CN101061127A - 1,4-hydroquinone functionalized phosphinates and phosphonates - Google Patents
1,4-hydroquinone functionalized phosphinates and phosphonates Download PDFInfo
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- CN101061127A CN101061127A CNA2005800391790A CN200580039179A CN101061127A CN 101061127 A CN101061127 A CN 101061127A CN A2005800391790 A CNA2005800391790 A CN A2005800391790A CN 200580039179 A CN200580039179 A CN 200580039179A CN 101061127 A CN101061127 A CN 101061127A
- Authority
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- China
- Prior art keywords
- deutero
- composition
- epoxy
- resin
- quinhydrones
- Prior art date
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- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 title abstract 2
- 239000000203 mixture Substances 0.000 claims abstract description 69
- 125000003118 aryl group Chemical group 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 7
- 229920000642 polymer Polymers 0.000 claims abstract 4
- 229920005989 resin Polymers 0.000 claims description 89
- 239000011347 resin Substances 0.000 claims description 89
- 239000004593 Epoxy Substances 0.000 claims description 57
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical class C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 claims description 30
- 239000000126 substance Substances 0.000 claims description 26
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 25
- -1 2,5-naphthalenediol deutero-phosphinate Chemical compound 0.000 claims description 14
- 239000002966 varnish Substances 0.000 claims description 14
- 239000011521 glass Substances 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- 150000002148 esters Chemical class 0.000 claims description 11
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical class OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 claims description 6
- 239000011889 copper foil Substances 0.000 claims description 6
- GEQQZMCZSRHICC-UHFFFAOYSA-N 2-[(2,6-dimethylphenoxy)-phenylphosphoryl]benzene-1,4-diol Chemical compound CC1=CC=CC(C)=C1OP(=O)(C=1C(=CC=C(O)C=1)O)C1=CC=CC=C1 GEQQZMCZSRHICC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 3
- 229920001187 thermosetting polymer Polymers 0.000 claims description 3
- 229920005992 thermoplastic resin Polymers 0.000 claims description 2
- 150000000191 1,4-naphthoquinones Chemical class 0.000 claims 5
- GEOXNZQKJROKPQ-UHFFFAOYSA-N 5-[(2,6-dimethylphenoxy)-phenylphosphoryl]naphthalene-1,6-diol Chemical compound CC1=CC=CC(C)=C1OP(=O)(C=1C2=CC=CC(O)=C2C=CC=1O)C1=CC=CC=C1 GEOXNZQKJROKPQ-UHFFFAOYSA-N 0.000 claims 3
- 150000001721 carbon Chemical group 0.000 claims 3
- INXGPROTGZXDBZ-UHFFFAOYSA-N (2,5-dihydroxyphenyl)phosphonic acid Chemical class OC1=CC=C(O)C(P(O)(O)=O)=C1 INXGPROTGZXDBZ-UHFFFAOYSA-N 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- DNVKZTOVWHIZBQ-UHFFFAOYSA-N [2-(2,5-dihydroxyphenyl)phenyl]-(2,6-dimethylphenoxy)phosphinic acid Chemical group CC1=CC=CC(C)=C1OP(O)(=O)C1=CC=CC=C1C1=CC(O)=CC=C1O DNVKZTOVWHIZBQ-UHFFFAOYSA-N 0.000 claims 1
- 239000003063 flame retardant Substances 0.000 abstract description 35
- 239000003795 chemical substances by application Substances 0.000 abstract description 29
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 2
- 229920003986 novolac Polymers 0.000 description 36
- 239000000463 material Substances 0.000 description 35
- 239000003822 epoxy resin Substances 0.000 description 33
- 229920000647 polyepoxide Polymers 0.000 description 33
- 150000003008 phosphonic acid esters Chemical class 0.000 description 32
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 31
- 150000001875 compounds Chemical class 0.000 description 24
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 21
- 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 19
- 229920001568 phenolic resin Polymers 0.000 description 18
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 17
- 150000002989 phenols Chemical class 0.000 description 17
- 238000002360 preparation method Methods 0.000 description 17
- 229910052736 halogen Inorganic materials 0.000 description 14
- 150000002367 halogens Chemical class 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000011159 matrix material Substances 0.000 description 12
- 239000004744 fabric Substances 0.000 description 11
- 239000000945 filler Substances 0.000 description 11
- 235000013824 polyphenols Nutrition 0.000 description 11
- 239000000654 additive Substances 0.000 description 10
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 10
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 10
- 238000005470 impregnation Methods 0.000 description 10
- 150000001299 aldehydes Chemical class 0.000 description 9
- 230000000996 additive effect Effects 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 6
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- VOOLKNUJNPZAHE-UHFFFAOYSA-N formaldehyde;2-methylphenol Chemical compound O=C.CC1=CC=CC=C1O VOOLKNUJNPZAHE-UHFFFAOYSA-N 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 239000012745 toughening agent Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229920000877 Melamine resin Polymers 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 229940015043 glyoxal Drugs 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000000979 retarding effect Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- LHENQXAPVKABON-UHFFFAOYSA-N 1-methoxypropan-1-ol Chemical compound CCC(O)OC LHENQXAPVKABON-UHFFFAOYSA-N 0.000 description 4
- 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 description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- CGXBXJAUUWZZOP-UHFFFAOYSA-N formaldehyde;phenol;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.OC1=CC=CC=C1.NC1=NC(N)=NC(N)=N1 CGXBXJAUUWZZOP-UHFFFAOYSA-N 0.000 description 4
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 4
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- CMQUQOHNANGDOR-UHFFFAOYSA-N 2,3-dibromo-4-(2,4-dibromo-5-hydroxyphenyl)phenol Chemical compound BrC1=C(Br)C(O)=CC=C1C1=CC(O)=C(Br)C=C1Br CMQUQOHNANGDOR-UHFFFAOYSA-N 0.000 description 3
- 229930192627 Naphthoquinone Natural products 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 239000004922 lacquer Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000002791 naphthoquinones Chemical class 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 229920003987 resole Polymers 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- JEFSTMHERNSDBC-UHFFFAOYSA-N 1,2-dimethylcyclohexa-2,4-dien-1-ol Chemical compound CC1=CC=CCC1(C)O JEFSTMHERNSDBC-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical class O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- IXQGCWUGDFDQMF-UHFFFAOYSA-N 2-Ethylphenol Chemical compound CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
- YBZNIXITXQQEBY-UHFFFAOYSA-N 2-diphenylphosphoryloxy-1,3-dimethylbenzene Chemical compound CC1=CC=CC(C)=C1OP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 YBZNIXITXQQEBY-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- NUZWLKWWNNJHPT-UHFFFAOYSA-N anthralin Chemical compound C1C2=CC=CC(O)=C2C(=O)C2=C1C=CC=C2O NUZWLKWWNNJHPT-UHFFFAOYSA-N 0.000 description 2
- TZIQWQARHPGHIG-UHFFFAOYSA-N anthrarobin Chemical compound C1=CC=CC2=CC3=C(O)C(O)=CC=C3C(O)=C21 TZIQWQARHPGHIG-UHFFFAOYSA-N 0.000 description 2
- GGNQRNBDZQJCCN-UHFFFAOYSA-N benzene-1,2,4-triol Chemical compound OC1=CC=C(O)C(O)=C1 GGNQRNBDZQJCCN-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000013068 control sample Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 150000001896 cresols Chemical class 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 229960002311 dithranol Drugs 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 239000012764 mineral filler Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 2
- 229940124530 sulfonamide Drugs 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004634 thermosetting polymer Substances 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- WOPMSHPJMFBJDG-UHFFFAOYSA-N (2,5-dihydroxyphenyl)-phenylphosphinic acid Chemical compound C1=CC=C(C=C1)P(=O)(C2=C(C=CC(=C2)O)O)O WOPMSHPJMFBJDG-UHFFFAOYSA-N 0.000 description 1
- YCIHPQHVWDULOY-FMZCEJRJSA-N (4s,4as,5as,6s,12ar)-4-(dimethylamino)-1,6,10,11,12a-pentahydroxy-6-methyl-3,12-dioxo-4,4a,5,5a-tetrahydrotetracene-2-carboxamide;hydrochloride Chemical compound Cl.C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(=O)C(C(N)=O)=C(O)[C@@]4(O)C(=O)C3=C(O)C2=C1O YCIHPQHVWDULOY-FMZCEJRJSA-N 0.000 description 1
- AAOADXIHXYIOMT-UHFFFAOYSA-N 1,1'-biphenyl;phosphoric acid Chemical compound OP(O)(O)=O.C1=CC=CC=C1C1=CC=CC=C1 AAOADXIHXYIOMT-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000963007 Anelosimus may Species 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VAHZFXYRJIFJRT-UHFFFAOYSA-N C(C1CO1)N(C(NC(CO)=O)=O)CC1CO1 Chemical compound C(C1CO1)N(C(NC(CO)=O)=O)CC1CO1 VAHZFXYRJIFJRT-UHFFFAOYSA-N 0.000 description 1
- WMNZJWSCGYPOTF-UHFFFAOYSA-N CC(C(C(C1=CC=CC=C1)(O)O)(C)C)C Chemical compound CC(C(C(C1=CC=CC=C1)(O)O)(C)C)C WMNZJWSCGYPOTF-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 206010020843 Hyperthermia Diseases 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 239000004844 aliphatic epoxy resin Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- RREGISFBPQOLTM-UHFFFAOYSA-N alumane;trihydrate Chemical compound O.O.O.[AlH3] RREGISFBPQOLTM-UHFFFAOYSA-N 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
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- YUTJCNNFTOIOGT-UHFFFAOYSA-N anthracene-1,8,9-triol Chemical compound C1=CC(O)=C2C(O)=C3C(O)=CC=CC3=CC2=C1 YUTJCNNFTOIOGT-UHFFFAOYSA-N 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- WVHBHPATSLQXGC-UHFFFAOYSA-N benzene;ethanol Chemical class CCO.C1=CC=CC=C1 WVHBHPATSLQXGC-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- IUTYMBRQELGIRS-UHFFFAOYSA-N boric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OB(O)O.NC1=NC(N)=NC(N)=N1 IUTYMBRQELGIRS-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000012612 commercial material Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- IMDXZWRLUZPMDH-UHFFFAOYSA-N dichlorophenylphosphine Chemical compound ClP(Cl)C1=CC=CC=C1 IMDXZWRLUZPMDH-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical group 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- BEQVQKJCLJBTKZ-UHFFFAOYSA-N diphenylphosphinic acid Chemical compound C=1C=CC=CC=1P(=O)(O)C1=CC=CC=C1 BEQVQKJCLJBTKZ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 150000002118 epoxides Chemical group 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000036031 hyperthermia Effects 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate Chemical compound [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 229940100630 metacresol Drugs 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 125000001918 phosphonic acid ester group Chemical group 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- QQOWHRYOXYEMTL-UHFFFAOYSA-N triazin-4-amine Chemical compound N=C1C=CN=NN1 QQOWHRYOXYEMTL-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
-
- 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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/32—Esters thereof
- C07F9/3205—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/3229—Esters of aromatic acids (P-C aromatic linkage)
-
- 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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4021—Esters of aromatic acids (P-C aromatic linkage)
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
There is presented novel 1,4-hydroquinone derivatized phosphinates and phosphonates. The novel compositions here presented are useful as polymer curing agents and as flame retardants. Where R, R' each independently are the same or different aryl, aralkyl or alkyl comprising from one to 15 carbon atoms.
Description
The application requires the U.S. Provisional Patent Application No.60/611 of submission on September 21st, 2004,782 right of priority.
Summary of the invention
Present invention relates in general to novel 1,4-quinhydrones and 1, the phosphinate that the 4-naphthoquinones is functionalized and the preparation of phosphonic acid ester and they are as the purposes of the flame retardance element of epoxy-resin systems.Phosphinate of the present invention and phosphonic acid ester can be used as the curing agent for epoxy resin with reinforced flame retardant performance.Though phosphinate of the present invention and phosphonic acid ester can be used for cured epoxy resin separately, combine as the co-curing agent with polyol and can find bigger applicability.1,4-quinhydrones or 1, phosphinate/phenolic varnish that the 4-naphthoquinones is functionalized and phosphonic acid ester/novolac resin co-curing agent is suitable for fire-retardant printed-wiring board (PWB).The present invention also can be used as the co-curing agent in the epoxy-resin systems of prepreg (prepreg), veneer sheet, especially copper clad laminate, and described prepreg, veneer sheet, especially copper clad laminate can be used for making the not electronic component of halogen-containing flame retardant.
Background of invention
Matrix material based on Resins, epoxy gets the nod in multiple application for a long time substantially, and because this matrix material of its versatility continues to have sizable importance.A specific examples of this application includes, but are not limited to, and is used for printed circuit board (PCB) (printed-wiring board (PWB), electric veneer sheet PWB).The Resins, epoxy that is used for is wherein processed easily and has especially been obtained popularizing owing to it.The feature of those Resins, epoxy also is favorable mechanical and chemical property, toughness and for example to the patience of multiple organic solvent, and show good chemical reagent resistance and moisture resistance.These performances make epoxide resin material can adapt to multiple application purpose, and make the material of forming matrix material obtain favourable use.
Usually, can easily Resins, epoxy be machined for the PWB composite applications by making prepreg (B-stage (B-staging)).For example, use the resin impregnation base material, this base material is inorganic or organic toughener of fiber, pile fabric and fabric or textile materials form normally.This can be by realizing with the resin solution coated substrate in easy volatilization or the volatilizable solvent.Can comprise that roller coat, dip-coating, spraying and their combination apply by multiple familiar technology.This prepreg of heating desolvates and partly solidifies this resin to remove in baking oven then.Advantageously, the prepreg that obtains after this processing can not adhere to certainly, but they should not be completely crued yet.In addition, prepreg should show storage stability.Being processed in the composite material subsequently, this prepreg should apply under the heat and the condition of pressure fusible so that as far as possible closely and for good and all bond together with toughener or insertion component and the material that provides for matrix material; That is, crosslinked epoxy resin-base must and toughener, and the interface that material to be bonded together such as metal, pottery, inorganic and organic materials form height adheres to.
Flame retardant resistance is an important performance for some application that relates to polymer materials.In some purposes, flame retardant resistance has been endowed first priority, and this is because for example danger that human and goods and materials is caused in the structural material that is used for aircraft and motor vehicle structure and is used for public transport.In electronic application, flame retardant resistance is necessary, because element may produce sizable localized hyperthermia on veneer sheet.The calcination of veneer sheet may cause the loss of assembling electronic component thereon.In addition, for the human fire savety of the device that comprises the PWB element, guarantee high explosion-proof/flameproof protection level.
Therefore, in the preparation of the veneer sheet that contains Resins, epoxy, in composition epoxy resin, introduce various additives and/or reactive component has been a convention with the flame retardant resistance of improving the gained veneer sheet.Used the fire retardant matter of many types, yet, up to the present commercial the most frequently used be for example tetrabromo-bisphenol of halogen-containing compound.Usually by this material being introduced Resins, epoxy with the diglycidylether reaction of dihydroxyphenyl propane.Usually, in order to reach required flame retardancy level (in standard " Underwriters Laboratory " test method UL 94, reaching V-0), require the level of this brominated fire retardant matter to satisfy: based on the gross weight in the product, the bromine content that provides is that 10wt% is to 25wt%.
Usually, halogen-containing fire retarding epoxide resin is considered to safety and effectively as those that comprise tetrabromo-bisphenol.Yet, use and more and more do not favored based on the fire retarding epoxide resin system of halogen-containing chemical substance.For these type materials, hope can be satisfied the needs of flame retardant resistance and show and identical or bigger mechanical property, toughness and the solvent resistance that halogenated materials provided used at present and the advantage of moisture resistance.
A kind of such method that is proposed by numerous research workers is to use phosphine flame retardant.Referring to for example, EP 0 384 939; EP 0 384 940; EP 0 408 990; DE 4 308 185; DE 4 308 187; WO 96/07685; WO 96/07686; U.S. Patent No. 5,648,171; U.S. Patent No. 5,587,243; U.S. Patent No. 5,576,357; U.S. Patent No. 5,458,978; And U.S. Patent No. 5,376,453; All documents are incorporated herein by reference in this integral body.In all these reference, by forming a kind of preparation, then its linking agent with amino crosslinker such as Dyhard RU 100, sulfanilamide (SN) or some other nitrogenous element is solidified to form the thermosetting polymer network derived from the fire retardant of phosphorus compound and the reaction of Resins, epoxy.
The specific examples of commercially available phosphorus based flame retardant additives comprises Antiblaze
TM1045 (Albright and Wilson Ltd, United Kingdom), it is a phosphonic acid ester.Phosphoric acid ester also is used as additive, for example, PX-200 (Diahachi, Japan).The disclosed commercially available reactive P contained compound that is suitable for Resins, epoxy comprise Sanko HCA and SankoHCA-HQ (Sanko Chemical Co., Ltd., Japan).
The phosphonic acid ester that alkyl and aryl replace also is used for fire retarding epoxide resin.More particularly, phosphonic C
1-C
4Therefore alkyl ester is valuable, because they comprise a high proportion of phosphorus, and can give resin flame retardant properties comprising them.Yet, being used for preparing the surrogate of the Resins, epoxy of electric veneer sheet as halogenated fire-retardants, phosphonic acid ester is not also accepted extensively, because often cause undesirable performance.For example, these phosphonic acid esters are known softening agent and therefore often show undesirable low second-order transition temperature (T by its veneer sheet that forms
g).Another defective is to use these phosphonic acid esters to improve the tendency of gained cured epoxy resin absorption moisture with the amount of the flame retardant resistance that is enough to provide necessary.The water absorption of cured layer pressing plate is very important because when be introduced into temperature be approximately 260 ℃ liquid solder bathe in the time (printed-wiring board (PWB) make in exemplary steps), the veneer sheet of contained high levels moisture often bubbles and lost efficacy.
Other method of giving flame retardant resistance relates to uses resin material and mineral filler, as the not halogen-containing fire retarded epoxy resin composition of binding substances preparation of aluminum trihydrate (EP 0 795 570 A1) or magnesium hydroxide (JP 2001213980 A2).Depend on physicals, these materials may make the processing of Resins, epoxy become more difficult, because they are insoluble to resin system.In addition, may need quite high load level, this performance that can detract.Usually referring to, U.S. Patent No. 6,097,100, WO01/42359 and the reference that is used to describe various mineral fillers quoted in them.
Be the hydroxyaryl phosphine oxide co-curing agent that epoxy-resin systems provides not other trial of halogen-containing fire retardant to comprise to be used for Resins, epoxy, described epoxy-resin systems is advantageously used in prepreg, veneer sheet, copper clad laminate and printed-wiring board (PWB).Fire-retardant co-curing agent like this is in U.S. Patent No. 6,887, discloses in 950.
An object of the present invention is to provide economical, useful 1,4-quinhydrones or 1, phosphinate that the 4-naphthoquinones is functionalized and functionalized phosphonic acid ester are as the flame retardant composition that is used for cured epoxy resin.Of the present invention 1,4-quinhydrones or 1, phosphinate that the 4-naphthoquinones is functionalized and the preparation of functionalized phosphonic acid ester are used for the hydrolysis-stable and the application heat-staple, not halogen-containing epoxy-resin systems of PWB material can find special effectiveness.
It is halogen-containing 1 that another object of the present invention provides, 4-quinhydrones or 1, and phosphinate that the 4-naphthoquinones is functionalized and functionalized phosphonic acid ester composition epoxy resin, it can be used as the surrogate of the tetrabromo-bisphenol of non-combustible high pressure laminate in using.
These and other objects of the present invention and advantage will be found out from following detailed description.
The present invention relates to be used for the structure (I) of flame-proofed polymer material (particularly including printed-wiring board (PWB)) and the preparation of phosphinate (II) and phosphonic acid ester.
R and R ' limit below.
Except top quinhydrones based structures I and II, the applicant also discloses the naphthalene compound of diol substituted in the present invention, that is: according to 1 of structure III and IV, and phosphinate that the 4-naphthoquinones is functionalized and phosphonic acid ester.
Unless context has needs in addition, when relating to quinhydrones hereinafter, be to be understood that these naphthalenediol compositions also are described.
More particularly, the present invention relates to be used for preparing prepreg, veneer sheet, and the fire retarding epoxide resin of copper clad laminate particularly, this prepreg, veneer sheet and particularly copper clad laminate are used under the situation of not using halogen contained compound makes electronic component.The invention still further relates to the method for flame retardant thermoset resins and the manufacture method of fire-retardant printed-wiring board (PWB), prepreg and veneer sheet.
Curable, the fire retarding epoxide resin that is fit to be used for to make resin formulation, prepreg and veneer sheet can be reacted with the advancement of halogen-containing Resins, epoxy not by structure (I) and compound (II) and prepare.The hydroxyl structure of structure I, II, III and IV part easily with standard epoxy in epoxide group react.By using suitable reactive chemistry metering can in the copolymer products resin, obtain various molecular weight.The Resins, epoxy that is fit to is, but is not limited to novolac epoxy and bisphenol A diglycidyl ether.Quinhydrones of the present invention and naphthoquinones can also be used as curing agent for epoxy resin.The use of can using alone or combine of these solidifying agent with other solidifying agent that is fit to such as lacquer resins.
Can be the compound of structure I and II is functionalized to obtain the epoxy intermediate of structure I A and IIA in the reactive site of phenol.For example, the compound of structure I and II can react to produce difunctional epoxy compound with Epicholorohydrin.Can use then with the same mode of commercial epoxy resin and use these compounds, that is, they can be used as Resins, epoxy, can improve or promote with difunctionality oxy-compound such as dihydroxyphenyl propane, or solidify with the solidifying agent that is fit to.
Structure III forms similar epoxy compounds with IV when reacting to Epicholorohydrin.
Composition of the present invention is described to " not halogen-containing ".Should be understood that, add Epicholorohydrin and may add the chlorine of trace, to form structure (IA) and epoxidised compound (IIA) as reactant.Similarly, the halogen of trace may be present in the phosphinate and phosphonic acid ester of structure I, II, III and IV.Such halogen is not enough to influence significantly flame retardant resistance.The halogen that has a trace is negligible as the by product of the precursor of making the present application composition.
R, R ' are identical or different aryl, aralkyl, alkenyl independently of one another or contain C
1-C
15Alkyl.Aryl comprises phenyl, xenyl, naphthyl and is selected from the analogue that following group replaces: the alkoxyl group of straight chain or branching such as methoxy or ethoxy, the alkyl of straight chain or branching such as methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group and nonyl substituting group.Kiki alkenyl group comprises vinyl, propenyl and butenyl, and condition is the ability that this substituting group can not hinder phosphorus compound and selected polymkeric substance to react.For example, when R is phenylene, the R of suitable replacement be adjacent-,-or, be commonly referred to ortho-cresol base, meta-cresol base or p-cresol base to hydroxyl-methyl-phenyl.Alkyl can be the saturated substituting group of straight chain, branching or ring-type of a common 1-15 carbon atom, comprises methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl and decyl substituting group.The feature of aralkyl can be by one or more alkyl carbon atoms keyed jointing aromatic kernels.The example of aralkyl comprises hydrocinnamyl or benzene butyl substituting group.
A preferred embodiment is to use compound 1B:2,5-dihydroxy phenyl-phenyl phosphinic acid 2,6-dimethyl-phenylester and 2B:2, two (2, the 6-3,5-dimethylphenyl) esters of 5-dihydroxy phenyl phosphonic acids.2, the existence of 6-3,5-dimethylphenyl structure division provides improved moisture resistance, thermotolerance and good chemical stability.
Compound I B Compound I IB
Can prepare aforesaid compound and preparaton to influence curing speed, strengthen flame retardant resistance and to improve physicals with extra additive and filler.These compounds and preparaton are intended to be used for making the prepreg and the glass enhancement layer pressing plate of the manufacturing that is used for printed-wiring board (PWB).
Generally speaking, 1,4-quinhydrones or 1, both account for the about 85 moles of % of about 25-of the epoxy curing agent part of Resins, epoxy phosphinate that the 4-naphthoquinones is functionalized or phosphonic acid ester or they.Advantageously, this quinhydrones or naphthoquinones partly provide explosion-proof/flameproof protection, and can influence the structure and the electrical property of gained electricity veneer sheet sharply.This quinhydrones or naphthoquinones part can be 90 moles of % or even 100 moles of % of curing agent for epoxy resin part.
The poly-hydroxy mixture also comprises the phenols co-crosslinking composition with two or more hydroxy functionalities, and can comprise any suitable phenols component, as the resin that obtains by the reaction of phenol or alkylated phenol and formaldehyde, for example novolac resin, resole, Dicyclopentadiene (DCPD) phenol phenolic varnish; Or other hydroxy-functionalized polymer's resin of the cinnamic residue of hydroxyl for example.The multifunctional phenolic monomers and/or the oligomeric compound that are fit to comprise three (hydroxy phenyl) methane; Three (hydroxy phenyl) ethane; 1,3, the 5-trihydroxybenzene; Four phenolic group ethane; 3,4,5-trihydroxybenzoic acid (also claiming gallic acid) or derivatives thereof, or pyrogallol (also claiming 1); Or 1,2,4-trihydroxybenzene (also claiming hydroxyhydrochinon); 1,8,9-trihydroxy-anthracene (also claiming Dithranol or dithranol), or 1,2,10-trihydroxy-anthracene (also claiming leucoalizarin (anthrarobine)); 2,4, the 5-trihydroxy-pyrimidine; And the mixture of these compounds and reaction product.Other phenols component can also be referring to U.S. Patent No. 6,645,631, and its disclosure is hereby incorporated by.If necessary, can be with the phenols component blend of monomer, oligopolymer and polymkeric substance, with preparation phenols co-crosslinking composition.
Preferred poly-hydroxy co-crosslinking material is that class novolac resin that comprises resol, Cresol Formaldehyde Resin and their mixture.Perhaps most preferred poly-hydroxy novolac resin is those of residue that comprise azaheteroaryl, phenol and aldehyde, and this resin can be selected from: benzoguanamine phenol formaldehyde resin, acetylguanamine phenol formaldehyde resin, melamine phenol formaldehyde resin, benzoguanamine Cresol Formaldehyde Resin, acetylguanamine Cresol Formaldehyde Resin, melamine Cresol Formaldehyde Resin and their mixture.Phenols, many other reaction product that contain between azaheteroaryl and the aldehyde will be used for forming suitable hydroxy-containing resin by those skilled in the art's approval.
On the other hand, the present invention includes curable composition epoxy resin, it comprises:
Resins, epoxy;
Co-crosslinking poly-hydroxy mixture, it comprises:
1,4-quinhydrones or 1, phosphinate that the 4-naphthoquinones is functionalized and functionalized phosphonic acid ester, or both and
This poly-hydroxy mixture also comprises phenols co-crosslinking composition, and said composition comprises above-mentioned phenols component with two or more hydroxy functionalities.
In some embodiments, Resins, epoxy is novolac epoxy, and in other embodiments, and Resins, epoxy can be based on Epicholorohydrin and dihydroxyphenyl propane, and perhaps in other embodiment still, Resins, epoxy is based on Epicholorohydrin and Bisphenol F.Curable composition epoxy resin preferably has the phosphorus content of the about 5wt% of about 0.2wt%-, and wherein approximately the about 4wt% of 1wt%-is slightly typical.Approximately the about 3wt% of 2wt%-is especially preferred.Usually, the poly-hydroxy mixture has the total hydroxy radical content with the needed stoichiometric about 50 moles of about 150 moles of % of %-of existing epoxy resin cure, wherein under many circumstances hydroxy radical content for being preferred with the about 125 moles of % of the needed stoichiometric about 75 moles of %-of epoxy resin cure.Still preferred can be that hydroxy radical content is with the about 110 moles of % of the needed stoichiometric about 85 moles of %-of epoxy resin cure.
In many embodiments, the hydroxyl structure of 1 mole of about 99 moles of % of %-is the novolac resin oh group partly in the curing agent mixture, and the hydroxyl structure of about 15 moles of about 75 moles of % of %-is typical for the novolac resin oh group partly in the curing agent mixture.In addition, the hydroxyl structure of about 1 mole of about 99 moles of % of %-partly is 1 in curing agent mixture, 4-quinhydrones or 1,4-naphthaquinone part, and the hydroxyl structure of about 25 moles of about 85 moles of % of %-partly is 1 in curing agent mixture, 4-quinhydrones or 1,4-naphthaquinone partly are typical.
Aspect another, provide a kind of matrix material of resin impregnation of the present invention, this matrix material comprises enhancement component and partly solidified at least fire retarded epoxy resin composition described herein.This matrix material comprises that glass filler, glass fibre or glass fabric also randomly comprise the copper foil layer on the matrix material that adheres to this resin impregnation.This type of veneer sheet generally includes the glass fabric layer of a plurality of resin impregnations, and they are pressed into the structure that can not be separated into the stratified integration basically of its structure usually.Though often selecting glass is strongthener, also provide within the scope of the present invention to comprise carbon fiber, aromatic polyamide fibre and quartzy matrix material.
The present invention relates to 1 of described herein and poly-hydroxy co-curing agent blend, phosphinate that 4-quinhydrones or naphthoquinones are functionalized and the phosphonic acid ester purposes in the Resins, epoxy preparaton.Typical curable preparaton is made of following material, but be not limited to following material, A) of the present invention 1,4-quinhydrones or 1, phosphinate that the 4-naphthoquinones is functionalized and functionalized phosphonic acid ester, perhaps they both, B) novolac resin, C) Resins, epoxy or Resins, epoxy binding substances, D) filler or filler binding substances, E) curing catalyst, and F) suitable solvent or solvent binding substances.This preparaton can also comprise additive that those skilled in the art select or reactive component to obtain the performance of some needs.
A preferred embodiment of the present invention is 1,4-quinhydrones or 1, phosphinate that the 4-naphthoquinones is functionalized and functionalized phosphonic acid ester or their both as with the purposes of the blend of poly-hydroxy novolac resin.By means of the solvent that is fit to, described herein 1,4-quinhydrones or 1, phosphinate that the 4-naphthoquinones is functionalized and functionalized phosphonic acid ester dissolve easily as the mixture with various novolac resins.These resin solutions provide the resin solidification solution of giving excellent processing and easy usability.These resin solidification solution are stable and suppress 1,4-quinhydrones or 1, the crystallization of the phosphinate that the 4-naphthoquinones is functionalized and functionalized phosphonic acid ester or selected phenolic varnish.Perhaps, under the situation of selecting, can be by with 1,4-quinhydrones or 1, both form blend with the phenolic varnish melt blending that is fit to phosphinate that the 4-naphthoquinones is functionalized and functionalized phosphonic acid ester or they.If this novolac resin is a solid, so 1,4-quinhydrones or 1, the mixture of phosphinate that the 4-naphthoquinones is functionalized and functionalized phosphonic acid ester or they both and novolac resin can be used as the processing of solid blend thing and with solid-state use.An optional embodiments is with 1,4-quinhydrones or 1, and phosphinate that the 4-naphthoquinones is functionalized and functionalized phosphonic acid ester or their both and novolac resin add in the curable resin preparaton individually.
Except as otherwise noted, or as can be seen by context, term lacquer resins and analogue are meant and comprise the hydroxy-functional resin combination that it comprises one or more replacements or unsubstituted phenolic compound and one or more aldehyde, the condensation product of preferred formaldehyde.As following pointed, this resinoid can randomly comprise heteroaryl component such as melamine and guanamines.
Be suitable for making prepreg and veneer sheet curable, fire retarded epoxy resin composition can be by 1,4-quinhydrones or 1, the phosphinate, 1 that the 4-naphthoquinones is functionalized, 4-quinhydrones or 1, the preparaton of the phosphonic acid ester that the 4-naphthoquinones is functionalized or they both and novolac resin and commercially available Resins, epoxy prepares.1,4-quinhydrones or 1, the phosphinate, 1 that the 4-naphthoquinones is functionalized, 4-quinhydrones or 1, the phosphonic acid ester that the 4-naphthoquinones is functionalized or their both products distribution make to be solidified and some physical property of uncured resin is affected easily.The performance that relates to is for example, but to be not limited to molecular weight, viscosity, second-order transition temperature and gelation point.The types and sources of the aromatic hydroxy that exists in its reason and the curing agent mixture is relevant.
Resins, epoxy can with phenols co-crosslinking composition together 1,4-quinhydrones or 1, the phosphinate, 1 that the 4-naphthoquinones is functionalized, 4-quinhydrones or 1, both are crosslinked for the phosphonic acid ester that the 4-naphthoquinones is functionalized or they.Phenols co-crosslinking composition comprises novolac resin, as phenol-formaldehyde resin, cresol-formaldehyde resin and their mixture.The polymkeric substance of phenol, azaheteroaryl and aldehyde also is fit to.Example comprises benzoguanamine-phenol-formaldehyde resin, acetylguanamine-phenol-formaldehyde resin, melamine-phenol-formaldehyde resin, benzoguanamine-cresol-formaldehyde resin, acetylguanamine-cresol-formaldehyde resin, melamine-cresol-formaldehyde resin and their mixture.
This co-curing composition also comprises the phenolic material with two or more hydroxy functionalities.Typical phenolic compound is:
A) resin that is obtained by the reaction of phenol or alkylated phenol and formaldehyde is as novolac resin or resole.
B) polyhydroxy aromatic material, as: aforesaid three (hydroxy phenyl) methane; Three (hydroxy phenyl) ethane; 1,3, the 5-trihydroxybenzene; Four phenolic group ethane etc.
Preferred phenols co-curing component is that class novolac resin that comprises phenol formaldehyde resin, Cresol Formaldehyde Resin and their mixture.Preferred poly-hydroxy novolac resin comprises the residue of azaheteroaryl, phenol and aldehyde, and these resins can be selected from: benzoguanamine phenol formaldehyde (PF), acetylguanamine phenol formaldehyde (PF), melamine phenol formaldehyde (PF), benzoguanamine cresoform, acetylguanamine cresoform, melamine cresoform and their mixture.Phenols, many other reaction product that contain between azaheteroaryl and the aldehyde will be used for forming suitable hydroxy-containing resin for those skilled in the art's approval.
The poly-hydroxy novolac resin that comprises phenol/aldehyde copolymer (as multipolymer of the residue of the benzene that replaces of one or more or various other hydroxyl of comprising the phenol (as cresols or dihydroxyphenyl propane) of formaldehyde and phenol or replacement) is especially preferred in some embodiments.This component and of the present invention 1,4-quinhydrones or 1, phosphinate that the 4-naphthoquinones is functionalized and functionalized phosphonic acid ester are together as the co-curing agent.The phenol novolac resin is the commercial materials that easily obtains, and is characterized by general chemical structure V usually:
Wherein R can represent hydrogen, alkyl such as methyl etc.
The novolac resin that is fit to comprises, for example, but is not limited to: can be from HexionSpecialty Chemicals, and the Durite that Inc. obtains
SD-1708, SL-1710, SD-1502, SD-1702, SD-1731, SD-1734, SD-241A, SD-423A, RD-2414, SD-5132, SD-7280, SD-1502, SD-500C; Can be from GP-2074,5300,5833, the 834D54 of Georgia Pacific acquisition; Can be from HRJ-11040,1166,1583,2210,2355,2901, CRJ-406 and the FRJ-425/200 of Schenectady International acquisition.
In some cases, comprise that the poly-hydroxy novolac resin of multipolymer is especially preferred, this multipolymer comprises the reaction product of azaheteroaryl, phenol and aldehyde.As pointed before this, these resins can be selected from benzoguanamine phenol formaldehyde (PF), acetylguanamine phenol formaldehyde (PF), melamine phenol formaldehyde (PF), benzoguanamine cresoform, acetylguanamine cresoform, melamine cresoform and their mixture.Phenols, many other reaction product that contain between azaheteroaryl and the aldehyde will be used for forming suitable hydroxy-containing resin for those skilled in the art's approval.If desired, can use other aldehyde and/or other triaizine compounds.As at " Encyclopedia of PolymerScience and Engineering ", the 2nd edition, the 11st volume, the 50th page; Or at " Kirk-Othmer Encyclopedia of Chemical Technology ", the 4th edition, the 18th volume, disclosed such these resins for preparing in the 606th page.
Being suitable for representative Resins, epoxy of the present invention is shown in
Epoxy Resins Chemistry and Technology, second edition,Edit (MarcelDekker, Inc.New York, 1988) by Clayton A.May,
Chemistry and Technology of Epoxy Resins,Edit (Blackie Academic ﹠amp by B.Ellis; Professional, Glasgow, 1993),
Handbook of Epoxy Resins,In H.E.Lee and K.Neville work (McGraw Hill, New York, 1967) and EP 1116774 A2.The Resins, epoxy that is fit to is, but be not limited to, based on bis-phenol and polyphenol, for example dihydroxyphenyl propane, tetramethyl-dihydroxyphenyl propane, Bisphenol F, bisphenol S, four benzene hydroxyl ethanes, Resorcinol, 4,4 '-Resins, epoxy of biphenyl, dihydroxy naphthlene, with derived from phenolic varnish, phenol for example: formaldehyde novolac, cresols: formaldehyde novolac, bisphenol-A phenolic varnish, biphenyl-, toluene-, dimethylbenzene-or the phenol of sym-trimethylbenzene-modification: the Resins, epoxy of formaldehyde novolac, derived from the aminotriazine novolac resin and the heterocyclic ring epoxy resins of p-aminophenol and cyanuric acid.In addition, for example, derived from 1, the aliphatic epoxy resin of 4-butyleneglycol, glycerine and Dicyclopentadiene (DCPD) skeleton is fit to.Many epoxy-resin systems that other is fit to are obtainable and are also thought to be fit to by those skilled in the art.
Use each molecule on average to have more than 1, preferably at least 1.8, more preferably the Resins, epoxy of at least 2 epoxy group(ing) is normally favourable.Under most preferred situation, this Resins, epoxy is the novolac epoxy that each molecule has at least 2.5 epoxy group(ing).In wide region of the present invention, this Resins, epoxy can be to have more than 11, any saturated or undersaturated aliphatic series of 2-epoxy group(ing), alicyclic, aromatics or heterogeneous ring compound.The example of heterocyclic ring oxygen compound is diglycidyl glycolylurea or triglycidyl group isocyanuric acid ester (TGIC).
Resins, epoxy does not preferably contain low alkyl group aliphatic series substituent Resins, epoxy, for example glycidyl ether of the glycidyl ether of phenol phenolic varnish or bisphenol-f.Preferred Resins, epoxy is novolac epoxy (be sometimes referred to as the epoxidation lacquer resins, this term is intended to contain epoxy phenol novolac resin and cresol novolac epoxy varnish resin they both).
Novolac epoxy (comprising the cresol novolac epoxy varnish resin) can be easily for example with trade(brand)name D.E.N.
TM, Quatrex
TM, (trade mark of Dow Chemical Company) and Epon
TM(Hexion Specialty Chemicals, the trade mark of Inc) is purchased.
1,4-quinhydrones or 1, phosphinate that the 4-naphthoquinones is functionalized and functionalized phosphonic acid ester or they both can be randomly as the fire retardant of a lot of thermosets and thermoplastic resin, for example multipolymer of polycarbonate, polyester, vinyl ester, cyanate, polymeric amide, polyimide, polyolefine (comprising polyethylene, polypropylene, poly--the 4-methylpentene, polystyrene), acrylonitrile-styrene-divinyl, urethane and many other materials; But the fire retardant that more particularly, is used for Resins, epoxy is general method.
Those skilled in the art can be with 1,4-quinhydrones or 1, both are transformed into the functional group of any number phosphinate that the 4-naphthoquinones is functionalized and functionalized phosphonic acid ester or they, for example, but be not limited to, ether, carbonic ether, carbamate and ester change the performance of material to improve the consistency in given resin system.Particularly, can be in the Resins, epoxy preparaton with these materials directly as linking agent.These materials are intended to be used for fire-retardant printed-wiring board (PWB).In addition, the resin of the present invention's description can be prepared to influence curing speed, strengthen flame retardant resistance and to improve physicals with extra additive and filler.
In addition, the present composition can be mixed with common additive with present composition with other fire retardant material to improve performance.These altogether-the FR material can be inorganic or organic, and can be reactivity or additive kind compound.The example of inorganic additives types of material includes but not limited to, hibbsite (ATH), magnesium hydroxide, hydrated barta, lime carbonate, titanium dioxide and silicon-dioxide.Be particularly useful altogether-the FR filler is ATH.The self-gravitation character of co-curing agent of the present invention can further be enhanced to satisfy UL-94 V-0 requirement by adding suitable fire-retardant auxiliary.Aforesaid other filler will be thought flame retardant properties useful by those skilled in the art.The example of organic class additive or reactive component comprises, but be not limited to, triphenylphosphate, Resorcinol two (two-2,6-xylyl phosphoric acid ester), 9, the 10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene-10-oxide compound, dihydroxyphenyl propane two (phenylbenzene-phosphoric acid ester), melamines, melamine phosphate, melamine borate and many other materials well known to those skilled in the art.
Can use filler to influence physicals and to reduce cost in the present invention.Usually, filler and toughener comprise glass fibre, granulated glass sphere (solid or hollow), silicon-dioxide or the silicon carbide whisker etc. of mica, talcum, kaolin, wilkinite, wollastonite, glass fibre, glass fabric, glassmat, grinding.Many these materials are at Encyclopedia of MaterialsScience and Engineering, and the 3rd rolls up, the 1745-1759 page or leaf, and MIT press, Cambridge, MA enumerates in (1986), and its disclosure is hereby incorporated by.The binding substances of filler is preferred in some embodiments; As under the situation of the glass fabric of prepreg that is used for printed-wiring board (PWB) and veneer sheet, toughener constitutes the major part of matrix material of the present invention yet in other embodiments.
The curing catalyst or the catalyzer that are fit to that can be used for this preparaton comprise, still are not limited to, and replacement or unsubstituted imidazoles be imidazoles, glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-phenylimidazole etc. for example.Other catalyzer comprises tertiary amine and acid amides.Also can use phosphine catalyst, for example triphenylphosphine.Also can use separately or combine with other catalyzer and use Lewis acid, this is convention to those skilled in the art.The example of typical Lewis acid comprises the oxide compound and the oxyhydroxide of zinc, tin, silicon, aluminium, boron and iron; Also can use boron trifluoride or boric acid.
Put into practice according to the present invention, the matrix material of resin impregnation is provided, it comprises the curable compositions at least a and described herein in filler or the toughener, and this matrix material solidifies at least in part.For example, of the present invention 1,4-quinhydrones or 1, phosphinate that the 4-naphthoquinones is functionalized and functionalized phosphonic acid ester mixture, polyhydroxy resin and Resins, epoxy are advantageously used in the manufacturing of the prepreg that is used for preparing printed-wiring board (PWB) and veneer sheet.The resin that to describe preparation by this paper and one or more solidifying agent and optional promotor (one or more) are mixed and are applied on the woven fiber glass.In being generally 150 ℃-200 ℃ baking oven, the sheet material or the prepreg of resin impregnation solidified several minutes at least in part then; For example 1-5 minute.
In order to prepare the sort of veneer sheet that is used for printed-wiring board (PWB), pile up the layer of resin impregnation shown in it with a plurality of prepregs are adjacent one another are.Each side at this stacked body provides copper foil layer, for example multilayer.Then this stacked body (comprising layer of cloth and paper tinsel layer) is arrived 50psi 20 in press, compacting 1 hour or longer time are to prepare the veneer sheet of compacting under the pressure of preferred 30-35psi, 170-220 ℃ high temperature.Therefore veneer sheet comprises a plurality of fused layers of the glass fabric of resin impregnation.If desired, depend on required structure, can use more or less preimpregnation bed of material or paper tinsel layer.
In embodiment subsequently, use hereinafter to be referred as:
The ATH hibbsite
DEN 438 can be from the epoxidised novolaks resin of Dow Chemical Co acquisition
Dowanol PM 1-methoxyl group-2-propyl alcohol
The DSC dsc
The FR fire retardant
The 2MI glyoxal ethyline
31The nuclear magnetic resonance spectrum of P NMR phosphorus
The PWB printed-wiring board (PWB)
Phr part/hundred part resin
The Tg second-order transition temperature
SD-1708 can be from Hexion Specialty Chemicals, the phenol that Inc obtains
Formaldehyde resin (novolac resin)
The TGA thermogravimetric analysis
Embodiment
Embodiment 1.
2,5-dihydroxy phenyl-phenyl phosphinic acid 2, the preparation of 6-dimethyl-phenylester (Compound I B):
With 2 of 390g (3.2mol), the 6-xylenol adds in the reaction vessel and is heated to 60 ℃, produces melt.Subsequently, under agitation, add 572g (3.2mol) phenyl dichloro phosphine.After two hours, temperature is risen to 95 ℃, rise to 135 ℃ then and kept two hours, rise to 185 ℃ and keep two hours to remove HCl gas.Mixture is cooled to envrionment temperature and adds 2.1 liters of toluene.In 0.5 hour, add stoichiometric water.Observe this reaction mixture and rise to 45 ℃ maximum value, and under agitation in 4 hours, return to envrionment temperature from envrionment temperature.The acetate that adds 1.8g (0.03mol) is as catalyzer.This mixture heating up to 80-85 ℃, and was added 1 of 3.4mol continuously in 6 hours, 4-benzoquinones (4.7 liters solution in toluene).Finish after the interpolation, stirred this mixture 20 hours down at 95 ℃.By crystallization with the crude product purifying.This material has 172 ℃ fusing point and dissolves in acetone.By
31This product is identified in P NMR spectrum and ultimate analysis.
Embodiment 2.
2, the preparation of two (2, the 6-3,5-dimethylphenyl) esters (Compound I IB) of 5-dihydroxy phenyl phosphonic acids.
Can be with 2 of 100.0g, the 6-xylenol adds in the reaction vessel and is heated to 60 ℃, produces melt.The phosphorus trichloride that under agitation can dropwise add subsequently, 56.2g.Temperature can be continued to rise to 95 ℃ after 2 hours, keep 2 hours; Rising to 135 ℃ kept 2 hours; Rise to 185 ℃ and keep 2 hours to remove HCl.Mixture can be cooled to envrionment temperature and can add 200 gram toluene.In 0.5 hour, can add 7.38g water, and can under situation about not heating, stir 4 hours.Can add 400g toluene.Can add 0.22g acetate as catalyzer.This mixture heating up 80-90 ℃ can be arrived, and 1 of 44.2g, 4-benzoquinones can be in 6 hours, added.Down this reaction mixture was heated other 10-20 hour at 110 ℃.Can be by crystallization or column chromatography with the crude product purifying.Can pass through
31This product is identified in P NMR spectrum and ultimate analysis.
Embodiment 3.
Use compound 1 as co-curing agent prepared layer pressing plate
Preparation 64.5phr passes through 2 of embodiment 1 preparation, 5-dihydroxy phenyl-phenyl phosphinic acid 2,6-dimethyl-phenylester and the 17.7phr SD-1708 solution in 127phr Dowanol PM.100phr DEN 438 Resins, epoxy and 0.0013phr glyoxal ethyline are added in the solution." the glass fabric synusia carries out about 2 minutes of B-stageization to form prepreg to eight 12 * 12 of gained varnish impregnations then in the baking oven under 170 ℃.The 1 ounce copper foil sheet in eight 11 * 11 " prepreg and 2 outsides 12 * 12 " is stacked, and at 185 ℃, 33PSI down compacting 160 minutes to produce veneer sheet.
Embodiment 4.
Use 2,5-dihydroxy phenyl-phenyl phosphinic acid 2,6-dimethyl-phenylester are as the co-curing agent, and ATH is as being total to-FR material preparation veneer sheet:
Preparation 64.6phr passes through 2 of embodiment 1 preparation, 5-dihydroxy phenyl-phenyl phosphinic acid 2,6-dimethyl-phenylester and the 17.7phr SD-1708 solution in 127phr Dowanol PM.100phr DEN 438,78.2phr ATH and 0.0010phr glyoxal ethyline are added in this solution to form slurry.Eight 12 * 12 " 7628 glass fabric synusia also carry out B-stageization under 170 ℃ to use the gained varnish impregnation.The 1 ounce copper foil sheet in eight 11 * 11 " prepreg and 2 outsides 12 * 12 " is stacked, and at 185 ℃, 33PSI down compacting 160 minutes to produce veneer sheet.
Embodiment 5.
Use 2, two (2, the 6-3,5-dimethylphenyl) esters of 5-dihydroxy phenyl phosphonic acids are as the description of the veneer sheet of co-curing agent:
Can be with 2 of 72.5phr embodiment 2, two (2, the 6-3,5-dimethylphenyl) esters of 5-dihydroxy phenyl phosphonic acids and 17.7phr SD 1708 stir with 127phr Dowanol PM.Can add 100phr DEN 438 and 0.0013phr glyoxal ethyline then.Gained varnish can flood eight 12 * 12 " 7628 glass fabric synusia, and can under 170 ℃, carry out B-stageization.The 1 ounce copper foil sheet in eight 11 * 11 " prepreg and 2 outsides 12 * 12 " can be stacked, and can be at 185 ℃, 33PSI down compacting 160 minutes to produce veneer sheet.
Embodiment 6.
Veneer sheet by the preparation of phenolic varnish solidifying agent:
Use the unique solidifying agent prepared layer pressing plate that is used for Resins, epoxy according to the novolac resin conduct of structure V according to the step of embodiment 3.
The performance of the material by the foregoing description preparation provides in table 1.
Table 1
| Preparaton numbering (phr) | |||
| Composition/embodiment | 4 | 3 | 6 |
| DEN 438 | 100 | 100 | 100 |
| Structure 1B 2,5-dihydroxy phenyl-phenyl phosphinic acid 2,6-dimethyl-phenylester | 64.6 | 64.5 | Do not have |
| SD-1708 | 17.7 | 17.7 | 72.6 |
| 2-MI | 0.001 | 0.001 | 0.05 |
| ATH | 78.2 | Do not have | Do not have |
| The veneer sheet performance | |||
| TGA. 15％ ℃ | 344 | 376 | 387 |
| Tg ℃ (passing through DSC) | 116 | 133 | 174 |
| T-260， 2Minute | Not failure | Not failure | N/A |
| T-288， 2Minute | ＞90 | 46 | N/A |
| Pressure cooker/immersed solder (% moisture content/grade; 5=is best) | 0.218/5 | 0.219/5 | N/A/5 |
| UL-94 combustion test Ave T1/T2 | 18/13 | 44/0 | 67/0 |
| Total combustion time 3, second | 155 | 219 | 335 |
| Burning is observed | Weak flame, 1 inch (2.5cm) of slow edge burning, self-gravitation | Weak flame, 2 inches (5cm) of slow edge burning, self-gravitation | Veneer sheet all burns down |
Footnote:
1. TGA experiment: analytic sample in thermogravimetric analyzer.Under nitrogen atmosphere, with 10 ℃/minute speed the temperature in the analyser is elevated to 700 ℃ maximum value from room temperature.The temperature that is write down is the temperature when 5% mass loss takes place.
2. T-260 is meant by IPC (Association Connecting ElectronicsIndustries) the use thermomechanical analyzer (TMA) that limits and is determined at the detection method of 260 ℃ of lower leaf times.Use detection side's religious name 2.4.24.1.Similarly carrying out T-288 to measure the stratified time, is under 288 ℃ temperature still.
3. total combustion time of five test samples, wherein each sample has two kinds of flames application.
Data in the table 1 show: comprise 2, and 5-dihydroxy phenyl-phenyl phosphinic acid 2, the preparaton of 6-dimethyl-phenylester shows the inherent flame retardant properties.Though these preparatons are not optimized with regard to V-0 FR performance, from very weak flame front and self-gravitation characteristic, its inherent FR performance is conspicuous.By contrast, non-FR control sample has much strong flame front, and this flame front causes this veneer sheet sample all to burn down.
Use the basic preparatons of these of this material to show very good thermostability by following character representation: with the temperature value of the approaching higher TGA 5wt% loss of non-fire-retardant control sample, and considerably beyond the T-260 and the T-288 result of pb-free solder application need.
Claims (20)
1. composition, it comprises according to 1 of following structure I, II, III, IV, 4-quinhydrones deutero-phosphinate, 1,4-quinhydrones deutero-phosphonic acid ester, 1,4-naphthoquinones deutero-phosphinate, 1,4-naphthoquinones deutero-phosphonic acid ester, or their binding substances:
Wherein R, R ' are identical or different aryl, aralkyl or the alkyl that contains 1-15 carbon atom independently of one another, but for structure I, R cannot be methyl or ethyl, and for structure I I, R and R ' cannot be methyl, ethyl or sec.-propyl simultaneously.
2. the composition of claim 1, wherein structure I is 2,5-dihydroxy phenyl-phenyl phosphinic acid 2,6-dimethyl-phenylester.
3. the composition of claim 1, wherein structure I I is 2, two (2, the 6-3,5-dimethylphenyl) esters of 5-dihydroxy phenyl phosphonic acids.
4. polymer composition, it comprises in the structure of claim 1 one or more.
5. the polymer composition of claim 4, wherein this polymkeric substance is a thermosetting resin.
6. the polymer composition of claim 4, wherein this polymkeric substance is a thermoplastic resin.
7. the composition of claim 5, wherein this polymkeric substance is a Resins, epoxy.
8. the composition of claim 7, wherein this Resins, epoxy also reacts with phenolic varnish.
9. the composition of claim 8, it also comprises strongthener.
10. the composition of claim 9, wherein this strongthener is glass, carbon, polyaramide or quartzy fiber.
11. the composition of claim 9 wherein partly solidifies this resin and strongthener to form prepreg.
12. the compacted lift pressing plate that forms by a plurality of prepregs according to claim 11.
13. according to the veneer sheet of claim 12, it also comprises Copper Foil.
14. the composition of claim 7, wherein this structure is selected from 2,5-dihydroxy phenyl-phenyl phosphinic acid 2,6-dimethyl-phenylester, 2, two (2, the 6-3,5-dimethylphenyl) esters of 5-dihydroxy phenyl phosphonic acids; 2,5-dihydroxyl naphthyl-phenyl phosphinic acid 2,6-dimethyl-phenylester; 2, two (2, the 6-3,5-dimethylphenyl) ester or their binding substancess of 5-dihydroxyl naphthyl-phosphonic acids.
15. the resin of claim 13, wherein this 1,4-quinhydrones deutero-phosphonic acid ester is selected from 2,5-dihydroxy phenyl-phenyl-phosphonic acid 2,6-dimethyl-phenylester or 2,5-dihydroxy phenyl phosphonic acids two (2, the 6-3,5-dimethylphenyl) ester, 2,5-dihydroxyl naphthyl-phenyl phosphinic acid 2,6-dimethyl-phenylester, 2, two (2, the 6-3,5-dimethylphenyl) ester or their binding substancess of 5-dihydroxyl naphthyl-phosphonic acids.
16. Resins, epoxy, it comprises according to 1 of following structure I, II, III, IV, 4-quinhydrones deutero-phosphinate, 1,4-quinhydrones deutero-phosphonic acid ester, 1,4-naphthoquinones deutero-phosphinate, 1, the reaction product of 4-naphthoquinones deutero-phosphonic acid ester or their binding substances and Epicholorohydrin:
Wherein R, R ' are identical or different aryl, aralkyl or the alkyl that contains 1-15 carbon atom independently of one another.
17. Resins, epoxy, it comprises 1,4-quinhydrones deutero-phosphinate, 1,4-quinhydrones deutero-phosphonic acid ester, 2,5-naphthalenediol deutero-phosphinate, 2, the reaction product of 5-naphthalenediol deutero-phosphonic acid ester or their binding substances and Epicholorohydrin.
18. the composition of claim 1, wherein structure III is 2,5-dihydroxyl naphthyl-phenyl phosphinic acid 2,6-dimethyl-phenylester
19. the composition of claim 1, wherein structure I V is 2, two (2, the 6-3,5-dimethylphenyl) esters of 5-dihydroxyl naphthyl-phosphonic acids.
20. composition, it comprises according to 1 of following structure I, II, III, IV, 4-quinhydrones deutero-phosphinate, 1, and 4-quinhydrones deutero-phosphonic acid ester, 1,4-naphthoquinones deutero-phosphinate, 1,4-naphthoquinones deutero-phosphonic acid ester or their binding substances:
Wherein R, R ' are identical or different aryl, aralkyl or the alkyl that contains 1-15 carbon atom independently of one another;
And polymkeric substance.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US61178204P | 2004-09-21 | 2004-09-21 | |
| US60/611,782 | 2004-09-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101061127A true CN101061127A (en) | 2007-10-24 |
Family
ID=35464163
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2005800391790A Pending CN101061127A (en) | 2004-09-21 | 2005-09-21 | 1,4-hydroquinone functionalized phosphinates and phosphonates |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP1791850A1 (en) |
| JP (1) | JP2008513585A (en) |
| CN (1) | CN101061127A (en) |
| IN (1) | IN2007DE02386A (en) |
| WO (1) | WO2006034445A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115806653A (en) * | 2022-12-21 | 2023-03-17 | 江苏扬农锦湖化工有限公司 | Naphthalene-series halogen-free flame-retardant epoxy resin and preparation method and application thereof |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2334691A1 (en) * | 2008-08-28 | 2011-06-22 | Dow Global Technologies LLC | Phosphorus-containing compounds and polymeric compositions comprising same |
| WO2012113829A1 (en) | 2011-02-23 | 2012-08-30 | Basf Se | Sulfonium sulfates, their preparation and use |
| JP6038284B2 (en) | 2012-04-19 | 2016-12-07 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Sulfonium compounds, their production and use |
| JP6637253B2 (en) * | 2015-05-12 | 2020-01-29 | 株式会社Adeka | Epoxy resin composition and fiber reinforced plastic using the same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2553417A (en) * | 1950-02-23 | 1951-05-15 | Us Rubber Co | Adducts of quinones and dialkyl phosphites |
| US3159537A (en) * | 1960-12-20 | 1964-12-01 | American Cyanamid Co | Potentiation of tetracycline by phosphinic acid |
| DE19612481C2 (en) * | 1996-03-29 | 2003-11-13 | Sennheiser Electronic | Electrostatic converter |
-
2005
- 2005-09-21 WO PCT/US2005/034134 patent/WO2006034445A1/en not_active Application Discontinuation
- 2005-09-21 CN CNA2005800391790A patent/CN101061127A/en active Pending
- 2005-09-21 JP JP2007532683A patent/JP2008513585A/en active Pending
- 2005-09-21 EP EP05798431A patent/EP1791850A1/en not_active Withdrawn
-
2007
- 2007-03-29 IN IN2386DE2007 patent/IN2007DE02386A/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115806653A (en) * | 2022-12-21 | 2023-03-17 | 江苏扬农锦湖化工有限公司 | Naphthalene-series halogen-free flame-retardant epoxy resin and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2008513585A (en) | 2008-05-01 |
| IN2007DE02386A (en) | 2007-08-03 |
| WO2006034445A1 (en) | 2006-03-30 |
| EP1791850A1 (en) | 2007-06-06 |
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