO and novolac type epoxy resin, o-cresol aldehyde asphalt mixtures modified by epoxy resin
The generation of the high costs such as fat, bisphenol-A phenolic type epoxy resin, polyfunctional epoxy resin and DOPO reactions
Thing (abbreviation DOPO epoxy resin) is extensively using the epoxide resin material as copper-clad plate purposes.
These have good fire resistance, but cohere using the copper-clad plate manufactured by DOPO epoxy resin
Property, heat resistance, processability etc. the defects of many be present, be not suitable for manufacturing the height that modern communicationses need more
Layer, high reliability, high cohesiveness, the product of excellent machinability, and due to high cost, no
The civil goods fields such as inexpensive consumer electronics are required beneficial to such as mobile phone is spread to.
With development of the electronic product to short, small, thin, high multiple stratification direction, people will to its high reliability
Further raising, and the factor such as increasingly severeer pollution pressure are asked, there is an urgent need to good in market
The copper-clad plate material of anti-flammability, heat resistance, good mechanical performance and the dielectric properties got well.
The content of the invention
In view of this, one aspect of the present invention provides a kind of phosphazene compound with azacyclo-, the phosphazene compound
With good flame-retardance, heat resistance, good mechanical performance and dielectric properties.
A kind of phosphazene compound with azacyclo-, it has the molecular structure as shown in formula I：
In formula I, R is the nucleophilic group with azacyclo-；Y is meet its chemical environment arbitrary non-anti-
Answering property nucleophilic group；A is the integer more than or equal to 1, and b is the integer more than or equal to zero, while a and b
Sum is 2 times of number of phosphorus atoms in M groups；M is the phosphonitrile base M of ring three1, the phosphonitrile base of ring more than four
M2Or non-annularity polyphosphazene base M3In one kind or at least two combination.
In the present invention, R Z-R1-O-、R2-Z-O-、Z-R3-S-、R4-Z-S-、Z-R5-NH-、R6-Z-NH-、Z-R9- COO- or R10Any one in-Z-COO-；Z is pyridine radicals, pyrimidine radicals, pyrrole
Oxazolyl, pyrazinyl, pyrrole radicals, imidazole radicals, morpholinyl, piperazinyl, oxazinyls, indyl, quinolyl,
Any one in benzimidazolyl, triazine radical, benzodiazine base, phentriazine base or BTA base；
R1、R3、R5、R7And R9Independently be substituted or unsubstituted straight or branched alkyl, substitution or not
Substituted cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substitution or
Unsubstituted aryl alkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted alkyl heteroaryl
Any one in base or substituted or unsubstituted heteroaryl alkyl；R2、R4、R6、R8And R10It is independent
Ground be substituted or unsubstituted straight or branched alkyl, substituted or unsubstituted cycloalkyl, substitution or not
Substituted alkoxy, substituted or unsubstituted cycloalkyloxy, substituted or unsubstituted aryl, substitution
Or unsubstituted heteroaryl, substituted or unsubstituted substituted or unsubstituted aryloxy group, substitution or unsubstituted
Alkoxy aryl, substituted or unsubstituted alkyl-aryloxy, substituted or unsubstituted heteroarylalkoxy,
Substituted or unsubstituted alkoxy heteroaryl, substituted or unsubstituted heteroaryl oxyalkyl, substitution or unsubstituted
Miscellaneous alkyl aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl alkyl, substitution or
Unsubstituted miscellaneous alkyl aryl, substituted or unsubstituted carboxylic acid ester groups, substituted or unsubstituted carbonate group,
Any one in substituted or unsubstituted sulfonate group or substituted or unsubstituted phosphonate group.
Preferably, Y be substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyloxy, substitution or
Unsubstituted aryloxy group, substituted or unsubstituted alkoxy aryl, substituted or unsubstituted heteroarylalkoxy,
Substituted or unsubstituted carboxylic acid ester groups, substituted or unsubstituted carbonate group, substituted or unsubstituted sulphonic acid ester
Any one in base or substituted or unsubstituted phosphonate group；The alkoxy, cycloalkyloxy, aryloxy group,
Alkoxy aryl, heteroarylalkoxy, carbonate group, sulfonate group or phosphonate group substituent independently
For straight or branched alkyl, alkoxy, cycloalkyloxy, aryl, aryloxy group, alkoxy aryl, heteroaryl,
In carboxylic acid ester groups, carbonate group, sulfonate group or phosphonate group any one or at least two combination,
The substituent does not contain reactive end-capping group.
In the present invention, the inertia end-capping group refers to that performance comparision is stable under the conditions of popular response, no
Continue to participate in the group of reaction；The reactive end-capping group refers to there is active chemical reactivity, can
The group of chemical reaction is participated in, carries not referring to containing OH ,-CN ,-NH in the present invention2、-SH、-COOH、
-CHO、-CONH2The group of isoreactivity group.Because Y is inertia end-capping group in the present invention,
Therefore it is the group for not containing the reactive end-capping 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.
As in the structural formula of phosphonitrile, it should be understood that the group being connected with M is the phosphorus for being connected to M
On atom, i.e., the side base on phosphorus atoms in M1, M2 and M3 structure.Further illustrate, M1,
Two singly-bounds occurred in M2 and M3 structures on P atoms are not to be construed as two methyl, two lists
Key is merely representative of M1, M2 and connects side base by its P atom with M3.
Pay attention to, M1、M2In the expression of structural formula, there is symbolOnly to " ring-type "
A kind of signal of structure.
In the present invention, substituted or unsubstituted straight chained alkyl or branched alkyl are preferably substituted or unsubstituted
C1~C12 (such as C1, C2, C3, C4, C5, C6, C7, C8, C9, C10 or C11) straight chain
Alkyl or branched alkyl, further preferred C1~C8 straight chained alkyls or branched alkyl, when carbon number is 1
When be methyl, when carbon number is 2, as 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 alkoxy be preferably substituted or unsubstituted C1~C12 (such as C2, C3,
C4, C5, C6, C7, C8, C9, C10 or C11) alkoxy.
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, more preferably substituting or do not take
The furyl or pyridine radicals in generation.
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 be preferably C7-C13 (such as C8, C9, C10, C11 or
C12) alkoxy aryl.
Substituted or unsubstituted heteroaryl alkyl be preferably C7-C13 (such as C8, C9, C10, C11 or
C12) heteroaryl alkyl.
Substituted or unsubstituted miscellaneous alkyl aryl be preferably C7-C13 (such as C8, C9, C10, C11 or
C12) miscellaneous alkyl aryl.
Substituted or unsubstituted alkoxy heteroaryl is preferably C7-C13 (such as C8, C9, C10, C11
Or C12) alkoxy heteroaryl.
Substituted or unsubstituted heteroarylalkoxy is preferably C7-C13 (such as C8, C9, C10, C11
Or C12) heteroarylalkoxy.
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) aralkyl
Epoxide.
Substituted or unsubstituted alkyl-aryloxy is preferably C7-C12 (such as C8, C9, C10 or C11)
Alkyl-aryloxy.
Term " substituted " used in the present invention refers to any one or more hydrogen atoms on specified atom
Substituted by the substituent selected from designated groups, condition is that the specified atom is no more than normal valency, and is substituted
Result be to produce stable compound.When substituent is oxo group or ketone group (i.e.=O), then
2 hydrogen atoms on atom are substituted.Ketone substituent is not present on aromatic rings." stable compound "
It is to refer to that sufficiently strong separation to effective purity and is configured to effective chemical combination from reactant mixture strongly
Thing.
In the present invention, M is the phosphonitrile base M of ring three1, the phosphonitrile base M of ring more than four2Or non-annularity polyphosphazene base
M3In one kind or at least two combination.
Preferably, M includes 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%,
M1For bulk composition.Work as M1When content is 100wt%, then M is not contained2And M3.Typical case of the invention but
Nonrestrictive M1Content 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%, that is, is referred to, M2Content can be 0~30wt%.
Work as M2When content is 0wt%, that is, refers 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%, that is, is referred to, M3Content can be 0~45wt%.
Work as M3When content is 0wt%, that is, refers 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%.
If M1Content is less than 50wt%, or M2More than 30wt%, then with the reacted life of epoxy resin
Heat resistance, water resistance and mechanical performance etc. will be damaged in use into thing must performance；M3Content extremely
Account for the 45% of phosphazenium groups gross mass more.If exceeding the content, exist with the reacted product of epoxy resin
It would be possible in use because viscosity is excessive, inconvenient for use, and its performance is damaged because molecular weight is excessive
The bad results such as evil.
In the structural formula I of the present invention, a is integer more than or equal to 1, for example, a can be but be not limited to 1,
2nd, 3,4,5,6,7,8,9 or 10, b be integer more than or equal to zero, such as b can be but unlimited
In 0,1,2,3,4,5,6,7,8,9 or 10.And a and b sums are phosphorus atoms in M groups
Several 2 times, that is, ensure that phosphorus atoms reach the saturation state that chemical valence is pentavalent on M.
Preferably, the phosphazene compound of the present invention with azacyclo- is one in the compound with following structure
Kind or at least two combination：
Wherein M is the phosphonitrile base of ring three.
Another aspect of the present invention provides a kind of preparation method of the phosphazene compound with azacyclo-, by party's legal system
Standby phosphazene compound has good flame-retardance, heat resistance, good mechanical performance.
A kind of to prepare the above-mentioned method for stating phosphazene compound, the phosphazene compound with azacyclo- is to pass through phosphorus
Nitrile chloride is carried out with nitrogen heterocyclic obtained by nucleophilic substitution.
In the present invention, in the phosphazene compound with azacyclo- in addition to azacyclo-, also with energy
Enough and phosphonitrile chloride carries out the active group of necleophilic reaction, such as-OH ,-NH2、-SH、-COOH、
- CN (can first be hydrolyzed into-COOH, then carry out necleophilic reaction with phosphonitrile chloride) etc., these groups can
To be connected directly on azacyclo-, can also be indirectly connected to by other groups on azacyclo-, it is described other
Group can be alkyl, cycloalkyl, aromatic radical etc..
Preferably, nitrogen heterocyclic be triazine, benzodiazine, 1,2,3- phentriazine -4- ketone, imidazoles,
Benzimidazolyl or benzotriazole compound.
Preferably, the structural formula of the phosphonitrile chloride is：Wherein a, b and Y
It is as defined above.The phosphonitrile chloride can be widest raw material hexachlorocyclotriph,sphazene, or using chlordene
The phosphonitrile of ring three is prepared using known method, can also be bought certainly from commercially available.
Preferably, the nitrogen heterocyclic is Wherein X is anti-for that nucleophilic displacement of fluorine can occur with phosphonitrile chloride
The group answered, R11、R12、R13、R14And R15Independently selected from H or meet that any of chemical environment has
Machine group；
Preferably, X is with-OH ,-NH2,-SH ,-COOH or-CN organic group in it is any
It is a kind of；Such as X can be but be not limited to-OH ,-NH2、-SH、-COOH、-CN、-CH2OH、
-CH2CH2SH、-CH2CH2NH2、-CH2SH、-CH2COOH、-CH2CH2CN、 In any one；
Preferably, R11、R12、R13、R14And R15Independently selected from H, substituted or unsubstituted straight chain or
Branched alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkoxy, substitution or not
Substituted cycloalkyloxy, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substitution or
Unsubstituted aryloxy group, substituted or unsubstituted alkoxy aryl, substituted or unsubstituted alkyl-aryloxy,
Substituted or unsubstituted heteroarylalkoxy, substituted or unsubstituted alkoxy heteroaryl, substitution or unsubstituted
Heteroaryl oxyalkyl, substituted or unsubstituted miscellaneous alkyl aryl, substituted or unsubstituted alkylaryl, take
Generation or unsubstituted aryl alkyl, substituted or unsubstituted miscellaneous alkyl aryl, substitution are unsubstituted or unsubstituted
Carboxylic acid ester groups, substituted or unsubstituted carbonate group, substituted or unsubstituted sulfonate group or substitution or not
Any one in substituted phosphonate group.
In the nucleophilic substitution, the chlorine in phosphonitrile chloride is substituted.Necleophilic reaction can use ability
Method known to domain is completed, such as refers to " progress of polyphosphazene, Zhang Hongwei etc., material Leader
The 7th phase of volume 24 in 2010 ".The instantiation of the catalyst used in necleophilic reaction has zinc chloride, chlorination
The lewis base such as the metal chlorides such as magnesium, aluminium chloride, boron trifluoride and its complex compound, sodium hydroxide.These
Catalyst can one or more be used in mixed way, the present invention in have no special regulation.Here " phosphorus cyanogen chlorination
Thing " refers to the compound that M groups are connected with Cl in formula (I).It can be used as phosphonitrile chloride
Known solvent, catalyst synthesize in known reaction scheme, can also be pressed using phosphorus pentachloride with ammonium chloride
It is synthesized according to known method after phosphorus chloride cyanogen compound, handles purification by physical method or do not purify straight
Manufacture is connect, its PCl5+NH4Cl→1/n(NPCl2) n+4HCl, it is mainly trimerization in the reaction product
Body (PNCl2)3(that is, hexachlorocyclotriph,sphazene) and the tetramer (PNCl2)4, reaction product is again by passing through 60 DEG C
Slowly distillation can obtain pure hexachlorocyclotriph,sphazene in vacuum.The phosphonitrile of chloro ring more than four and chloro non-annularity
Polyphosphazene can also be prepared by prior art.
Further aspect of the present invention offer is a kind of to have good flame-retardance, heat resistance, good mechanical performance and Jie
The composition epoxy resin of electrical property.
The composition epoxy resin includes the above-mentioned phosphazene compound with azacyclo-.
Known asphalt mixtures modified by epoxy resin can be used as the epoxy resin of composition epoxy resin, curing agent, other fillers
Fat.
Above-mentioned epoxy resin flame retardant can be according to being actually needed as plastic packaging material and pre-impregnated sheet.
A kind of pre-impregnated sheet, it is impregnated with or is coated on base material by fire-retardant combination described above and forms.
Preferably, the base material can be fiberglass substrate, polyester base material, polyimide base material, ceramics
Base material or carbon fiber base material etc..
In the present invention, it is not particularly limited for the concrete technology condition for being impregnated with or being coated with." pre-impregnated sheet "
" bonding sheet " being well known to those skilled in the art.
A kind of composite metal substrate, it covers metal by least one such as above-mentioned pre-impregnated sheet by carrying out surface successively
Layer is overlapping, pressing forms.
Preferably, the material of the surface metal-clad is the alloy of aluminium, copper, iron and its any combination.It is multiple
The instantiation for closing metal substrate has CEM-1 copper-clad plates, CEM-3 copper-clad plates, FR-4 copper-clad plates, FR-5
Appointing in copper-clad plate, CEM-1 aluminium bases, CEM-3 aluminium bases, FR-4 aluminium bases or FR-5 aluminium bases
Meaning is a kind of.
A kind of wiring board, formed in the Surface Machining circuit of above-mentioned composite metal substrate.
The raw material of above-mentioned composition epoxy resin or composition epoxy resin is by being solidificated in composite metal substrate
It is upper to form the coating with good flame-retardance energy, the anti-flammability, heat resistance, good machine of wiring board can be improved
Tool performance and low-dielectric energy, can be widely applied to electronic industry, electrically, Electric Industrial, communications and transportation,
The fields such as Aero-Space, toy industry.
Above-mentioned term " ××× base or group ", which refers in ××× molecular structure of compounds, sloughs one or more
Remaining part after hydrogen atom or other atoms or atomic group.
Relative to prior art, the invention has the advantages that：
The composition epoxy resin of the phosphazene compound with azacyclo- comprising the present invention, there is well fire-retardant
Property, its solidfied material has good heat resistance, water resistance, cohesiveness, mechanical performance and dielectric properties, is
A kind of fire retardant matter also with larger economy and environmentally friendly friendly.Covered by what said composition was prepared
The dielectric constant (1GHz) of copper coin is 3.25-3.32, and dielectric loss (1GHz) is 0.005-0.006, Tg
Can reach 155 DEG C and more than, T- peel strengths can reach 1.862kg/mm2More than and, interlaminar strength
It can reach 1.68kg/mm2More than and, saturated water absorption can reach less than 0.35%, and heat decomposition temperature is reachable
To 392 DEG C and more than, bending strength can reach 12.1kg/mm2More than and, flammability (UL-94) reaches
V-0 ranks.
Embodiment
Technical scheme is further illustrated with reference to embodiment.
Embodiment 1
The structural formula of the phosphazene compound of the present embodiment is as follows：
The phosphorus cyanogen 1mol of chlordene ring three, acetone are put into three mouthfuls of 2000ml glass reactors with agitating device
200ml, 2,4- dihydroxy -6- phenyl-triazine 3mol, sodium methoxide 3mol, stir, while lead to nitrogen,
60 DEG C are warming up to, 20% sodium hydroxide solution 620g is instilled with 60min, keeps 60 DEG C of temperature, stirring is instead
Answer 15 hours.After reaction, with inorganic constituents and moisture in the method removal system of physics, body is distilled
Solvent in system, obtains nitrogenous heterocyclic phosphazene compound 1mol, and this product is named as into A.
Proton nmr spectra sign is carried out to obtained compound A, it is as a result as follows：
1H NMR(CDCl3,500MHz):δ ppm 7.22-7.48 (m, 15H, phenyl ring on hydrogen), 5.0 (m,
3H,-OH),3.42(s,9H,OCH 3)。
The position of infrared spectrum characteristic peak：The characteristic absorption peak 1217cm of P=N keys in phosphazene backbone-1, phosphorus
P-N 874cm in nitrile skeleton-1, the absworption peak 2995cm- of methyl ether1, P-O-C key absworption peaks 1035cm-1,
CH2- O absworption peak 2983cm-1, triazine ring absworption peak, 3473-3121cm-1、1650cm-1、1457cm-1,
Single-substituted 770cm-1。
Using above-mentioned phosphazene compound A 132g as curing agent, the adjacent first that epoxide equivalent is 200g/eq is added
Novolac epoxy resin 100g, curing accelerator 2-methylimidazole 0.2g, prepares composition epoxy resin.Adopt
It is made with the composition epoxy resin according to general copper-clad plate production process and meets the standards such as national standard, UL
Standard copper-clad plate sample, a copper-clad plates are named as, test the performance of a copper-clad plates, its result table in table -1
Show.
Embodiment 2
The structural formula of the phosphazene compound of the present embodiment is as follows：
The phosphorus cyanogen 1mol of chlordene ring three, acetone are put into three mouthfuls of 2000ml glass reactors with agitating device
200ml, 4- pyridine ethanol 1mol, sodium methoxide 5mol, stir, while lead to nitrogen, one be warming up to 60 DEG C,
With 60min instill 20% sodium hydroxide solution 620g, keep 60 DEG C of temperature, 15 hours of stirring reaction,
After reaction, with inorganic constituents and moisture in the method removal system of physics, solvent in system is distilled, is obtained
Nitrogenous heterocyclic phosphazene compound 1mol, this product is named as B.
Proton nmr spectra sign is carried out to obtained compound B, it is as a result as follows：
1H NMR(CDCl3,500MHz):δ ppm 8.6 (m, 2H, the hydrogen on pyridine ring 2 and 6),
7.28 (m, 2H, the hydrogen on pyridine ring 3 and 5), 3.56 (m, 4H ,-CH 2CH 2OP-),2.0(s,15H,
-OCH 3)。
The position of infrared spectrum characteristic peak：The characteristic absorption peak 1217cm of P=N keys in phosphazene backbone-1, phosphorus
P-N 874cm in nitrile skeleton-1, the absworption peak 2995cm- of methyl ether1, P-O-C key absworption peaks 1035cm-1,
CH2- O absworption peak 2983cm-1, pyridine ring absworption peak, 3424cm-1、1511cm-1。
Using above-mentioned phosphazene compound B 206g as curing agent, the adjacent first that epoxide equivalent is 200g/eq is added
Novolac epoxy resin 100g, curing accelerator 2-methylimidazole 0.2g, prepares composition epoxy resin.Adopt
It is made with the composition epoxy resin according to general copper-clad plate production process and meets the standards such as national standard, UL
Standard copper-clad plate sample, b copper-clad plates are named as, test the performance of b copper-clad plates, its result table in table -1
Show.
Embodiment 3
The structural formula of the phosphazene compound of the present embodiment is as follows：
The phosphorus cyanogen 1mol of chlordene ring three, acetone are put into three mouthfuls of 2000ml glass reactors with agitating device
200ml, 1- hydroxy benzo triazole 1mol and sodium methoxide 5mol, stir, while leading to nitrogen, heat up
To 60 DEG C, 20% sodium hydroxide solution 621g is instilled with 60min, keeps 60 DEG C of temperature, stirring reaction 15
Individual hour, after reaction, with inorganic constituents and moisture in the method removal system of physics, distill molten in system
Agent, obtains nitrogenous heterocyclic phosphazene compound 1mol, and this product is named as into C.
Proton nmr spectra sign is carried out to obtained compound C, it is as a result as follows：
1H NMR(CDCl3,500MHz):δ5.1(m,1H,-POCHCH2OP-),4.1(s,2H,
-POCHCH 2OP-),3.42(s,21H,OCH 3),2.0(m,1H,-OH)。
The position of infrared spectrum characteristic peak：The characteristic absorption peak 1217cm of P=N keys in phosphazene backbone-1, phosphorus
P-N 874cm in nitrile skeleton-1, the absworption peak 2995cm- of methyl ether1, P-O-C key absworption peaks 1035cm-1,
CH2- O absworption peak 2983cm-1, BTA absworption peak, 3010cm-1、1625cm-1、1510cm-1,
Ortho position substituted benzene ring 750cm-1。
Using above-mentioned phosphazene compound C 210g as curing agent, the adjacent first that epoxide equivalent is 200g/eq is added
Novolac epoxy resin 100g, curing accelerator 2-methylimidazole 0.2g, prepares composition epoxy resin.Adopt
It is made with the composition epoxy resin according to general copper-clad plate production process and meets the standards such as national standard, UL
Standard copper-clad plate sample, c copper-clad plates are named as, test the performance of c copper-clad plates, its result table in table -1
Show.
Embodiment 4
The structural formula of the phosphazene compound of the present embodiment is as follows：
The phosphorus cyanogen 1mol of chlordene ring three, acetone are put into three mouthfuls of 2000ml glass reactors with agitating device
The methylisoxazole 1mol of 200ml, 3- hydroxyl -5, sodium methyl mercaptide 5mol, stir, while lead to nitrogen,
60 DEG C are warming up to, 20% sodium hydroxide solution 621g is instilled with 60min, keeps 60 DEG C of temperature, stirring is instead
10 hours are answered, after reaction, with inorganic constituents and moisture in the method removal system of physics, distill body
Solvent in system, obtains nitrogenous heterocyclic phosphazene compound 1mol, and this product is named as into D.
Proton nmr spectra sign is carried out to obtained compound D, it is as a result as follows：
1H NMR(CDCl3,500MHz):δ 7.2 (m, 1H, isoxazole ring hydrogen), 2.0 (s, 15H,
SCH 3), 2.36 (m, 3H, the hydrogen on methyl being connected with isozole ring).
The position of infrared spectrum characteristic peak：The characteristic absorption peak 1217cm of P=N keys in phosphazene backbone-1, phosphorus
P-N 874cm in nitrile skeleton-1, the absworption peak 2995cm- of methyl ether1, P-O-C key absworption peaks 1035cm-1,
CH2- O absworption peak 2983cm-1, methylisoxazole absworption peak, 1625cm-1、1500cm-1、1380cm-1、
1240cm-1。
Orthoresol of the epoxide equivalent as 200g/eq is added using above-mentioned phosphazene compound D 194g as curing agent
Formaldehyde epoxy resin 100g, curing accelerator 2-methylimidazole 0.2g, prepares composition epoxy resin.Using
The mark for meeting the standards such as national standard, UL is made according to general copper-clad plate production process for the composition epoxy resin
Quasi- copper-clad plate sample, d copper-clad plates are named as, test the performance of d copper-clad plates, its result represents in table -1.
Comparative example 1
Epoxide equivalent is 200g/eq o-cresol formaldehyde epoxy resin 200g, adds phenolic hydroxyl equivalent and is
105g/eq linear phenol-aldehyde resin curing agent 105g and as fire retardant hexaphenoxycyclotriphosphazene 70g with
And 0.2g 2-methylimidazole, solution is dissolved into appropriate butanone, with normal glass cloth, according to routine
Preparation method, obtain the copper-clad plate e that resinous amount is 50%, cover the copper e properties table in table -1
Show.
Comparative example 2
Epoxide equivalent is 200g/eq o-cresol formaldehyde epoxy resin 200g, and adding, there is formula (1) such as to tie
The resin compound 220g of structure, ester equivalent are 220g/eq and the hexaphenoxycyclotriphosphazene as fire retardant
70g and 0.2g pyridine azoles, solution is dissolved into appropriate butanone, with normal glass cloth, according to routine
Preparation method, obtain the copper-clad plate f that resinous amount is 50%.The properties for covering copper f represent in table -1.
Embodiment and the test result of comparative example are as shown in following table -1 (in view of specific method of testing has been this area
Known to technical staff, method is no longer described in detail at this).
Table -1
The test data of above table, show fire-retardant compound and its derivative of the present invention when use is in epoxy
When in resin curing system and other systems, there is good anti-flammability and dielectricity, its solidfied material has good
Heat resistance, water resistance, cohesiveness and mechanical performance well, electrical property.The fire-retardant compound category of the present invention
In the ring of low cost, the novel environmental friendly for the energy-saving and emission-reducing that raw material sources are abundant, properties are good
Guarantor's type anti-flammability material.
Applicant state, the present invention by above-described embodiment come illustrate the present invention containing the phosphonitrile with azacyclo-
Compound, plastic packaging material and composite metal substrate, but the invention is not limited in above-described embodiment, that is, do not mean that
The present invention, which has to rely on above-described embodiment, to be implemented.Person of ordinary skill in the field is it will be clearly understood that right
Any improvement of the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention are added, specifically
Way choice etc., within the scope of all falling within protection scope of the present invention and disclosing.
Claims (10)
1. a kind of phosphazene compound with azacyclo-, it is characterised in that it has the molecule as shown in formula I
Structure：
In formula I, R is the nucleophilic group with azacyclo-；Y is any non-reaction for meeting its chemical environment
Property nucleophilic group；A is integer more than or equal to 1, and b is the integer more than or equal to zero, and a and b sums
For 2 times of number of phosphorus atoms in M groups；M is the phosphonitrile base M of ring three1, the phosphonitrile base M of ring more than four2Or
Non-annularity polyphosphazene base M3In one kind or at least two combination.
2. the phosphazene compound according to claim 1 with azacyclo-, it is characterised in that R is
Z-R1-O-、R2-Z-O-、Z-R3-S-、R4-Z-S-、Z-R5-NH-、R6-Z-NH-、Z-R9-COO-
Or R10Any one in-Z-COO-；Z be pyridine radicals, pyrimidine radicals, pyrazolyl, pyrazinyl, pyrrole radicals,
Imidazole radicals, morpholinyl, piperazinyl, oxazinyls, indyl, quinolyl, benzimidazolyl, triazine radical,
Any one in benzodiazine base, phentriazine base or BTA base；R1、R3、R5、R7With
R9It independently is substituted or unsubstituted straight or branched alkyl, substituted or unsubstituted cycloalkyl, substitution
Or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted aryl alkyl,
Substituted or unsubstituted alkylaryl, substituted or unsubstituted miscellaneous alkyl aryl or substituted or unsubstituted
Heteroaryl alkyl in any one；R2、R4、R6、R8And R10It independently is substituted or unsubstituted
Straight or branched alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkoxy, substitution
Or unsubstituted cycloalkyloxy, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl,
Substituted or unsubstituted substituted or unsubstituted aryloxy group, substituted or unsubstituted alkoxy aryl, substitution
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, substitution
Or unsubstituted alkylaryl, substituted or unsubstituted aryl alkyl, substituted or unsubstituted miscellaneous alkyl aryl,
Substituted or unsubstituted carboxylic acid ester groups, substituted or unsubstituted carbonate group, substituted or unsubstituted sulphonic acid ester
Any one in base or substituted or unsubstituted phosphonate group；
Preferably, Y be substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyloxy, substitution or
Unsubstituted aryloxy group, substituted or unsubstituted alkoxy aryl, substituted or unsubstituted heteroarylalkoxy,
Substituted or unsubstituted carboxylic acid ester groups, substituted or unsubstituted carbonate group, substituted or unsubstituted sulphonic acid ester
Any one in base or substituted or unsubstituted phosphonate group；The alkoxy, cycloalkyloxy, aryloxy group,
Alkoxy aryl, heteroarylalkoxy, carbonate group, sulfonate group or phosphonate group substituent independently
For straight or branched alkyl, alkoxy, cycloalkyloxy, aryl, aryloxy group, alkoxy aryl, heteroaryl,
In carboxylic acid ester groups, carbonate group, sulfonate group or phosphonate group any one or at least two combination,
The substituent does not contain reactive end-capping 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.
3. the phosphazene compound according to claim 1 or 2 with azacyclo-, it is characterised in that M
Include at least 50wt%M1, at most 30wt%M2And at most 45wt%M3。
4. the phosphazene compound with azacyclo- according to any one of claim 1-3, its feature exist
In, the phosphazene compound with azacyclo- be a kind of in the compound with following structure or at least two
Combination：
Wherein M is the phosphonitrile base of ring three.
A kind of 5. side for preparing the phosphazene compound with azacyclo- as any one of claim 1-4
Method, it is characterised in that the phosphazene compound with azacyclo- is by phosphonitrile chloride and azacyclo- chemical combination
Thing is carried out obtained by nucleophilic substitution.
6. a kind of composition epoxy resin, it is characterised in that comprising any one of claim 1-4
The phosphazene compound with azacyclo-.
7. a kind of plastic packaging material, it is characterised in that it includes composition epoxy resin described in claim 6.
8. a kind of pre-impregnated sheet, it is characterised in that it is contained by composition epoxy resin as claimed in claim 6
Soak or be coated on base material and form；
Preferably, the base material is fiberglass substrate, polyester base material, polyimide base material, ceramic base material
Or carbon fiber base material.
9. a kind of composite metal substrate, it is characterised in that it is pre- as claimed in claim 7 by least one
Leaching plate carries out surface metal-clad successively, overlapping, pressing forms；
Preferably, the material of the surface metal-clad is the alloy of aluminium, copper, iron and its any combination；
Preferably, the composite metal substrate is that CEM-1 copper-clad plates, CEM-3 copper-clad plates, FR-4 cover copper
Plate, FR-5 copper-clad plates, CEM-1 aluminium bases, CEM-3 aluminium bases, FR-4 aluminium bases or FR-5 aluminium bases
Any one in plate.
10. a kind of wiring board, it is characterised in that in the surface of the composite metal substrate described in claim 9
Processing line forms.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610290368.5A CN107337695A (en) | 2016-05-03 | 2016-05-03 | Phosphazene compound, plastic packaging material and composite metal substrate with azacyclo- |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610290368.5A CN107337695A (en) | 2016-05-03 | 2016-05-03 | Phosphazene compound, plastic packaging material and composite metal substrate with azacyclo- |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107337695A true CN107337695A (en) | 2017-11-10 |
Family
ID=60222227
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610290368.5A Pending CN107337695A (en) | 2016-05-03 | 2016-05-03 | Phosphazene compound, plastic packaging material and composite metal substrate with azacyclo- |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107337695A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101560227A (en) * | 2009-05-26 | 2009-10-21 | 瓮福（集团）有限责任公司 | Flame-retarding compound, flame-retardant prepared thereby and preparation method thereof |
| CN102099942A (en) * | 2008-06-20 | 2011-06-15 | 巴斯夫欧洲公司 | Cyclic phosphazene compounds and use thereof in organic light emitting diodes |
-
2016
- 2016-05-03 CN CN201610290368.5A patent/CN107337695A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102099942A (en) * | 2008-06-20 | 2011-06-15 | 巴斯夫欧洲公司 | Cyclic phosphazene compounds and use thereof in organic light emitting diodes |
| CN101560227A (en) * | 2009-05-26 | 2009-10-21 | 瓮福（集团）有限责任公司 | Flame-retarding compound, flame-retardant prepared thereby and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| MIN ZHANG ET AL.: ""Dendritic organic–inorganic hybrid polyphenol and branched benzoxazine monomers with low curing temperature"", 《RSC ADV》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Phosphorus‐containing epoxy resin for an electronic application | |
| JP6318191B2 (en) | Flame retardant compounds, curing agents and polyphenolic epoxy resins | |
| CN105348563A (en) | Flame-retardant compound, flame-retardant epoxy resin and flame-retardant composition | |
| CN102369227A (en) | Phosphorus-containing phenol novolac resin, hardener comprising the same and epoxy resin composition | |
| CN107337694A (en) | A kind of phosphazene compound with silanol, fire retardant, composition epoxy resin and composite metal substrate | |
| CN105646862B (en) | Polyester, pre-impregnated sheet, composite metal substrate and wiring board containing phosphonitrile | |
| CN107522744A (en) | A kind of phosphazene compound, phosphonitrile epoxy resin, pre-impregnated sheet and composite metal substrate | |
| CN1238422C9 (en) | Phosphorus-containing nitrogen-containing halogen-free flame-retardant epoxy resin composition, and prepreg and laminated board containing composition | |
| CN104892898A (en) | Phosphorus-nitrogen epoxy resin with bisphenol S radicals, flame-retardant composition, composite metal substrate | |
| CN106946937A (en) | A kind of phosphazene compound of cyano-containing, preparation method and purposes | |
| CN107573485A (en) | Phosphazene compound, curing agent, composition epoxy resin, pre-impregnated sheet and composite metal substrate | |
| CN106916281A (en) | Flame-retardant compound, curing agent and polyphenol base epoxy | |
| EP3187501B1 (en) | A phosphazene compound, and a composition, a prepreg and a wiring board comprising the same | |
| CN107337696A (en) | Phosphazene compound, curing agent, phosphonitrile epoxy resin and composite metal substrate and plastic packaging material with aldehyde radical | |
| CN104893243B (en) | The curing agent and epoxy composite of the phosphorus-nitrogen compound of base containing bisphenol S | |
| CN107344952A (en) | A kind of phosphazene compound with alkynyl, composition epoxy resin, plastic packaging material and composite metal substrate | |
| CN105646588A (en) | Phosphazene compound with carboxylic ester, presoaked plate, composite metal substrate and circuit board | |
| CN107337695A (en) | Phosphazene compound, plastic packaging material and composite metal substrate with azacyclo- | |
| CN107337697A (en) | Phosphazene compound, plastic packaging material and the composite metal substrate of the base containing DOPO | |
| CN107337693A (en) | Phosphazene compound, plastic packaging material and composite metal substrate containing phosphinate | |
| CN104892906B (en) | The curing agent and epoxy composite of the phosphorus-nitrogen compound of phenolic group containing single aromatic ring | |
| CN103304809A (en) | Halogen-free flame-retardant prepolymer and prepreg and laminated board made from same | |
| CN107337698A (en) | Phosphazene compound, curing agent, phosphonitrile epoxy resin and composite metal substrate and plastic packaging material with amide groups | |
| CN107337806A (en) | Phosphazene compound, plastic packaging material and composite metal substrate containing phosphonate group | |
| TWI618713B (en) | Phosphazene compound, prepreg and composite metal substrate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20171110 |