CN108503671A - A kind of phosphazene compound containing benzoxazine, phosphonitrile composition epoxy resin, pre-impregnated sheet and composite metal substrate - Google Patents
A kind of phosphazene compound containing benzoxazine, phosphonitrile composition epoxy resin, pre-impregnated sheet and composite metal substrate Download PDFInfo
- Publication number
- CN108503671A CN108503671A CN201710108481.1A CN201710108481A CN108503671A CN 108503671 A CN108503671 A CN 108503671A CN 201710108481 A CN201710108481 A CN 201710108481A CN 108503671 A CN108503671 A CN 108503671A
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- CN
- China
- Prior art keywords
- phosphonitrile
- substituted
- unsubstituted
- epoxy resin
- anhydride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- -1 phosphazene compound Chemical class 0.000 title claims abstract description 104
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 49
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 48
- ZSTLPJLUQNQBDQ-UHFFFAOYSA-N azanylidyne(dihydroxy)-$l^{5}-phosphane Chemical compound OP(O)#N ZSTLPJLUQNQBDQ-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000000203 mixture Substances 0.000 title claims abstract description 36
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 15
- 239000002184 metal Substances 0.000 title claims abstract description 15
- 239000000758 substrate Substances 0.000 title claims abstract description 15
- 239000002131 composite material Substances 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims description 27
- 239000001257 hydrogen Substances 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000000126 substance Substances 0.000 claims description 21
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 20
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 238000006467 substitution reaction Methods 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 17
- 229920005989 resin Polymers 0.000 claims description 17
- 239000011347 resin Substances 0.000 claims description 17
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 125000004437 phosphorous atom Chemical group 0.000 claims description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 14
- 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 14
- 239000000853 adhesive Substances 0.000 claims description 13
- 230000001070 adhesive effect Effects 0.000 claims description 13
- 239000003063 flame retardant Substances 0.000 claims description 13
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 12
- 239000011521 glass Substances 0.000 claims description 10
- 125000000962 organic group Chemical group 0.000 claims description 10
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 claims description 8
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-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
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 8
- 239000000835 fiber Substances 0.000 claims description 8
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 8
- 150000008064 anhydrides Chemical group 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000003365 glass fiber Substances 0.000 claims description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 125000001118 alkylidene group Chemical group 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229920002627 poly(phosphazenes) Polymers 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 239000004305 biphenyl Substances 0.000 claims description 5
- 235000010290 biphenyl Nutrition 0.000 claims description 5
- 229940106691 bisphenol a Drugs 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 150000002576 ketones Chemical class 0.000 claims description 5
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical group CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic acid anhydride Natural products CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 4
- 150000008065 acid anhydrides Chemical class 0.000 claims description 4
- 125000004171 alkoxy aryl group Chemical group 0.000 claims description 4
- 125000004647 alkyl sulfenyl group Chemical group 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000004104 aryloxy group Chemical group 0.000 claims description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 4
- 238000002485 combustion reaction Methods 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- 125000005114 heteroarylalkoxy group Chemical group 0.000 claims description 4
- 239000003112 inhibitor Substances 0.000 claims description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 4
- 239000000347 magnesium hydroxide Substances 0.000 claims description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 4
- 229940043265 methyl isobutyl ketone Drugs 0.000 claims description 4
- 230000000269 nucleophilic effect Effects 0.000 claims description 4
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims description 4
- 150000003222 pyridines Chemical class 0.000 claims description 4
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 4
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 4
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 3
- 229930185605 Bisphenol Natural products 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 claims description 3
- 239000011888 foil Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229940014800 succinic anhydride Drugs 0.000 claims description 3
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 claims description 2
- URJFKQPLLWGDEI-UHFFFAOYSA-N 1-benzyl-2-methylimidazole Chemical compound CC1=NC=[C]N1CC1=CC=CC=C1 URJFKQPLLWGDEI-UHFFFAOYSA-N 0.000 claims description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 2
- MFGALGYVFGDXIX-UHFFFAOYSA-N 2,3-Dimethylmaleic anhydride Chemical compound CC1=C(C)C(=O)OC1=O MFGALGYVFGDXIX-UHFFFAOYSA-N 0.000 claims description 2
- ICQLQVWXFUWFRI-UHFFFAOYSA-N 2-(2-methylimidazol-1-yl)propanenitrile Chemical class N#CC(C)N1C=CN=C1C ICQLQVWXFUWFRI-UHFFFAOYSA-N 0.000 claims description 2
- YTWBFUCJVWKCCK-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole Chemical class CCCCCCCCCCCCCCCCCC1=NC=CN1 YTWBFUCJVWKCCK-UHFFFAOYSA-N 0.000 claims description 2
- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical compound C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-UHFFFAOYSA-N 0.000 claims description 2
- 150000004941 2-phenylimidazoles Chemical class 0.000 claims description 2
- FUOZJYASZOSONT-UHFFFAOYSA-N 2-propan-2-yl-1h-imidazole Chemical compound CC(C)C1=NC=CN1 FUOZJYASZOSONT-UHFFFAOYSA-N 0.000 claims description 2
- ACJPFLIEHGFXGP-UHFFFAOYSA-N 3,3-dimethyloxolane-2,5-dione Chemical class CC1(C)CC(=O)OC1=O ACJPFLIEHGFXGP-UHFFFAOYSA-N 0.000 claims description 2
- HMMBJOWWRLZEMI-UHFFFAOYSA-N 4,5,6,7-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CCCC2=C1C(=O)OC2=O HMMBJOWWRLZEMI-UHFFFAOYSA-N 0.000 claims description 2
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 claims description 2
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052582 BN Inorganic materials 0.000 claims description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- IWBUYGUPYWKAMK-UHFFFAOYSA-N [AlH3].[N] Chemical compound [AlH3].[N] IWBUYGUPYWKAMK-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 239000000010 aprotic solvent Substances 0.000 claims description 2
- 125000005605 benzo group Chemical group 0.000 claims description 2
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 claims description 2
- 125000006267 biphenyl group Chemical group 0.000 claims description 2
- 229910001593 boehmite Inorganic materials 0.000 claims description 2
- 235000012241 calcium silicate Nutrition 0.000 claims description 2
- 125000005587 carbonate group Chemical group 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- UQSHIDHNLKIYGN-UHFFFAOYSA-N diphenoxyphosphoryl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OP(=O)(OC=1C=CC=CC=1)OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 UQSHIDHNLKIYGN-UHFFFAOYSA-N 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 239000011152 fibreglass Substances 0.000 claims description 2
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 2
- 150000002460 imidazoles Chemical group 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims description 2
- 239000011325 microbead Substances 0.000 claims description 2
- 229910052863 mullite Inorganic materials 0.000 claims description 2
- FZZQNEVOYIYFPF-UHFFFAOYSA-N naphthalene-1,6-diol Chemical compound OC1=CC=CC2=CC(O)=CC=C21 FZZQNEVOYIYFPF-UHFFFAOYSA-N 0.000 claims description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 claims description 2
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 150000003003 phosphines Chemical class 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 2
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 238000005576 amination reaction Methods 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 239000012965 benzophenone Substances 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 150000001924 cycloalkanes Chemical class 0.000 claims 1
- 239000000395 magnesium oxide Substances 0.000 claims 1
- BYVCTYDTPSKPRM-UHFFFAOYSA-N naphthalene-1-carbonyl naphthalene-1-carboxylate Chemical class C1=CC=C2C(C(OC(=O)C=3C4=CC=CC=C4C=CC=3)=O)=CC=CC2=C1 BYVCTYDTPSKPRM-UHFFFAOYSA-N 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 229910001868 water Inorganic materials 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000005452 bending Methods 0.000 abstract description 3
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 229920006395 saturated elastomer Polymers 0.000 abstract description 3
- 239000002585 base Substances 0.000 description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 23
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical class CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 239000011889 copper foil Substances 0.000 description 8
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- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
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- 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 2
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- 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
- 239000010426 asphalt Substances 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 125000000000 cycloalkoxy group Chemical group 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 125000001072 heteroaryl group Chemical group 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 2
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000008054 signal transmission Effects 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
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- LEHNQGSPRXHYRT-UHFFFAOYSA-N 2-dodecyl-1h-imidazole Chemical class CCCCCCCCCCCCC1=NC=CN1 LEHNQGSPRXHYRT-UHFFFAOYSA-N 0.000 description 1
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- RDOXTESZEPMUJZ-UHFFFAOYSA-N COc1ccccc1 Chemical compound COc1ccccc1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 244000248349 Citrus limon Species 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
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- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004622 benzoxazinyl group Chemical group O1NC(=CC2=C1C=CC=C2)* 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
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- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 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
- VGGRCVDNFAQIKO-UHFFFAOYSA-N formic anhydride Chemical compound O=COC=O VGGRCVDNFAQIKO-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004043 oxo group Chemical group O=* 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 125000002653 sulfanylmethyl group Chemical group [H]SC([H])([H])[*] 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
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- 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
- C07F9/659—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 having three phosphorus atoms as ring hetero atoms in the same ring
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- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention provides a kind of phosphazene compound containing benzoxazine, phosphonitrile composition epoxy resin, pre-impregnated sheet and composite metal substrate, the phosphazene compound containing benzoxazine has molecular structure shown in formula I, the Tg for the copper-clad plate that the present invention is obtained using the phosphazene compound can reach 167 187 DEG C, and T peel strengths can reach 2.0kg/mm2More than, interlaminar strength can reach 1.90kg/mm2More than, saturated water absorption can reach 0.22% hereinafter, heat decomposition temperature can reach 420 DEG C or more, and bending strength can reach 12.6kg/mm2More than, flammability (UL 94) reaches 0 ranks of V, has good anti-flammability, good heat resistance, water resistance, cohesiveness and mechanical performance, electrical property.The preparation low cost of the phosphazene compound containing benzoxazine colophony of the present invention, raw material sources are abundant, properties are good, are with a wide range of applications.
Description
Technical field
The invention belongs to copper-clad plate technical field, it is related to a kind of phosphazene compound containing benzoxazine, phosphonitrile asphalt mixtures modified by epoxy resin
Fat, pre-impregnated sheet and composite metal substrate.
Background technology
Using mobile phone, computer, video camera, electronic game machine as the electronic product of representative, with air-conditioning, refrigerator, television image, sound
The various products that articles for use etc. use for the household of representative, office electric equipment products and other field are rung, for safety, significant portion
Product require that it has low-dielectric and heat resistance.
For electrical properties, the factor that need to mainly consider further includes the dielectric constant and dielectric loss of material.Generally
For, since the square root of the dielectric constant of the signal transmission speed and baseplate material of substrate is inversely proportional, therefore Jie of baseplate material
Electric constant is usually the smaller the better；On the other hand, the loss that signal transmission is represented since dielectric loss is smaller is fewer, therefore dielectric loss
The transmission quality that smaller material can be provided is also better.Therefore, how to develop with low-k and low Jie
The material of electrical loss, and be applied to the manufacture of high frequency printed circuit board is that printed circuit board material field is urgently at this stage
The problem of to be solved.
CN105112001A discloses a kind of three phosphonitrile type benzoxazine colophony of ring, three phosphonitrile type benzoxazine tree of the ring
Fat is below containing any one or the two or more mixtures in three phosphonitrile type benzoxazine chemical structural formula I-IV of ring：
Wherein, R=-CH3、-CH2CH3、 In any one.Although the invention is prepared by described containing three phosphonitrile type benzoxazine colophony of ring
Laminate there is good anti-flammability, heat resistance and lower absorptivity, but it is in dielectric constant, dielectric dissipation factor
And the performance of strength of glass etc. still waits further increasing.
Therefore, it is expected in the art using benzoxazine resinoid obtain it is a kind of have good flame-retardance, heat resistance with
And the laminate of good dielectric properties and mechanical performance.
Invention content
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of phosphazene compound containing benzoxazine,
Phosphonitrile epoxy resin, pre-impregnated sheet and composite metal substrate.
For this purpose, the present invention uses following technical scheme：
On the one hand, the present invention provides a kind of phosphazene compound containing benzoxazine, the phosphonitrile containing benzoxazine
Compound has molecular structure shown in formula I：
Wherein, M is three phosphonitrile base M of ring1, four or more phosphonitrile base M of ring2Or non-annularity polyphosphazene base M3In any one or
At least two combination；R1、R2、R3、R4、R5And R6It independently is the arbitrary organic group for meeting its chemical environment；X be-O- ,-
NH- ,-S- ,-COO- or-X1- R-, X1For any one in-O- ,-NH- ,-S- or-COO-, R is to meet its chemical environment
Arbitrary organic group；Y1And Y2It independently is the arbitrary organic group for meeting its chemical environment；A, b, d, e, f and g independently are big
In null integer, a+b+1 is equal to 2 times of phosphorus atoms number in M, and d+e+2 is equal to 2 times of phosphorus atoms number in M, and f+g+2 is equal to M
2 times of middle phosphorus atoms number, n are the integer more than or equal to zero.
In the present invention, described its chemical environment that meets is to refer to atom adjacent thereto to be connected, and obtains stable change
Learn connecting key.
Preferably, R1、R2、R3、R4、R5And R6It independently is the arbitrary inertia nucleophilic group for meeting its chemical environment or appoints
The reactive nucleophilic group of meaning.
Preferably, R1、R2、R3、R4、R5And R6It independently is substituted or unsubstituted alkoxy, substituted or unsubstituted ring
Alkoxy, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkoxy aryl, substituted or unsubstituted heteroarylalkoxy
Base, substituted or unsubstituted alkyl sulfenyl, substituted or unsubstituted artyl sulfo, substituted or unsubstituted carboxylate, substitution
Or it is any one in unsubstituted carbonate group, substituted or unsubstituted sulfonate group or substituted or unsubstituted phosphonate group
Kind.
Specifically, R1、R2、R3、R4、R5And R6CH can independently be3O-、HO-CH2O-、CH3CH2O-、CH3S-、
CH3CH2CH2S-、HS-CH2CH2CH2S-、CH3Any one in COO-, HO-PhO- or PhO- (Ph indicate phenyl).
R in the present invention1、R2、R3、R4、R5And R6Can be identical group may be different group.
Preferably, R is substituted or unsubstituted straight-chain alkyl-sub, substituted or unsubstituted branched alkylidene, substitution or not
Substituted arlydene, substituted or unsubstituted alkylenearylene, substituted or unsubstituted arylidene alkylene or substitution is
Any one in substituted cycloalkylidene.
Specifically, R can be-CH2CH2-、
Deng.
Preferably, Y1And Y2It independently is any one in-NH-R'- ,-O-R'- ,-S-R'- or-OOC-R'-, R' is
Substituted or unsubstituted straight-chain alkyl-sub, substituted or unsubstituted branched alkylidene, substituted or unsubstituted arlydene, substitution or
Unsubstituted alkylenearylene, substituted or unsubstituted arylidene alkylene or substitution are appointing in substituted cycloalkylidene
Meaning is a kind of.
Specifically, R' can be-CH2CH2-、
Deng.
In the present invention, the substituted or unsubstituted alkoxy be preferably C1~C12 (such as C2, C3, C4, C5,
C6, C7, C8, C9, C10 or C11) substituted or unsubstituted alkoxy.
Substituted or unsubstituted cycloalkyloxy is preferably C3~C12 (such as C4, C5, C6, C7, C8, C9, C10 or C11)
Substituted or unsubstituted cycloalkyloxy.
Substituted or unsubstituted aryloxy group be preferably C6-C13 (such as C7, C8, C9, C10, C11 or C12) substitution or not
Substituted aryloxy group.
Substituted or unsubstituted alkoxy aryl is preferably C7-C12 (such as C8, C9, C10 or C11) substitutions or unsubstituted
Alkoxy aryl.
Substituted or unsubstituted heteroarylalkoxy be preferably C7-C13 (such as C8, C9, C10, C11 or C12) substitution or
Unsubstituted heteroarylalkoxy.
Substituted or unsubstituted alkyl sulfenyl be preferably C1-C8 (such as C1, C2, C3, C4, C5, C6, C7 or C8) substitution or
Unsubstituted alkyl sulfenyl.
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 that C5-C13 (such as C6, C7, C8, C9, C10, C11 or C12) takes
Generation or unsubstituted inferior heteroaryl.
Substituted or unsubstituted alkylenearylene is preferably C7-C13 (such as C8, C9, C10, C11 or C12) substitutions
Or unsubstituted alkylenearylene.
Substituted or unsubstituted arylidene alkylene is preferably C7-C13 (such as C8, C9, C10, C11 or C12) substitutions
Or unsubstituted alkylenearylene.
Substituted or unsubstituted artyl sulfo is that preferably C7-C12 (such as C8, C9, C10 or C11) replaces or does not take
The artyl sulfo in generation.
Term " substituted " used in the present invention refer to any one or more hydrogen atoms on specified atom by selected from
The substituent group of designated groups replaces, and condition is that the specified atom is no more than normal valency, and replaces the result is that generating stabilization
Compound.When substituent group is oxo group or ketone group (i.e.=O), then 2 hydrogen atoms on atom are substituted.Ketone replaces
Base is not present on aromatic rings." stable compound " be refer to it is sufficiently strong strongly from reaction mixture separation to effective
Purity is simultaneously configured to compounds effective.
In the present invention, M is three phosphonitrile base M of ring1, four or more phosphonitrile base M of ring2, 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%, M1Based at
Point.Work as M1When content is 100wt%, then M is not contained2And 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%, that is, is referred to, M2Content can be 0~30wt%.Work as M2Content is
When 0wt%, that is, refer to, does 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 M3Content is
When 0wt%, that is, refer to, does 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 M3The sum of mass percent is 100%.
In the structural formula I of the present invention, a, b, d, e, f and g independently are the integer more than or equal to zero, such as can be 0,
1,2,3,4,5 or 6 etc..
In the structural formula I of the present invention, the group being connect with M is connect with the phosphorus atoms in M.And in formula
For a+b+1 equal to 2 times of phosphorus atoms number in M, d+e+2 is equal to 2 times of phosphorus atoms number in M in I, and f+g+2 is equal to phosphorus atoms number in M
2 times, that is, ensure that phosphorus atoms reach the saturation state that chemical valence is pentavalent on M.
In the structural formula I of the present invention, n is integer more than or equal to zero, for example, n can be 0,1,2,3,4,5,6,7,8,
9 or 10.Preferably, n is the integer more than zero, it is highly preferred that n is the integer of 1-10, further preferred n is the integer of 1-5.
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 that M1、M2In the expression of structural formula, occurred symbolOnly to one kind of " ring-type " structure
Signal.
Preferably, the phosphazene compound containing benzoxazine is in the compound of structure as shown in following formula a-f
It is a kind of or at least two combination：
Wherein M is three phosphazenium groups of ring, and n is the integer more than or equal to zero, and preferably n is the integer of 1-10, further preferred n
For the integer of 1-5.
On the other hand, the present invention provides a kind of preparation method of the phosphazene compound containing benzoxazine as described above,
It the described method comprises the following steps：
(1) phosphazene compound containing benzoxazine passes through shown in phosphonitrile diamine compound shown in Formula II and formula III
Polymerizate shown in formula IV is obtained by the reaction in phosphonitrile oxybenzene compound and formaldehyde, and reaction equation is as follows：
(2) polymerizate shown in formula IV is obtained by the reaction with phosphonitrile chloride shown in Formula V contains Ben Bing Evil shown in Formulas I
The phosphazene compound of piperazine, reaction equation are as follows：
Wherein, M is three phosphonitrile base M of ring1, four or more phosphonitrile base M of ring2Or non-annularity polyphosphazene base M3In any one or
At least two combination；R1、R2、R3、R4、R5And R6It independently is the arbitrary organic group for meeting its chemical environment；X be-O- ,-
NH- ,-S- ,-COO- or-X1- R-, X1For any one in-O- ,-NH- ,-S- or-COO-, R is to meet its chemical environment
Arbitrary organic group；Y1And Y2It independently is the arbitrary organic group for meeting its chemical environment；A, b, d, e, f and g independently are big
In null integer, a+b+1 is equal to 2 times of phosphorus atoms number in M, and d+e+2 is equal to 2 times of phosphorus atoms number in M, and f+g+2 is equal to M
2 times of middle phosphorus atoms number, n are the integer more than or equal to zero.
Preferably, phosphonitrile diamine compound shown in step (1) described Formula II and phosphonitrile oxybenzene compound shown in formula III
Molar ratio be 1:(1-1.5), such as 1:1、1:1.1、1:1.2、1:1.3、1:1.4 or 1:1.5.
Preferably, the molar ratio of phosphonitrile diamine compound and formaldehyde shown in step (1) described Formula II is 1:(2-2.5),
Such as 1:2、1:2.1、1:2.2、1:2.3、1:2.4 or 1:2.5.
Preferably, the temperature of step (1) described reaction be 80-120 DEG C, such as 80 DEG C, 85 DEG C, 90 DEG C, 95 DEG C, 100 DEG C,
105 DEG C, 110 DEG C, 115 DEG C or 120 DEG C.
Preferably, the time of step (1) described reaction be 2-10h, such as 2h, 2.5h, 3h, 3.5h, 4h, 5h, 6h, 7h,
8h, 9h or 10h.
Preferably, the solvent of step (1) described reaction is DMF or Isosorbide-5-Nitrae-dioxane.
Preferably, phosphonitrile diamine compound shown in step (1) described Formula II and phosphonitrile shown in step (2) described Formula V
The molar ratio of chloride is 1:(2-5), such as 1:2、1:2.3、1:2.5、1:2.8、1:3、1:3.2、1:3.4、1:3.6、1:
3.8、1:4、1:4.2、1:4.5、1:4.8 or 1:5.
Preferably, the temperature of step (2) described reaction be 60-80 DEG C, such as 60 DEG C, 63 DEG C, 65 DEG C, 68 DEG C, 70 DEG C, 72
DEG C, 75 DEG C, 78 DEG C or 80 DEG C.
Preferably, the time of step (2) described reaction be 2-8h, such as 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h,
5.5h, 6h, 6.5h, 7h, 7.5h or 8h.
Preferably, step (2) carries out in the presence of a basic；
Preferably, the alkaline matter is any one in sodium hydroxide, potassium hydroxide or ammonium hydroxide or at least two
Combination.
Preferably, the solvent of step (2) described reaction is DMF or Isosorbide-5-Nitrae-dioxane.
The used raw material in preparation method of the present invention, such as phosphonitrile diamine compound shown in the Formula II,
Phosphonitrile chloride can be obtained according to prior art preparation shown in phosphonitrile oxybenzene compound, Formula V shown in formula III, or
It can be by being commercially available.The preparation of these raw materials is prepared by phosphonitrile chloride by nucleophilic substitution, is prepared
Chlorine atom in journey in phosphonitrile chloride occurs nucleophilic substitution to nucleopilic reagent and obtains the phosphonitrile with corresponding substituent group
Compound, such as when preparing phosphonitrile diamine compound, be using phosphonitrile chloride and the suitable nucleopilic reagent with amino into
Row reaction is obtained containing there are two the phosphazene compounds of amino.The specific example of the catalyst used in necleophilic reaction have zinc chloride,
The metal chlorides such as magnesium chloride, aluminium chloride either lewis bases such as boron trifluoride and its complex compound or sodium hydroxide.These are urged
Agent one or more can be used in mixed way, and special regulation is had no in the present invention.Here " phosphonitrile chloride " refers to M in formula (I)
Compound made of group is connected with Cl.Well known solvent, catalyst can be used in well known anti-as for phosphonitrile chloride
It answers route to synthesize, phosphorus pentachloride can also be used to be synthesized according to known methods after phosphonitrilic chloride compound with ammonium chloride,
Purification is handled by physical method or does not purify direct manufacture, PCl5+NH4Cl→1/n(NPCl2) n+4HCl, the reaction product
In for mainly tripolymer (PNCl2)3(that is, hexachlorocyclotriph,sphazene) and the tetramer (PNCl2)4, reaction product is again by passing through
Slowly distillation can obtain pure hexachlorocyclotriph,sphazene in 60 DEG C of vacuum.Four or more phosphonitrile of chloro ring and chloro non-annularity polyphosphazene
It can also be prepared by prior art.
On the other hand, the present invention provides a kind of phosphonitrile composition epoxy resin, and it includes contain Ben Bing Evil as described above
The phosphazene compound and epoxy resin of piperazine.
Preferably, mass percent of the phosphazene compound containing benzoxazine in phosphonitrile composition epoxy resin
For 1-20%, such as 1%, 3%, 5%, 8%, 10%, 12%, 15%, 18% or 20%, preferably 5-10%.
Due to containing multiple phosphazenium groups and benzoxazinyl group in the phosphazene compound of the present invention, its resistance is substantially increased
Fire performance, the flame retardant property of bigger can be played when it is applied, when applied to phosphonitrile composition epoxy resin, can with compared with
Few flame retardant effect for measuring excellent, in addition, phosphorus of the phosphazene compound containing benzoxazine of the present invention compared with small molecule
Nitrile compound, it is more preferable with the compatibility of epoxy resin, can composition be had when composition is used to prepare copper-clad plate
Better compatibility so that the cooperation between component is better able to reach preferable state, and obtains whole more excellent property
Energy.
Preferably, the epoxy resin is liquid bisphenol A types epoxy resin, liquid bisphenol F types epoxy resin, solid-state bis-phenol
A types epoxy resin, solid-state bisphenol f type epoxy resin resin, bisphenol-s epoxy resin, biphenyl type epoxy resin, phenol aldehyde type epoxy resin
In dicyclopentadiene type epoxy resin any one or at least two mixture.
Preferably, the phosphonitrile composition epoxy resin further includes curing agent；
Preferably, the curing agent is anhydride curing agent or active ester curing agent.
Preferably, the anhydride curing agent be selected from maleic anhydride of styrene, methyl vinyl ether-maleic acid copolymer,
Methyl hexahydrophthalic anhydride, hexahydrophthalic anhydride, phenylsuccinic acid acid anhydride, succinic anhydride, oxa- acid anhydrides, dimethyl maleic anhydride, glutaric anhydride,
2- methyl succinics acid anhydrides, phthalic anhydride, norbornene dianhydride, four acid anhydride of equal benzene, 1,2- cyclohexyl dicarboxylic acids acid anhydride, 4- fluorine neighbours benzene two
Formic anhydride, 3- difluorophthalic anhydrides, 2,2- dimethyl succinic anhydrides, 1,1- cyclohexanediacetic acids acid anhydride, phenyl cis-butenedioic anhydride, lemon health
Acid anhydride, 1,8- naphthalic anhydrides, 4,4 '-biphenyl ether dianhydrides, 3,3'4,4'- bibenzene tetracarboxylic dianhydrides, equal benzene dianhydride, 3,3'4,4'-
Dianhydride diphenyl ether, 4,4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids, 1,2,3,4- cyclobutanetetracarboxylics dianhydride, 3,3'4,4'- hexichol first
Ketone tetracarboxylic dianhydride, 1,4,5,8- benzene tetracarboxylic acids acid anhydride, -1,4,9,10- tetrabasic carboxylic acids acetic anhydride, 3,4,5,6- tetrahydrophthalic anhydride or cis-
In 1,2,3,6- tetrabydrophthalic anhydrides any one or at least two mixture.
Preferably, the phosphonitrile composition epoxy resin further includes curing accelerator.
Preferably, the curing accelerator is imidazoles or pyridine compounds and their.
Preferably, the glyoxaline compound is selected from 2-methylimidazole, -4 methylimidazole of 2- ethyls, 2- phenylimidazoles, 2-
Undecyl imidazole, 1 benzyl 2 methyl imidazole, 2- heptadecyl imidazoles, 2 isopropyl imidazole, 2- phenyl -4-methylimidazole,
In 2- dodecyl imidazoles or 1- 1-cyanoethyl-2-methylimidazoles any one or at least two mixture.
Preferably, the pyridine compounds and their is 4-dimethylaminopyridine.
Preferably, the resin combination also includes fire retardant.
Preferably, the fire retardant is selected from organic fire-retardant and/or inorganic combustion inhibitor；
Preferably, the organic fire-retardant is selected from three (2,6- 3,5-dimethylphenyl) phosphines, bis- [two (2, the 6- diformazans of resorcinol
Base phenyl) phosphate], resorcinol tetraphenyldiphosphate, triphenyl phosphate, bisphenol-A bis- (diphenyl phosphoesters), phosphonitrile resistance
Fire agent, 10- (2,5- dihydroxy phenyls) -10- hydrogen -9- oxa- -10- phosphine phenanthrene -10- oxides, 10- (2,5- dihydroxy naphthalene) -
In 10- hydrogen -9- oxa-s -10- phosphines phenanthrene -10- oxides or the miscellaneous -10- phospho hetero phenanthrenes -10- oxide fire retardants of 9,10- dihydro-9-oxies
Any one or at least two mixture.
Preferably, any one of the inorganic combustion inhibitor in red phosphorus, aluminium hydroxide, magnesium hydroxide or antimony trioxide
Or at least two mixture.
Preferably, the phosphonitrile composition epoxy resin also includes filler.
Preferably, the filler is selected from silica, kaolin, talcum powder, magnesium hydroxide, aluminium hydroxide, boehmite, water
Talcum, titanium oxide, calcium silicates, beryllium oxide, boron nitride, glass powder, zinc borate, aluminium nitrogen compound, silicon nitride, silicon carbide, oxidation
Magnesium, zirconium oxide, mullite, titanium dioxide, potassium titanate, hollow glass microbead, polytetrafluorethylepowder powder, polystyrene powder, titanium
In sour potassium fiber, carborundum mono-crystal fiber, silicon nitride fiber, alumina single crystal fiber or staple glass fibre any one or extremely
Few two kinds of mixture.
On the other hand, the present invention provides a kind of resin adhesive liquid, and the resin adhesive liquid is by phosphonitrile asphalt mixtures modified by epoxy resin as described above
Oil/fat composition is dissolved or dispersed in solvent and obtains.
Preferably, the solvent is one kind or at least two in ketone, hydro carbons, ethers, esters or aprotic solvent
Combination, preferably acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), toluene, dimethylbenzene, methanol, ethyl alcohol, primary alconol, ethylene glycol list first
Ether, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, ethyl acetate, N,N-dimethylformamide or N, N- diethylformamides
In it is a kind of or at least two mixture.The solvent can be used alone, and can also be used in mixed way.Preferably, such as fourth is selected
Each ingredient such as ketone has the organic solvent that good dissolubility, toxicity is not strong, boiling point is more moderate；If in epoxy resin ingredient
Containing the substance that the crystallinity such as dicyandiamide not readily dissolve, part or all of nitrogenous class such as DMF, DMAC etc. can be used organic molten
Agent.It is understood that solvent is can to improve the speed of volatilization by heating in solidification process.
On the other hand, the present invention provides a kind of pre-impregnated sheet, and the pre-impregnated sheet is impregnated with or is coated with by resin adhesive liquid as described above
It is formed in base material.
Preferably, the base material is fiberglass substrate, polyester base material, polyimide base material, ceramic base material or carbon fiber
Base material.
In the present invention, the concrete technology condition for being impregnated with or being coated with is not particularly limited." pre-impregnated sheet " is also this field skill
" bonding sheet " known to art personnel.
On the other hand, the present invention provides a kind of composite metal substrate, and the composite metal substrate contains at least one as above
The metal foil of the pre-impregnated sheet and the pre-impregnated sheet one or both sides being overlying on after overlapping.
In the present invention, the metal foil can be the alloy arbitrarily combined in aluminium foil, copper foil, iron foil and aluminium, copper and iron
Foil.
On the other hand, the present invention provides a kind of wiring board, is formed in the surface processing line of above-mentioned composite metal substrate.
Compared with the existing technology, the invention has the advantages that：
The Tg for the copper-clad plate that the present invention is obtained using the phosphazene compound containing benzoxazine colophony can reach 167-187
DEG C, T- peel strengths can reach 2.0kg/mm2More than, interlaminar strength can reach 1.90kg/mm2More than, saturated water absorption can
Reach 0.22% hereinafter, heat decomposition temperature can reach 420 DEG C or more, bending strength can reach 12.6kg/mm2More than, flammability
(UL-94) reach V-0 ranks, show the solidfied material that the phosphazene compound containing benzoxazine colophony of the present invention is prepared,
With good anti-flammability, good heat resistance, water resistance, cohesiveness and mechanical performance, electrical property.The present invention's contains benzo
The phosphazene compound of oxazine resin belongs to low cost, raw material sources enrich, properties are good, is with a wide range of applications.
Specific implementation mode
The technical solution further illustrated the present invention below by specific implementation mode.Those skilled in the art should be bright
, the embodiment, which is only to aid in, understands the present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
In the present embodiment, it is prepared by the following method the phosphazene compound containing benzoxazine：
Three phosphonitrile diamine compound of 1mol rings is added in three mouthfuls of 2000mL glass reactors with agitating deviceThree phosphonitrile oxybenzene compound of 1,4- dioxane 500mL, 1mol ringFormaldehyde 2mol reacts 6h at 100 DEG C, is cooled to 60 DEG C, on one side stir, while
Logical nitrogen, and 20% sodium hydroxide solution 620g is instilled in backward reaction vessel, 2mol phosphonitrile chlorides are then added3h is reacted, the insoluble matter in removal system distills solvent in system, obtains having following knot
The phosphazene compound of structure：
, wherein M is three phosphazenium groups of ring, n=1.
Its nuclear-magnetism characterize data is as follows：
1H NMR(CDCl3,500MHz):6.6-6.7 (m, 4H,Hydrogen on phenyl ring on group), 6.3-6.5
(m, 9H, hydrogen on phenyl ring in benzoxazine ring), 5.0 (d, 6H,Hydrogen on group on the positions *), 3.6 (d, 6H,Hydrogen on group on the positions *), 3.4 (t, 54H, OCH 3),2.9(d,4H,-NHCH 2CH 2NH-),2.75(d,6H,Hydrogen on group on the positions *), 2.6 (d, 6H,On group on the positions *
Hydrogen), 2.0 (t, 24H, SCH 3)。
The position of infrared spectrum characteristic peak：The characteristic absorption peak 1217cm of P=N keys in phosphazene backbone-1, P- in phosphazene backbone
N 874cm-1, the absorption peak 2995cm of methyl ether-1, the absorption peak 1070cm of thioether bond-1, P-O-C key absorption peaks 1035cm-1, benzene
Ar-O ehter bonds stretching vibration characteristic peak 1246cm in Bing oxazines-1, the characteristic absorption peak 931cm of Liu Yuan oxazine rings-1And 928cm-1。
Embodiment 2
In the present embodiment, it is prepared by the following method the phosphazene compound containing benzoxazine：
Three phosphonitrile diamine compound of 1mol rings is added in three mouthfuls of 2000mL glass reactors with agitating deviceThree phosphonitrile phenol chemical combination of 1,4- dioxane 500mL, 1.2mol ring
ObjectFormaldehyde 2.3mol reacts 2h at 80 DEG C, is cooled to 60 DEG C, on one side stirring, one
Side leads to nitrogen, and instills 20% sodium hydroxide solution 620g in backward reaction vessel, and 2.5mol phosphonitrile chlorides are then added2h is reacted, the insoluble matter in removal system distills solvent in system, obtains having following knot
The phosphazene compound of structure：
, wherein M is three phosphazenium groups of ring, n=1.
Its nuclear-magnetism characterize data is as follows：
1H NMR(CDCl3,500MHz):6.7-7.1 (m, 80H,Hydrogen on phenyl ring on group), 6.5 (m, 4H,Hydrogen on phenyl ring on group), 6.3-6.5 (m, 9H, hydrogen on phenyl ring in benzoxazine ring), 5.0 (d, 6H,Hydrogen on group on the positions *), 3.6 (d, 6H,Hydrogen on group on the positions *), 3.4 (t, 30H,
OCH 3),2.9(d,4H,-NHCH 2CH 2NH-),2.75(d,6H,Hydrogen on group on the positions *), 2.6
(d,6H,Hydrogen on group on the positions *).
The position of infrared spectrum characteristic peak：The characteristic absorption peak 1217cm of P=N keys in phosphazene backbone-1, P- in phosphazene backbone
N 874cm-1, the absorption peak 2995cm of methyl ether-1, P-O-C key absorption peaks 1035cm-1, Ar-O ehter bonds are flexible in benzoxazine shakes
Dynamic characteristic peak 1246cm-1, the characteristic absorption peak 931cm of Liu Yuan oxazine rings-1And 928cm-1。
Embodiment 3
In the present embodiment, it is prepared by the following method the phosphazene compound containing benzoxazine：
Three phosphonitrile diamine compound of 2mol rings is added in three mouthfuls of 2000mL glass reactors with agitating deviceThree phosphonitrile oxybenzene compound of 1,4- dioxane 500mL, 2.4mol ringFormaldehyde 4.5mol reacts 6h at 80 DEG C, is cooled to 70 DEG C, on one side stir, while
Logical nitrogen, and 20% sodium hydroxide solution 620g is instilled in backward reaction vessel, 4.8mol phosphonitrile chlorides are then added5h is reacted, the insoluble matter in removal system distills solvent in system, obtains having following knot
The phosphazene compound of structure：
, wherein M is three phosphazenium groups of ring, n=2.
Its nuclear-magnetism characterize data is as follows：
1H NMR(CDCl3,500MHz):, 6.4-6.7 (m, 35H, phenyl ring on hydrogen), 5.0 (d, 10H,Group
Hydrogen on the upper positions *), 3.6 (d, 10H,Hydrogen on group on the positions *), 3.4 (t, 102H, OCH 3)。
The position of infrared spectrum characteristic peak：The characteristic absorption peak 1217cm of P=N keys in phosphazene backbone-1, P- in phosphazene backbone
N 874cm-1, the absorption peak 2995cm of methyl ether-1, P-O-C key absorption peaks 1035cm-1, Ar-O ehter bonds are flexible in benzoxazine shakes
Dynamic characteristic peak 1246cm-1, the characteristic absorption peak 931cm of Liu Yuan oxazine rings-1And 928cm-1。
Embodiment 4
In the present embodiment, it is prepared by the following method the phosphazene compound containing benzoxazine：
Three phosphonitrile diamine compound of 3mol rings is added in three mouthfuls of 2000mL glass reactors with agitating deviceThree phosphonitrile oxybenzene compound of 1,4- dioxane 500mL, 3.8mol ringFormaldehyde 6.5mol reacts 8h at 100 DEG C, is cooled to 80 DEG C, on one side stirring, one
Side leads to nitrogen, and instills 20% sodium hydroxide solution 620g in backward reaction vessel, and 8mol phosphonitrile chlorides are then added7h is reacted, the insoluble matter in removal system distills solvent in system, obtains having following knot
The phosphazene compound of structure：
, wherein M is three phosphazenium groups of ring, n=5.
Its nuclear-magnetism characterize data is as follows：
1H NMR(CDCl3,500MHz):6.4-6.7 (m, 75H, phenyl ring on hydrogen), 5.0 (d, 22H,Group
Hydrogen on the upper positions *), 3.6 (d, 22H,Hydrogen on group on the positions *), 3.4 (t, 132H, OCH 3),2.0(t,
48H,SCH 3)。
The position of infrared spectrum characteristic peak：The characteristic absorption peak 1217cm- of P=N keys in phosphazene backbone1, in phosphazene backbone
P-N 874cm-1, the absorption peak 2995cm of methyl ether-1, the absorption peak 1070cm of thioether bond-1, P-O-C key absorption peaks 1035cm-1,
Ar-O ehter bonds stretching vibration characteristic peak 1246cm in benzoxazine-1, the characteristic absorption peak 931cm of Liu Yuan oxazine rings-1And 928cm-1。
Embodiment 5
In the present embodiment, it is prepared by the following method the phosphazene compound containing benzoxazine：
Three phosphonitrile diamine compound of 2mol rings is added in three mouthfuls of 2000mL glass reactors with agitating device1,4- dioxane 500mL, 3mol three phosphonitriles of ring are phenolated
Close objectFormaldehyde 4mol reacts 10h at 120 DEG C, is cooled to 80 DEG C, stirring on one side,
Lead to nitrogen on one side, and 20% sodium hydroxide solution 620g is instilled in backward reaction vessel, 6mol phosphonitrile chlorides are then added2h is reacted, the insoluble matter in removal system distills solvent in system, obtains having following knot
The phosphazene compound of structure：
, wherein M is three phosphazenium groups of ring, n=3.
1H NMR(CDCl3,500MHz):6.4-7.2 (m, 162H, phenyl ring on hydrogen), 5.0 (d, 16H,Group
Hydrogen on the upper positions *), 3.6 (d, 32H,Hydrogen on hydrogen and methylene on group on the positions *), 3.4
(t,30H,OCH 3)。
The position of infrared spectrum characteristic peak：The characteristic absorption peak 1217cm of P=N keys in phosphazene backbone-1, P- in phosphazene backbone
N 874cm-1, the absorption peak 2995cm of methyl ether-1, P-O-C key absorption peaks 1035cm-1, Ar-O ehter bonds are flexible in benzoxazine shakes
Dynamic characteristic peak 1246cm-1, the characteristic absorption peak 931cm of Liu Yuan oxazine rings-1And 928cm-1。
Embodiment 6
5 parts by weight of phosphazene compound containing benzoxazine that in the present embodiment, embodiment 1 is prepared,
HP7200H (DCPD-containing epoxy resin, Japanese DIC) 70 parts by weight, 10 parts by weight of maleic anhydride of styrene, 2-methylimidazole
3.8 parts by weight of 0.2 parts by weight and silica 1, are scattered in butanone and resin adhesive liquid are prepared, be then impregnated with glass fibre
Base material forms pre-impregnated sheet after heat drying, and copper foil is placed on two sides, and copper-clad plate a is made in pressurized, heated.
Embodiment 7
10 parts by weight of phosphazene compound containing benzoxazine that in the present embodiment, embodiment 1 is prepared,
NC3000H (biphenyl epoxy resin, Japanese DIC) 70 parts by weight, HPC-8000-65T (active ester curing agent, Japanese DIC) 15 weights
Part is measured, 4.8 parts by weight of 0.2 parts by weight of 2-methylimidazole and silica are scattered in butanone and resin adhesive liquid is prepared, so
After be impregnated with carbon fiber base material, form pre-impregnated sheet after heat drying, copper foil is placed on two sides, and copper-clad plate b is made in pressurized, heated.
Embodiment 8
20 parts by weight of phosphazene compound containing benzoxazine that in the present embodiment, embodiment 1 is prepared,
60 parts by weight of EPIKOTE828EL bisphenol A epoxide resins (DOW Chemical), 5 parts by weight of phthalic anhydride, 2-methylimidazole 0.2
4.8 parts by weight of parts by weight and silica 1, are scattered in butanone and resin adhesive liquid are prepared, be then impregnated with ceramic base material, warp
Pre-impregnated sheet is formed after crossing heat drying, copper foil is placed on two sides, and copper-clad plate c is made in pressurized, heated.
Embodiment 9
5 parts by weight of phosphazene compound containing benzoxazine that in the present embodiment, embodiment 2 is prepared,
HP7200H (DCPD-containing epoxy resin, Japanese DIC) 70 parts by weight, 10 parts by weight of maleic anhydride of styrene, 2-methylimidazole
3.8 parts by weight of 0.2 parts by weight and silica 1, are scattered in butanone and resin adhesive liquid are prepared, be then impregnated with glass fibre
Base material forms pre-impregnated sheet after heat drying, and copper foil is placed on two sides, and copper-clad plate d is made in pressurized, heated.
Embodiment 10
5 parts by weight of phosphazene compound containing benzoxazine that in the present embodiment, embodiment 3 is prepared,
HP7200H (DCPD-containing epoxy resin, Japanese DIC) 70 parts by weight, 10 parts by weight of maleic anhydride of styrene, 2-methylimidazole
3.8 parts by weight of 0.2 parts by weight and silica 1, are scattered in butanone and resin adhesive liquid are prepared, be then impregnated with glass fibre
Base material forms pre-impregnated sheet after heat drying, and copper foil is placed on two sides, and copper-clad plate e is made in pressurized, heated.
Embodiment 11
5 parts by weight of phosphazene compound containing benzoxazine that in the present embodiment, embodiment 4 is prepared,
HP7200H (DCPD-containing epoxy resin, Japanese DIC) 70 parts by weight, 10 parts by weight of maleic anhydride of styrene, 2-methylimidazole
3.8 parts by weight of 0.2 parts by weight and silica 1, are scattered in butanone and resin adhesive liquid are prepared, be then impregnated with glass fibre
Base material forms pre-impregnated sheet after heat drying, and copper foil is placed on two sides, and copper-clad plate f is made in pressurized, heated.
Embodiment 12
5 parts by weight of phosphazene compound containing benzoxazine that in the present embodiment, embodiment 5 is prepared,
HP7200H (DCPD-containing epoxy resin, Japanese DIC) 70 parts by weight, 10 parts by weight of maleic anhydride of styrene, 2-methylimidazole
3.8 parts by weight of 0.2 parts by weight and silica 1, are scattered in butanone and resin adhesive liquid are prepared, be then impregnated with glass fibre
Base material forms pre-impregnated sheet after heat drying, and copper foil is placed on two sides, and copper-clad plate g is made in pressurized, heated.
Comparative example 1
With differing only in for embodiment 6, contain Ben Bing Evil using what hexachlorocyclotriph,sphazene alternate embodiment 1 was prepared
Copper-clad plate h is prepared in the phosphazene compound of piperazine.
Comparative example 2
With differing only in for embodiment 6, is substituted and implemented using the phosphazene compound containing benzoxazine of such as lower structure
The phosphazene compound containing benzoxazine is prepared in example 1：
Copper-clad plate i is prepared.
The performance of embodiment 6-12 and comparative example the 1-2 copper-clad plate being prepared is measured, result such as 1 institute of table
Show.
Table 1
The test data of above table, it can be seen that the phosphazene compound using the present invention containing benzoxazine colophony obtains
To the Tg of copper-clad plate can reach 167-187 DEG C, T- peel strengths can reach 2.0kg/mm2More than, interlaminar strength is reachable
To 1.90kg/mm2More than, saturated water absorption can reach 0.22% hereinafter, heat decomposition temperature can reach 420 DEG C or more, and bending is strong
Degree can reach 12.6kg/mm2More than, flammability (UL-94) reaches V-0 ranks, shows that the present invention's contains benzoxazine colophony
The solidfied material that is prepared of phosphazene compound, there is good anti-flammability, good heat resistance, water resistance, cohesiveness and machine
Tool performance, electrical property.It is abundant, each that the phosphazene compound containing benzoxazine colophony of the present invention belongs to low cost, raw material sources
Item is functional, is with a wide range of applications.
Applicant states that the present invention illustrates the phosphonitrile chemical combination containing benzoxazine of the present invention by above-described embodiment
Object, phosphonitrile composition epoxy resin, pre-impregnated sheet and composite metal substrate, but the invention is not limited in above-described embodiments, i.e.,
Do not mean that the present invention has to rely on above-described embodiment and could implement.Person of ordinary skill in the field is it will be clearly understood that this
Any improvement of invention, the addition of equivalence replacement and auxiliary element to each raw material of product of the present invention, the selection etc. of concrete mode,
It all falls within protection scope of the present invention and the open scope.
Claims (10)
1. a kind of phosphazene compound containing benzoxazine, which is characterized in that the phosphazene compound tool containing benzoxazine
Just like molecular structure shown in Formulas I：
Wherein, M is three phosphonitrile base M of ring1, four or more phosphonitrile base M of ring2Or non-annularity polyphosphazene base M3In any one or at least
Two kinds of combination；R1、R2、R3、R4、R5And R6It independently is the arbitrary organic group for meeting its chemical environment；X be-O- ,-NH- ,-
S- ,-COO- or-X1- R-, X1For any one in-O- ,-NH- ,-S- or-COO-, R is to meet the arbitrary of its chemical environment to have
Machine group；Y1And Y2It independently is the arbitrary organic group for meeting its chemical environment；A, b, d, e, f and g, which independently are, is more than or equal to
Zero integer, a+b+1 are equal to 2 times of phosphorus atoms number in M, and d+e+2 is equal to 2 times of phosphorus atoms number in M, and it is former that f+g+2 is equal to phosphorus in M
2 times of subnumber, n are the integer more than or equal to zero.
2. the phosphazene compound according to claim 1 containing benzoxazine, which is characterized in that R1、R2、R3、R4、R5And R6
It independently is the arbitrary inertia nucleophilic group for meeting its chemical environment or arbitrary reactive nucleophilic group；
Preferably, R1、R2、R3、R4、R5And R6It independently is substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkanes oxygen
Base, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkoxy aryl, substituted or unsubstituted heteroarylalkoxy,
Substituted or unsubstituted alkyl sulfenyl, substituted or unsubstituted artyl sulfo, substituted or unsubstituted carboxylate, substitution or not
Any one in substituted carbonate group, substituted or unsubstituted sulfonate group or substituted or unsubstituted phosphonate group；
Preferably, R is substituted or unsubstituted straight-chain alkyl-sub, substituted or unsubstituted branched alkylidene, substitution or unsubstituted
Arlydene, substituted or unsubstituted alkylenearylene, substituted or unsubstituted arylidene alkylene or substitution or for substitution
Cycloalkylidene in any one；
Preferably, Y1And Y2It independently is any one in-NH-R'- ,-O-R'- ,-S-R'- or-OOC-R'-, R' is substitution
Or it unsubstituted straight-chain alkyl-sub, substituted or unsubstituted branched alkylidene, substituted or unsubstituted arlydene, substitution or does not take
The alkylenearylene in generation, substituted or unsubstituted arylidene alkylene or substitution are any one in substituted cycloalkylidene
Kind；
Preferably, M includes at least 50wt%M1, at most 30wt%M2And at most 45wt%M3；
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 containing benzoxazine, which is characterized in that described to contain benzo
The phosphazene compound of oxazine is with a kind of in the compound of structure as shown in following formula a-f or at least two combinations：
Wherein M is three phosphazenium groups of ring, and n is the integer more than or equal to zero, and preferably n is the integer of 1-10, and further preferred n is 1-
5 integer.
4. the preparation method of the phosphazene compound according to any one of claim 1-3 containing benzoxazine, feature
It is, the described method comprises the following steps：
(1) phosphazene compound containing benzoxazine passes through phosphonitrile shown in phosphonitrile diamine compound shown in Formula II and formula III
Polymerizate shown in formula IV is obtained by the reaction in oxybenzene compound and formaldehyde, and reaction equation is as follows：
(2) polymerizate shown in formula IV is obtained by the reaction shown in Formulas I with phosphonitrile chloride shown in Formula V containing benzoxazine
Phosphazene compound, reaction equation are as follows：
Wherein, M is three phosphonitrile base M of ring1, four or more phosphonitrile base M of ring2Or non-annularity polyphosphazene base M3In any one or at least
Two kinds of combination；R1、R2、R3、R4、R5And R6It independently is the arbitrary organic group for meeting its chemical environment；X be-O- ,-NH- ,-
S- ,-COO- or-X1- R-, X1For any one in-O- ,-NH- ,-S- or-COO-, R is to meet the arbitrary of its chemical environment to have
Machine group；Y1And Y2It independently is the arbitrary organic group for meeting its chemical environment；A, b, d, e, f and g, which independently are, is more than or equal to
Zero integer, a+b+1 are equal to 2 times of phosphorus atoms number in M, and d+e+2 is equal to 2 times of phosphorus atoms number in M, and it is former that f+g+2 is equal to phosphorus in M
2 times of subnumber, n are the integer more than or equal to zero.
5. preparation method according to claim 4, which is characterized in that two amination of phosphonitrile shown in step (1) described Formula II
The molar ratio for closing object and phosphonitrile oxybenzene compound shown in formula III is 1:(1-1.5), such as 1:1、1:1.1、1:1.2、1:1.3、
1:1.4 or 1:1.5；
Preferably, the molar ratio of phosphonitrile diamine compound and formaldehyde shown in step (1) described Formula II is 1:(2-2.5)；
Preferably, the temperature of step (1) described reaction is 80-120 DEG C；
Preferably, the time of step (1) described reaction is 2-10h；
Preferably, the solvent of step (1) described reaction is DMF or Isosorbide-5-Nitrae-dioxane；
Preferably, phosphonitrile diamine compound shown in step (1) described Formula II and phosphonitrile chlorination shown in step (2) described Formula V
The molar ratio of object is 1:(2-5)；
Preferably, the temperature of step (2) described reaction is 60-80 DEG C；
Preferably, the time of step (2) described reaction is 2-8h；
Preferably, step (2) carries out in the presence of a basic；
Preferably, the alkaline matter be sodium hydroxide, potassium hydroxide or ammonium hydroxide in any one or at least two combination；
Preferably, the solvent of step (2) described reaction is DMF or Isosorbide-5-Nitrae-dioxane.
6. a kind of phosphonitrile composition epoxy resin, which is characterized in that it includes it is as claimed in any one of claims 1-3 containing
The phosphazene compound and epoxy resin of benzoxazine；
Preferably, mass percent of the phosphazene compound containing benzoxazine in phosphonitrile composition epoxy resin is 1-
20%, preferably 5-10%；
Preferably, the epoxy resin is liquid bisphenol A types epoxy resin, liquid bisphenol F types epoxy resin, solid-state bisphenol A-type
Epoxy resin, solid-state bisphenol f type epoxy resin resin, bisphenol-s epoxy resin, biphenyl type epoxy resin, phenol aldehyde type epoxy resin or
In dicyclopentadiene type epoxy resin any one or at least two mixture；
Preferably, the phosphonitrile composition epoxy resin further includes curing agent；
Preferably, the curing agent is anhydride curing agent or active ester curing agent；
Preferably, the anhydride curing agent is selected from maleic anhydride of styrene, methyl vinyl ether-maleic acid copolymer, methyl
Hexahydrophthalic anhydride, hexahydrophthalic anhydride, phenylsuccinic acid acid anhydride, succinic anhydride, oxa- acid anhydrides, dimethyl maleic anhydride, glutaric anhydride, 2- first
Base succinic anhydride, phthalic anhydride, norbornene dianhydride, four acid anhydride of equal benzene, 1,2- cyclohexyl dicarboxylic acids acid anhydride, 4- fluorine phthalic acids
Acid anhydride, 3- difluorophthalic anhydrides, 2,2- dimethyl succinic anhydrides, 1,1- cyclohexanediacetic acids acid anhydride, phenyl cis-butenedioic anhydride, citraconic anhydride, 1,
8- naphthalic anhydrides, 4,4 '-biphenyl ether dianhydrides, 3,3'4,4'- bibenzene tetracarboxylic dianhydrides, equal benzene dianhydride, 3,3'4,4'- dianhydrides two
Phenylate, 4,4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids, 1,2,3,4- cyclobutanetetracarboxylics dianhydride, 3,3'4,4'- benzophenone tetracarboxylic acids
Acid dianhydride, 1,4,5,8- benzene tetracarboxylic acids acid anhydride, -1,4,9,10- tetrabasic carboxylic acids acetic anhydride, 3,4,5,6- tetrahydrophthalic anhydride or cis- 1,2,3,
In 6- tetrabydrophthalic anhydrides any one or at least two mixture；
Preferably, the phosphonitrile composition epoxy resin further includes curing accelerator；
Preferably, the curing accelerator is imidazoles or pyridine compounds and their；
Preferably, the glyoxaline compound is selected from 2-methylimidazole, -4 methylimidazole of 2- ethyls, 2- phenylimidazoles, 2- 11
Alkyl imidazole, 1 benzyl 2 methyl imidazole, 2- heptadecyl imidazoles, 2 isopropyl imidazole, 2- phenyl -4-methylimidazole, 2- ten
In dialkylimidazolium or 1- 1-cyanoethyl-2-methylimidazoles any one or at least two mixture；
Preferably, the pyridine compounds and their is 4-dimethylaminopyridine；
Preferably, the phosphonitrile composition epoxy resin also includes fire retardant；
Preferably, the fire retardant is selected from organic fire-retardant and/or inorganic combustion inhibitor；
Preferably, the organic fire-retardant is selected from three (2,6- 3,5-dimethylphenyl) phosphines, bis- [two (2, the 6- dimethyl benzenes of resorcinol
Base) phosphate], resorcinol tetraphenyldiphosphate, triphenyl phosphate, bisphenol-A bis- (diphenyl phosphoesters), phosphonitrile it is fire-retardant
Agent, 10- (2,5- dihydroxy phenyls) -10- hydrogen -9- oxa- -10- phosphine phenanthrene -10- oxides, 10- (2,5- dihydroxy naphthalene) -10-
Appointing in hydrogen -9- oxa-s -10- phosphines phenanthrene -10- oxides or the miscellaneous -10- phospho hetero phenanthrenes -10- oxide fire retardants of 9,10- dihydro-9-oxies
It anticipates a kind of or at least two mixtures；
Preferably, the inorganic combustion inhibitor in red phosphorus, aluminium hydroxide, magnesium hydroxide or antimony trioxide any one or extremely
Few two kinds of mixture；
Preferably, the phosphonitrile composition epoxy resin also includes filler；
Preferably, the filler is selected from silica, kaolin, talcum powder, magnesium hydroxide, aluminium hydroxide, boehmite, neatly
Stone, titanium oxide, calcium silicates, beryllium oxide, boron nitride, glass powder, zinc borate, aluminium nitrogen compound, silicon nitride, silicon carbide, magnesia,
Zirconium oxide, mullite, titanium dioxide, potassium titanate, hollow glass microbead, polytetrafluorethylepowder powder, polystyrene powder, potassium titanate
Any one in fiber, carborundum mono-crystal fiber, silicon nitride fiber, alumina single crystal fiber or staple glass fibre or at least two
The mixture of kind.
7. a kind of resin adhesive liquid, which is characterized in that the resin adhesive liquid is by phosphonitrile epoxy resin group as claimed in claim 6
Conjunction object, which is dissolved or dispersed in solvent, to be obtained；
Preferably, the solvent be ketone, hydro carbons, ethers, esters or aprotic solvent in it is a kind of or at least two group
Close, preferably acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), toluene, dimethylbenzene, methanol, ethyl alcohol, primary alconol, glycol monoethyl ether,
Propylene glycol monomethyl ether, propylene glycol methyl ether acetate, ethyl acetate, N,N-dimethylformamide or N, in N- diethylformamides
It is a kind of or at least two mixture.
8. a kind of pre-impregnated sheet, which is characterized in that pre-impregnated sheet resin adhesive liquid described in claim 7 is impregnated with or is coated on base material
It forms；
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, which is characterized in that the composite metal substrate contains at least one as claimed in claim 8
Pre-impregnated sheet and be overlying on overlapping after pre-impregnated sheet one or both sides metal foil.
10. a kind of wiring board, which is characterized in that the surface processing line of the composite metal substrate described in claim 9 forms.
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|---|---|---|---|
| CN201710108481.1A CN108503671A (en) | 2017-02-27 | 2017-02-27 | A kind of phosphazene compound containing benzoxazine, phosphonitrile composition epoxy resin, pre-impregnated sheet and composite metal substrate |
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| CN201710108481.1A CN108503671A (en) | 2017-02-27 | 2017-02-27 | A kind of phosphazene compound containing benzoxazine, phosphonitrile composition epoxy resin, pre-impregnated sheet and composite metal substrate |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111925505A (en) * | 2020-08-14 | 2020-11-13 | 深圳市凯恩应用化学技术有限公司 | Modified epoxy resin, epoxy adhesive for optical fiber, preparation method and bonding method thereof |
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2017
- 2017-02-27 CN CN201710108481.1A patent/CN108503671A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111925505A (en) * | 2020-08-14 | 2020-11-13 | 深圳市凯恩应用化学技术有限公司 | Modified epoxy resin, epoxy adhesive for optical fiber, preparation method and bonding method thereof |
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