CN114752205A - Intrinsic halogen-free flame-retardant polyphenyl ether resin composition and application thereof - Google Patents
Intrinsic halogen-free flame-retardant polyphenyl ether resin composition and application thereof Download PDFInfo
- Publication number
- CN114752205A CN114752205A CN202210483113.6A CN202210483113A CN114752205A CN 114752205 A CN114752205 A CN 114752205A CN 202210483113 A CN202210483113 A CN 202210483113A CN 114752205 A CN114752205 A CN 114752205A
- Authority
- CN
- China
- Prior art keywords
- retardant
- resin composition
- flame
- polyphenyl ether
- ether resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 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 title claims abstract description 95
- 239000003063 flame retardant Substances 0.000 title claims abstract description 95
- 229920013636 polyphenyl ether polymer Polymers 0.000 title claims abstract description 53
- 239000011342 resin composition Substances 0.000 title claims abstract description 45
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 78
- 229920005989 resin Polymers 0.000 claims abstract description 45
- 239000011347 resin Substances 0.000 claims abstract description 45
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 239000004744 fabric Substances 0.000 claims abstract description 17
- -1 diaryl phosphine oxide Chemical compound 0.000 claims abstract description 14
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims abstract description 11
- 230000000694 effects Effects 0.000 claims abstract description 10
- 239000000835 fiber Substances 0.000 claims abstract description 6
- 239000000178 monomer Substances 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 239000010949 copper Substances 0.000 claims abstract description 5
- 229920001955 polyphenylene ether Polymers 0.000 claims description 23
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000003822 epoxy resin Substances 0.000 claims description 11
- 229920000647 polyepoxide Polymers 0.000 claims description 11
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 9
- 239000012752 auxiliary agent Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000003431 cross linking reagent Substances 0.000 claims description 9
- 229910052731 fluorine Inorganic materials 0.000 claims description 9
- 239000011737 fluorine Substances 0.000 claims description 9
- 230000002195 synergetic effect Effects 0.000 claims description 9
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 8
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 5
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims description 5
- NRNFFDZCBYOZJY-UHFFFAOYSA-N p-quinodimethane Chemical group C=C1C=CC(=C)C=C1 NRNFFDZCBYOZJY-UHFFFAOYSA-N 0.000 claims description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 4
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical group CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 150000002978 peroxides Chemical class 0.000 claims description 3
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 claims description 2
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 229920000388 Polyphosphate Polymers 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 claims description 2
- 239000004643 cyanate ester Substances 0.000 claims description 2
- BEQVQKJCLJBTKZ-UHFFFAOYSA-M diphenylphosphinate Chemical compound C=1C=CC=CC=1P(=O)([O-])C1=CC=CC=C1 BEQVQKJCLJBTKZ-UHFFFAOYSA-M 0.000 claims description 2
- 125000003700 epoxy group Chemical group 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 2
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 229920003052 natural elastomer Polymers 0.000 claims description 2
- 229920001194 natural rubber Polymers 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 229920006124 polyolefin elastomer Polymers 0.000 claims description 2
- 239000001205 polyphosphate Substances 0.000 claims description 2
- 235000011176 polyphosphates Nutrition 0.000 claims description 2
- 229920000734 polysilsesquioxane polymer Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 claims description 2
- 125000005504 styryl group Chemical group 0.000 claims description 2
- 229920003051 synthetic elastomer Polymers 0.000 claims description 2
- 239000005061 synthetic rubber Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 239000002952 polymeric resin Substances 0.000 abstract description 4
- 229920003002 synthetic resin Polymers 0.000 abstract description 4
- 229920006351 engineering plastic Polymers 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000011889 copper foil Substances 0.000 description 73
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 38
- 239000000758 substrate Substances 0.000 description 33
- 238000010030 laminating Methods 0.000 description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 13
- 239000003365 glass fiber Substances 0.000 description 12
- 238000005259 measurement Methods 0.000 description 11
- 230000000704 physical effect Effects 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 238000005470 impregnation Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 239000004593 Epoxy Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 238000003825 pressing Methods 0.000 description 6
- 238000001308 synthesis method Methods 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 5
- 239000004721 Polyphenylene oxide Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 229920006380 polyphenylene oxide Polymers 0.000 description 5
- 239000002966 varnish Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- 239000000805 composite resin Substances 0.000 description 4
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 4
- 229920013638 modified polyphenyl ether Polymers 0.000 description 4
- 229920006389 polyphenyl polymer Polymers 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 229940045803 cuprous chloride Drugs 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000010365 information processing Effects 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 239000012745 toughening agent Substances 0.000 description 2
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 1
- LLOXZCFOAUCDAE-UHFFFAOYSA-N 2-diphenylphosphorylbenzene-1,4-diol Chemical compound OC1=CC=C(O)C(P(=O)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 LLOXZCFOAUCDAE-UHFFFAOYSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- HHYPIHRXIVCVEN-UHFFFAOYSA-N 4-[1-chloro-2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound C=1C=C(O)C=CC=1C(CCl)(C)C1=CC=C(O)C=C1 HHYPIHRXIVCVEN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- LJUXFZKADKLISH-UHFFFAOYSA-N benzo[f]phosphinoline Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=P1 LJUXFZKADKLISH-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004870 electrical engineering Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/48—Polymers modified by chemical after-treatment
- C08G65/485—Polyphenylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/036—Multilayers with layers of different types
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08J2371/12—Polyphenylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The invention discloses an intrinsic halogen-free flame-retardant polyphenyl ether resin composition and application thereof, and relates to the field of modification of flame-retardant high polymer materials and application thereof in electronic related materials. The resin composition contains intrinsic halogen-free flame-retardant polyphenyl ether, halogen-free flame-retardant groups of diaryl phosphine oxide are introduced into the molecular structure of the polyphenyl ether, the polyphenyl ether can be directly used as high polymer resin with flame retardance, and the polyphenyl ether resin can also be used with other resins and auxiliaries to form a flame-retardant composition with multiple purposes. The polyphenyl ether resin composition obtained by the invention has the characteristics of good halogen-free flame retardant effect, low dielectric constant, dielectric loss and the like, and the flame retardance of polyphenyl ether can be controlled by controlling the content of the reaction monomer of the diaryl phosphine oxide flame retardant group. The prepared polyphenyl ether and the composition thereof can be widely used in the fields of films of printed circuit boards, high-speed and high-frequency copper clad plates and other fiber cloth laminated plates, electronic and electrical, engineering plastics and the like which have higher requirements on flame retardance and dielectric property.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to an intrinsic halogen-free flame-retardant polyphenyl ether resin composition and application thereof.
Background
With the rapid development of electronic technology, information processing of electronic products such as mobile communication, servers, and mainframe computers is continuously developing towards "high frequency and high speed digitization of signal transmission", and low dielectric resin materials are therefore the main development direction of high transmission rate substrates to meet the requirement of high speed information processing. The polyphenyl ether has the characteristics of extremely low dielectric constant, dielectric loss and water absorption, excellent heat resistance, good dimensional stability, excellent bonding performance with copper foil and the like, and has a very large application space in the field of electronics and electricity. Polyphenylene ether structures themselves are flame retardant, but flame resistance is greatly reduced due to introduction of reactive groups such as vinyl groups and reduction of molecular weight, and therefore flame retardant modification is required. At present, due to the trend of no halogenation, phosphorus flame retardants are widely used in industry for flame retardant modification. However, when DOPO and derivatives thereof are used as flame retardants at present, the prepared composite material has large addition amount, low flame retardant efficiency and high water absorption, thereby influencing the use stability of the material and having large influence on dielectric properties. In addition, the existing method for preparing the flame-retardant polyphenylene oxide material by using the additive flame retardant through melt blending has the problems of easy precipitation and great influence on other physical properties of the material.
Chinese patent No. CN104341766B discloses a low dielectric resin composition and a copper foil substrate and a printed circuit board using the same, which uses vinyl polyphenylene ether resin in combination with 60-150 parts by weight of brominated flame retardant, and does not meet the environmental-friendly flame retardant requirement. The Chinese patent with the publication number of CN105238000B discloses a low dielectric composite material, a laminated board and a circuit board thereof, diphenyl phosphine oxide is firstly prepared into an additive flame retardant, and a flame-retardant polyphenyl ether composite material is prepared in a melt blending mode, so that the problems of low flame-retardant efficiency, large addition amount, large influence on the mechanical property of polyphenyl ether and the like exist, and the use of downstream customers is influenced. The patent of the invention with the publication number of CN106700475B discloses a flame-retardant polyphenylene ether resin composition, which adopts phosphorus-containing polyphenylene ether resin containing DOPO flame-retardant group, because DOPO is easy to absorb moisture and form hydroxyl, the defects of high water absorption, insufficient heat resistance and poor dielectric property of the product exist.
Disclosure of Invention
Based on the technical problems, the invention provides an intrinsic halogen-free flame-retardant polyphenyl ether resin composition and application thereof.
The technical solution adopted by the invention is as follows:
An intrinsic halogen-free flame retardant polyphenylene ether resin composition comprises an intrinsic halogen-free flame retardant polyphenylene ether resin and an auxiliary agent;
the intrinsic halogen-free flame-retardant polyphenyl ether resin has a chemical structural formula shown as the following formula (1):
in the formula (1), A is selected from H, structural monomers with epoxy groups, vinyl groups, propenyl groups or styryl groups and with crosslinking activity;
R1，R2，R3，R4are respectively selected from H, aryl and C1-6Straight or branched chain alkyl;
Y1is an oxygen atom, a straight chain alkyl group, a branched alkyl group or no group; when Y is1When it is an oxygen atom or no group, X1Is free of radicals;
Y2is an oxygen atom, a straight chain alkyl group or a branched chain alkyl group;
X1is a structural unit bearing at least one flame retardant diarylphosphine oxide group or no group;
X2is a structural unit bearing at least one flame retardant diarylphosphine oxide group or with R1，R2，R3，R4The same groups; and in an intrinsic halogen-free flame-retardant polyphenylene ether resin molecular structure, X1And X2At least one of the two is a structural unit with an aryl phosphine oxide flame-retardant group;
a. b is a natural number between 0 and 60 respectively, but is not 0 at the same time.
Preferably, the structural unit of the flame retardant diarylphosphine oxide group has a chemical structural formula shown in formula (2) below:
In the formula (2), R5，R6One selected from hydrogen, fluorine-containing straight-chain alkyl or branched-chain alkyl and fluorine-containing aromatic group;
r7 is selected from one of oxygen, alkyl, biphenyl and naphthyl; or R7 is an unsubstituted group.
Preferably, X is1And X2Are respectively selected from one of the following formulas (3) to (13);
preferably, the dosage of the intrinsic halogen-free flame-retardant polyphenyl ether resin is 10-100 parts, and the dosage of the auxiliary agent is 0.1-30 parts; the auxiliary agent adopts a cross-linking agent and/or an accelerating agent.
Preferably, the crosslinking agent is selected from one or a mixture of more than two of triallyl isocyanurate, divinylbenzene and dicumyl peroxide.
Preferably, the accelerator is methyl imidazole or a peroxide hardening accelerator that can generate free radicals.
Preferably, the resin composition also comprises a polymer, and the amount of the polymer is 30-90 parts based on 100 parts of the intrinsic halogen-free flame-retardant polyphenylene ether resin;
the polymer is selected from one of epoxy resin, phenolic resin, vinyl benzyl ether compound derivative resin, maleimide resin, polyimide, cyanate ester resin, polyolefin, natural and synthetic rubber, polystyrene, polyacrylate, benzoxazine, polycarbonate, butadiene-styrene resin, polyurethane, polyamide and polyester, or a mixture of more than two of the above.
Preferably, the resin composition also comprises a synergistic flame retardant, and the dosage of the synergistic flame retardant is 5 to 10 parts by 100 parts of the dosage of the intrinsic halogen-free flame retardant polyphenylene oxide resin;
the synergistic flame retardant is selected from one or more of hexaphenoxycyclotriphosphazene, melamine cyanurate, hypophosphite, dialkyl phosphinate, diphenyl phosphinate, p-xylylene bis (diphenylphosphine oxide), melamine polyphosphate, aluminum hydroxide, silicon dioxide and polysilsesquioxane.
Preferably, the Y1 is oxygen atom, methylene, p-phenol group or 1, 4-naphthol.
The intrinsic halogen-free flame-retardant polyphenyl ether resin composition is applied to the preparation of printed circuit board films, high-speed high-frequency copper clad laminates or fiber cloth laminates.
Specifically, according to different application fields of the composition, the composition further comprises a solvent, a curing agent, inorganic reinforcing materials such as glass fibers and carbon fibers, a silane coupling agent, an antioxidant, a stabilizer, a filler, natural minerals, a dye, a toughening agent and other common auxiliary agents or a mixture of the common auxiliary agents. The solvent is preferably one or a mixture of more than two of acetone, butanone, toluene and dimethyl sulfoxide; the toughening agent is preferably one or a mixture of more than two of styrene-maleic anhydride copolymer and hydrogenated styrene-butadiene-divinylbenzene copolymer; the silane coupling agent may be at least one of an alkylsilane compound and an alkylsiloxane compound. The polyphenyl ether and the composition thereof prepared by the invention can be widely used in the fields of films of printed circuit boards, high-speed and high-frequency copper clad plates and other fiber cloth laminated plates, electronics, electrical engineering plastics and the like with higher requirements on flame retardance and dielectric property.
The beneficial technical effects of the invention are as follows:
the invention provides an intrinsic halogen-free flame-retardant polyphenyl ether resin composition and application thereof. The polyphenyl ether resin can form a flame-retardant composition with multiple purposes with other resins, has the advantages of no halogen, environmental protection, no precipitation, small addition amount, good flame-retardant effect, excellent mechanical property, high thermal stability, low water absorption, excellent dielectric property and the like, and can control the flame retardance of the polyphenyl ether by controlling the content of the reaction monomer with the aryl phosphine oxide flame-retardant group. The resin composition can be applied to the fields of films of circuit boards, high-speed and high-frequency copper-clad plates and other fiber cloth laminated plates, electronics, electrics, engineering plastics and the like.
Specifically, the resin composition mainly adopts the intrinsic halogen-free flame-retardant polyphenyl ether resin, the polyphenyl ether resin introduces flame-retardant groups containing aryl phosphine oxide at different positions of the structure, and the polyphenyl ether resin can be directly used as high polymer resin with flame-retardant property by controlling the quantity of the introduced flame-retardant groups. The intrinsic flame-retardant polyphenylene oxide resin can also be used as a polymeric flame retardant to form a flame-retardant composition with other high polymer resin materials for multiple purposes. The phosphorus-containing flame-retardant group is introduced to the side chain of the polyphenylene oxide molecule by means of chemical reaction, so that the stability of the polyphenylene oxide main chain is not influenced, and the material is endowed with excellent flame-retardant property. And the polyphenyl ether has excellent carbon forming property, and an acid source and a carbon source are combined into one molecular structure by introducing the phosphorus-containing flame-retardant group, so that the polyphenyl ether has an excellent flame-retardant effect. At present, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and derivatives thereof are commonly used as flame retardant groups to be grafted into different polymer resin structures, but because the phosphaphenanthrene ring is easy to absorb moisture to form hydroxyl, the application in the fields of electronic and electrical substrates and the like is limited. The diaryl flame retardant with the flame retardant group and the diaryl phosphine oxide flame retardant with the fluorine element successfully overcome the defects of easy moisture absorption, high water absorption, insufficient heat resistance and poor dielectric property of the DOPO. The flame retardant effect is improved through the synergistic effect of phosphorus and fluorine in the structure, the introduction of the fluorine element obviously reduces the dielectric constant and dielectric loss of a polyphenyl ether and epoxy resin system, solves the contradiction between the flame retardant property and the dielectric property, and achieves the ideal effect. The flame retardant has higher flame retardant efficiency when being used together with other phosphorus-nitrogen flame retardants.
Detailed Description
The following examples illustrate the raw materials used:
novolac epoxy PN-638, Laiwu Runda New materials, Inc.; SA9000 terminal methacrylate polyphenylene ether resin, Sabic corporation; hexaphenoxycyclotriphosphazene (HPCTP), p-xylylene bis (diphenylphosphine oxide) (DPO); melamine Cyanurate (MCA), shou guang weidong chemical co; electronic fiber cloth (2116 glass fiber cloth), purchased from south asian plastic; novolac SRW-9100, sierview materials science and technology ltd, hanan; dicyandiamide curing agent, azken, germany; the solvent toluene, butanone, TAIC, peroxide accelerator DCP are commercially available; synergistic flame retardant Aluminum Hydroxide (AH), a new flame retardant material of combined fertilizer Zhongke.
The structural formula of the intrinsic halogen-free flame retardant polyphenylene ether resin used in the following examples is as follows (number average molecular weight 2000-:
the synthesis method of the intrinsic halogen-free flame-retardant polyphenyl ether resin can be prepared by the conventional synthesis method of the existing allyl-terminated polyphenyl ether and the common synthesis method of low molecular weight polyphenyl ether. The preparation method listed in the invention is mainly different from the common method in monomer structure, proportion, change of reaction parameters and the like required by synthesis.
The specific embodiment is as follows:
(1) the synthesis method of the intrinsic halogen-free flame-retardant polyphenyl ether (A-1) comprises the following steps:
sequentially adding DMSO solvent into a three-neck flask, then adding 1mol of diphenyl phosphine oxide and 1mol of sodium hydroxide, controlling the temperature below 20 ℃, adding 1mol of 2, 2-bis (4' -hydroxyphenyl) chloropropane in batches, reacting for 2h, washing with ethanol and drying for later use to obtain an intermediate compound I.
1mo is mixedl intermediate compound I is dissolved in benzene, 4-chloro-2, 6-disubstituted phenol monomer is added, at 50 ℃, K is added3Fe(CN)6And (3) gradually adding 1mol of potassium hydroxide dropwise as a catalyst, continuously reacting for 2 hours, and performing suction filtration and drying to obtain an intermediate product II.
Dissolving 1mol of intermediate product II into tetrahydrofuran, adding 2mol of allyl acyl chloride, heating to 80 ℃, gradually dropping triethylamine acid-binding agent, and keeping the temperature for reaction for 4 hours; then filtering, washing and drying to obtain the polyphenyl ether A-1 product with intrinsic halogen-free flame retardant.
(2) The synthesis method of the intrinsic halogen-free flame-retardant polyphenyl ether (A-2) comprises the following steps:
adding a catalytic system consisting of toluene, cuprous chloride and diethylamine in a molar ratio of 30: 1: 19 into a three-neck flask in sequence, and carrying out complex reaction for 30min at the temperature of 1-40 ℃ under the conditions of oxygen supply and stirring. Then, a mixed toluene solution of 2, 6-dimethylphenol and 2, 5-dihydroxyphenyl (diphenyl) phosphine oxide (DPO-HQ) in a molar ratio of 2: 1 was added dropwise under the conditions of stable oxygen supply and stirring, and polymerization was carried out at 50 ℃ for 1 hour. Precipitating with anhydrous ethanol to separate out polymer, precipitating with anhydrous ethanol again, filtering, washing, and drying in a vacuum oven at 50 deg.C to constant weight.
(3) The synthesis method of the intrinsic halogen-free flame-retardant polyphenyl ether (A-3) comprises the following steps:
adding a catalytic system consisting of toluene, cuprous chloride and diethylamine in a molar ratio of 30: 1: 19 into a three-neck flask in sequence, and carrying out complex reaction for 30min at the temperature of 1-40 ℃ under the conditions of strong oxygen supply and stirring. A mixed 50% solids toluene solution of 2, 6-dimethylphenol and 2, 5-dihydroxyphenyl (phenyl-fluorophenyl) phosphine oxide (FDPO-HQ) in a molar ratio of 2: 1 was then added dropwise with constant oxygen supply and vigorous stirring and polymerized at 60 ℃ for 2 h. Precipitating with anhydrous ethanol to separate out polymer, precipitating with anhydrous ethanol again, filtering, washing, and drying in a vacuum oven at 50 deg.C to constant weight.
Example 1
100 parts of intrinsic halogen-free flame-retardant polyphenyl ether resin (A-1) is fully dissolved in a toluene solvent, and then a cross-linking agent TAIC, an accelerator di-tert-butyl peroxydiisopropylbenzene and other auxiliary agents are added and uniformly mixed to obtain a toluene solution of the polyphenyl ether resin composition, namely resin varnish with the concentration of 50-60%. The resin composition is attached to the glass fiber cloth by impregnation or coating, and then is heated and baked to be in a semi-cured state to obtain a semi-cured sheet. Taking four prepregs and two copper foils prepared by the method, laminating the prepregs according to the sequence of the copper foils, the four prepregs and the copper foils, laminating for 1-2 hours at the temperature of 210 ℃ under the vacuum condition to form a copper foil substrate, and respectively carrying out physical property measurement on the substrate containing the copper foil and the substrate without the copper foil after the copper foil is etched.
Example 2
Fully dissolving 100 parts of intrinsic halogen-free flame-retardant polyphenyl ether resin (A-1) in a toluene solvent, then adding 10 parts of silicon dioxide, 10 parts of aluminum hydroxide, a cross-linking agent TAIC, an accelerator di-tert-butyl dicumyl peroxide and other auxiliaries, and uniformly mixing to obtain a toluene solution of a polyphenyl ether resin composition, namely resin varnish with the concentration of 50-60%. The resin composition is adhered to the glass fiber cloth by impregnation or coating, and then is heated and baked to be in a semi-cured state to obtain a semi-cured sheet. Taking four prepregs and two copper foils prepared by the method, laminating the prepregs, the four prepregs and the copper foils in sequence, pressing the prepregs and the copper foils at the temperature of 180-210 ℃ for 1-2 hours under the vacuum condition to form a copper foil substrate, and respectively carrying out physical property measurement on the substrate containing the copper foil and the substrate without the copper foil after the copper foil is etched.
Example 3
100 parts of intrinsic halogen-free flame-retardant polyphenyl ether resin (A-1) is fully dissolved in a toluene solvent, then 10 parts of silicon dioxide, 10 parts of hexaphenoxycyclotriphosphazene, a cross-linking agent TAIC, a promoter di-tert-butyl peroxydiisopropylbenzene and other auxiliaries are added and uniformly mixed to obtain a toluene solution of the polyphenyl ether resin composition, namely resin varnish, with the mass percentage concentration of 50-60%. The resin composition is adhered to the glass fiber cloth by impregnation or coating, and then is heated and baked to be in a semi-cured state to obtain a semi-cured sheet. Taking four prepregs and two copper foils prepared by the method, laminating the prepregs according to the sequence of the copper foils, the four prepregs and the copper foils, laminating for 1-2 hours at the temperature of 210 ℃ under the vacuum condition to form a copper foil substrate, and respectively carrying out physical property measurement on the substrate containing the copper foil and the substrate without the copper foil after the copper foil is etched.
Example 4
Fully dissolving 50 parts of SA9000 polyphenyl ether and 50 parts of intrinsic halogen-free flame-retardant polyphenyl ether resin (A-1) in a toluene solvent, then adding 10 parts of silicon dioxide, 10 parts of p-xylylene bis (diphenylphosphine oxide), a cross-linking agent TAIC, an accelerator di-tert-butyl dicumyl peroxide and other auxiliaries, and uniformly mixing to obtain a toluene solution of the polyphenyl ether resin composition, namely resin varnish with the concentration of 50-60%. The resin composition is adhered to the glass fiber cloth by impregnation or coating, and then is heated and baked to be in a semi-cured state to obtain a semi-cured sheet. Taking four prepregs and two copper foils prepared by the method, laminating the prepregs according to the sequence of the copper foils, the four prepregs and the copper foils, laminating for 1-2 hours at the temperature of 210 ℃ under the vacuum condition to form a copper foil substrate, and respectively carrying out physical property measurement on the substrate containing the copper foil and the substrate without the copper foil after the copper foil is etched.
Example 5
80 parts of SA9000 polyphenyl ether and 20 parts of intrinsic halogen-free flame-retardant polyphenyl ether resin (A-2) are fully dissolved in a toluene solvent, and then 10 parts of silicon dioxide, 10 parts of p-xylylene bis (diphenylphosphine oxide), a cross-linking agent TAIC, an accelerator di-tert-butyl dicumyl peroxide and other auxiliaries are added and uniformly mixed to obtain a toluene solution of the polyphenyl ether resin composition, namely resin varnish with the concentration of 50-60%. The resin composition is adhered to the glass fiber cloth by impregnation or coating, and then is heated and baked to be in a semi-cured state to obtain a semi-cured sheet. Taking four prepregs and two copper foils prepared by the method, laminating the prepregs according to the sequence of the copper foils, the four prepregs and the copper foils, laminating for 1-2 hours at the temperature of 210 ℃ under the vacuum condition to form a copper foil substrate, and respectively carrying out physical property measurement on the substrate containing the copper foil and the substrate without the copper foil after the copper foil is etched.
Example 6
Fully dissolving epoxy resin (PN-638) in acetone, then adding hexaphenoxycyclotriphosphazene, dicyandiamide curing agent, 2-ethyl-4-methylimidazole and the like, uniformly mixing to obtain a solution of the epoxy resin composition, enabling the resin composition to be attached to glass fiber cloth in a manner of impregnation or coating and the like, and then heating and baking at 155 ℃ for 2min to be in a semi-cured state to obtain a semi-cured sheet. Taking four prepregs and two copper foils, laminating according to the sequence of the copper foils, the four prepregs and the copper foils, pressing at 150 ℃, 2 hours and 180 ℃ for 2 hours under a vacuum condition to form a copper foil substrate, and respectively carrying out physical property measurement on the substrate containing the copper foil and the substrate without the copper foil after the copper foil is etched.
Example 7
Fully dissolving the prepared modified polyphenyl ether (A-2) and epoxy resin (PN-638) in acetone, then adding dicyandiamide curing agent and 2-ethyl-4-methylimidazole, uniformly mixing to obtain solution of polyphenyl ether-epoxy composite resin composition, adhering the resin composition to glass fiber cloth in a manner of impregnation or coating, and then heating and baking at 155 ℃ for 2min to be in a semi-cured state to obtain a prepreg. Taking four prepregs and two copper foils, laminating according to the sequence of the copper foils, the four prepregs and the copper foils, pressing at 150 ℃, 2 hours and 180 ℃ for 2 hours under a vacuum condition to form a copper foil substrate, and respectively carrying out physical property measurement on the substrate containing the copper foil and the substrate without the copper foil after the copper foil is etched.
Example 8
Fully dissolving the modified polyphenyl ether (A-3) and the epoxy resin (PN-638) obtained in the preparation example in acetone, then adding hexaphenoxycyclotriphosphazene, dicyandiamide curing agent and 2-ethyl-4-methylimidazole, uniformly mixing to obtain polyphenyl ether-epoxy composite resin composition solution, adhering the resin composition to glass fiber cloth in a manner of impregnation or coating, and then heating and baking at 155 ℃ for 2min to obtain a semi-cured state to obtain a semi-cured sheet. Taking four prepregs and two copper foils, laminating according to the sequence of the copper foils, the four prepregs and the copper foils, pressing at 150 ℃, 2 hours and 180 ℃ for 2 hours under a vacuum condition to form a copper foil substrate, and respectively carrying out physical property measurement on the substrate containing the copper foil and the substrate without the copper foil after the copper foil is etched.
Example 9
Fully dissolving the modified polyphenyl ether (A-2) and the epoxy resin (PN-638) obtained in the preparation example in acetone, then adding melamine cyanurate, a phenolic curing agent and 2-methylimidazole, uniformly mixing to obtain a polyphenyl ether-epoxy composite resin composition solution, adhering the resin composition to glass fiber cloth in a manner of impregnation or coating, and then heating and baking at 155 ℃ for 2min to be in a semi-cured state to obtain a prepreg. Taking four prepregs and two copper foils, laminating according to the sequence of the copper foils, the four prepregs and the copper foils, pressing at 150 ℃, 2 hours and 180 ℃ for 2 hours under a vacuum condition to form a copper foil substrate, and respectively carrying out physical property measurement on the substrate containing the copper foil and the substrate without the copper foil after the copper foil is etched.
Example 10
Fully dissolving the modified polyphenyl ether (A-3) and the epoxy resin (PN-638) obtained in the preparation example in acetone, then adding a phenolic aldehyde curing agent and 2-methylimidazole, uniformly mixing to obtain a polyphenyl ether-epoxy composite resin composition solution, attaching the resin composition to glass fiber cloth in a soaking or coating mode, and then heating and baking at 155 ℃ for 2min to obtain a semi-cured state to obtain a semi-cured sheet. And taking four prepregs and two copper foils prepared in the above, laminating the prepregs according to the sequence of the copper foils, the four prepregs and the copper foils, pressing the prepregs and the copper foils at 150 ℃, 2 hours and 180 ℃ for 2 hours under a vacuum condition to form a copper foil substrate, and respectively carrying out physical property measurement on the substrate containing the copper foil and the substrate without the copper foil after the copper foil is etched.
The performance evaluation mode and the implementation standard of the intrinsic halogen-free flame-retardant polyphenylene ether resin composition prepared in the above embodiment are as follows:
the vertical burning test is carried out according to the GB/T2408-2008 method; oxygen Index (LOI) test according to GB/T2406.1-2008; glass transition temperature (Tg), DMA instrumental measurement; dielectric constant (Dk), dielectric loss (Df), and (10GHz) AET microwave dielectric analyzer.
The test results are given in table 1 below.
TABLE 1
As can be seen from Table 1, the copper clad laminate prepared by using the intrinsic flame retardant polyphenylene ether resin alone or in combination with the SA9000 resin has very good flame retardant property and dielectric property. The epoxy resin can be used alone or compounded with other flame retardants in an epoxy copper-clad plate to achieve V-0 level flame retardant grade and excellent dielectric property. Especially, in example 10, due to the introduction of fluorine element in the polyphenylene ether resin, the flame retardant effect is improved by the synergistic effect of phosphorus and fluorine, and the dielectric constant and dielectric loss of the epoxy resin system are very obviously reduced, so that an ideal effect is achieved. The invention can be used in the fields with higher flame retardant performance and lower dielectric constant and dielectric loss requirements.
Claims (10)
1. An intrinsic halogen-free flame-retardant polyphenyl ether resin composition is characterized in that: the resin composition comprises an intrinsic halogen-free flame-retardant polyphenyl ether resin and an auxiliary agent;
the intrinsic halogen-free flame-retardant polyphenyl ether resin has a chemical structural formula shown as the following formula (1):
in the formula (1), A is selected from H, structural monomers with epoxy groups, vinyl groups, propenyl groups or styryl groups and with crosslinking activity;
R1，R2，R3，R4are respectively selected from H, aryl and C1-6Straight or branched chain alkyl;
Y1is an oxygen atom, a straight chain alkyl group, a branched alkyl group or no group; when Y is1When it is an oxygen atom or no group, X1Is free of radicals;
Y2is an oxygen atom, a straight chain alkyl group or a branched chain alkyl group;
X1to bear at least one diarylphosphine oxide flame-retardant groupStructural units of groups or no groups;
X2is a structural unit bearing at least one flame retardant diarylphosphine oxide group or with R1，R2，R3，R4The same groups; and in an intrinsic halogen-free flame-retardant polyphenylene ether resin molecular structure, X1And X2At least one of the two is a structural unit with an aryl phosphine oxide flame-retardant group;
a. b is a natural number between 0 and 60 respectively, but is not 0 at the same time.
2. The polyphenylene ether resin composition of claim 1, wherein the structural unit of the flame retardant diarylphosphine oxide group has the following formula (2):
In the formula (2), R5，R6One selected from hydrogen, fluorine-containing linear alkyl or branched alkyl and fluorine-containing aromatic base;
r7 is selected from one of oxygen, alkyl, biphenyl and naphthyl.
3. The polyphenylene ether resin composition with an intrinsic halogen-free flame retardant property according to claim 1 or 2, wherein: said X is1And X2Are respectively selected from one of the following formulas (3) to (13);
4. the polyphenylene ether resin composition with an intrinsic halogen-free flame retardant property according to claim 1, wherein: the dosage of the intrinsic halogen-free flame-retardant polyphenyl ether resin is 10-100 parts, and the dosage of the auxiliary agent is 0.1-30 parts; the auxiliary agent adopts a cross-linking agent and/or an accelerating agent.
5. The polyphenylene ether resin composition according to claim 4, wherein the flame retardant is a halogen-free flame retardant comprising: the crosslinking agent is selected from one or a mixture of more than two of triallyl isocyanurate, divinyl benzene and dicumyl peroxide.
6. The polyphenylene ether resin composition according to claim 4, wherein the flame retardant is a halogen-free flame retardant comprising: the accelerator is methyl imidazole or peroxide hardening accelerator capable of generating free radicals.
7. The polyphenylene ether resin composition according to claim 1, wherein the flame retardant is one of the following: the resin composition also comprises a polymer, wherein the dosage of the polymer is 30-90 parts by taking 100 parts of the intrinsic halogen-free flame-retardant polyphenyl ether resin;
The polymer is selected from one of epoxy resin, phenolic resin, vinyl benzyl ether compound derivative resin, maleimide resin, polyimide, cyanate ester resin, polyolefin, natural and synthetic rubber, polystyrene, polyacrylate, benzoxazine, polycarbonate, butadiene-styrene resin, polyurethane, polyamide and polyester, or a mixture of more than two of the above.
8. The polyphenylene ether resin composition with an intrinsic halogen-free flame retardant property according to claim 1, wherein: the resin composition also comprises a synergistic flame retardant, and the dosage of the synergistic flame retardant is 5-10 parts by taking 100 parts of the dosage of the intrinsic halogen-free flame-retardant polyphenyl ether resin;
the synergistic flame retardant is selected from one or a mixture of more than two of hexaphenoxycyclotriphosphazene, melamine cyanurate, hypophosphite, dialkyl phosphinate, diphenyl phosphinate, p-xylylene bis (diphenylphosphine oxide), melamine polyphosphate, aluminum hydroxide, silicon dioxide and polysilsesquioxane.
9. The polyphenylene ether resin composition according to claim 1, wherein the flame retardant is one of the following: the Y1 adopts oxygen atom, methylene, p-phenol group or 1, 4-naphthol.
10. The use of the polyphenylene ether resin composition as defined in any one of claims 1 to 9 for the preparation of printed circuit board films, high-speed high-frequency copper clad laminates or fiber cloth laminates.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116102876A (en) * | 2022-12-29 | 2023-05-12 | 金发科技股份有限公司 | Thin-wall flame-retardant PA-PPE composition and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW201531502A (en) * | 2014-02-10 | 2015-08-16 | Chin Yee Chemical Industres Co Ltd | P-containing polyphenylene ether, P-containing phenol group-polyphenylene ether composition, P-containing unsaturated group-polyphenylene ether composition, P-containing epoxy group-polyphenylene ether composition, and its application |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW201531502A (en) * | 2014-02-10 | 2015-08-16 | Chin Yee Chemical Industres Co Ltd | P-containing polyphenylene ether, P-containing phenol group-polyphenylene ether composition, P-containing unsaturated group-polyphenylene ether composition, P-containing epoxy group-polyphenylene ether composition, and its application |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116102876A (en) * | 2022-12-29 | 2023-05-12 | 金发科技股份有限公司 | Thin-wall flame-retardant PA-PPE composition and preparation method and application thereof |
| CN116102876B (en) * | 2022-12-29 | 2024-05-14 | 金发科技股份有限公司 | Thin-wall flame-retardant PA-PPE composition and preparation method and application thereof |
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