CN115627065B - High-frequency low-dielectric polyphenyl ether composite resin with excellent comprehensive performance, preparation and application - Google Patents
High-frequency low-dielectric polyphenyl ether composite resin with excellent comprehensive performance, preparation and application Download PDFInfo
- Publication number
- CN115627065B CN115627065B CN202211203118.5A CN202211203118A CN115627065B CN 115627065 B CN115627065 B CN 115627065B CN 202211203118 A CN202211203118 A CN 202211203118A CN 115627065 B CN115627065 B CN 115627065B
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- CN
- China
- Prior art keywords
- benzoxazine
- resin
- polyphenyl ether
- prepolymer
- composite 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.)
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- 229920013636 polyphenyl ether polymer Polymers 0.000 title claims abstract description 149
- 239000000805 composite resin Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229920005989 resin Polymers 0.000 claims abstract description 201
- 239000011347 resin Substances 0.000 claims abstract description 201
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 claims abstract description 151
- 239000013032 Hydrocarbon resin Substances 0.000 claims abstract description 47
- 229920006270 hydrocarbon resin Polymers 0.000 claims abstract description 47
- 150000005130 benzoxazines Chemical class 0.000 claims abstract description 27
- 239000011218 binary composite Substances 0.000 claims abstract description 27
- 239000003063 flame retardant Substances 0.000 claims abstract description 27
- 239000011206 ternary composite Substances 0.000 claims abstract description 18
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 70
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 57
- 238000006243 chemical reaction Methods 0.000 claims description 49
- 229920001955 polyphenylene ether Polymers 0.000 claims description 46
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- 239000000126 substance Substances 0.000 claims description 35
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 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 claims description 24
- 239000012046 mixed solvent Substances 0.000 claims description 22
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 19
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 16
- DDRPCXLAQZKBJP-UHFFFAOYSA-N furfurylamine Chemical compound NCC1=CC=CO1 DDRPCXLAQZKBJP-UHFFFAOYSA-N 0.000 claims description 16
- -1 flame-retardant benzoxazine compounds Chemical class 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 10
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical group C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims description 9
- 150000001412 amines Chemical class 0.000 claims description 9
- 239000011889 copper foil Substances 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 7
- 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 claims description 7
- 229920000147 Styrene maleic anhydride Polymers 0.000 claims description 7
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 6
- 239000002966 varnish Substances 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 4
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 4
- 239000004745 nonwoven fabric Substances 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 2
- QEQVCPKISCKMOQ-UHFFFAOYSA-N 3h-benzo[f][1,2]benzoxazine Chemical class C1=CC=CC2=C(C=CNO3)C3=CC=C21 QEQVCPKISCKMOQ-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 2
- 239000004713 Cyclic olefin copolymer Substances 0.000 claims description 2
- 239000005062 Polybutadiene Substances 0.000 claims description 2
- 239000002174 Styrene-butadiene Substances 0.000 claims description 2
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 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
- 229920001971 elastomer Polymers 0.000 claims description 2
- 239000011256 inorganic filler Substances 0.000 claims description 2
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 2
- 239000012796 inorganic flame retardant Substances 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
- 229920001195 polyisoprene Polymers 0.000 claims description 2
- 239000005060 rubber Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000011115 styrene butadiene Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- 238000001723 curing Methods 0.000 description 24
- 230000009477 glass transition Effects 0.000 description 15
- 239000002244 precipitate Substances 0.000 description 12
- 239000011342 resin composition Substances 0.000 description 12
- 230000000930 thermomechanical effect Effects 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 238000001556 precipitation Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- 238000004891 communication Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 238000004132 cross linking Methods 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 229930040373 Paraformaldehyde Natural products 0.000 description 6
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 6
- 229920002866 paraformaldehyde Polymers 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical group N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 5
- 229930185605 Bisphenol Natural products 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 239000012454 non-polar solvent Substances 0.000 description 4
- XCRBXWCUXJNEFX-UHFFFAOYSA-N peroxybenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1 XCRBXWCUXJNEFX-UHFFFAOYSA-N 0.000 description 4
- 239000002798 polar solvent Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000010025 steaming Methods 0.000 description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000002114 nanocomposite Substances 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920013638 modified polyphenyl ether Polymers 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002952 polymeric resin Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000005476 soldering Methods 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- PWKNBLFSJAVFAB-UHFFFAOYSA-N 1-fluoro-2-nitrobenzene Chemical group [O-][N+](=O)C1=CC=CC=C1F PWKNBLFSJAVFAB-UHFFFAOYSA-N 0.000 description 1
- ICMZFZGUTLNLAJ-UHFFFAOYSA-N 2,6-dimethyl-7-oxabicyclo[4.1.0]hepta-2,4-diene Chemical compound CC1=CC=CC2(C)OC12 ICMZFZGUTLNLAJ-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- FGWQCROGAHMWSU-UHFFFAOYSA-N 3-[(4-aminophenyl)methyl]aniline Chemical compound C1=CC(N)=CC=C1CC1=CC=CC(N)=C1 FGWQCROGAHMWSU-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 150000001555 benzenes Chemical group 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 125000002243 cyclohexanonyl group Chemical group *C1(*)C(=O)C(*)(*)C(*)(*)C(*)(*)C1(*)* 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920006027 ternary co-polymer Polymers 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
- C08L71/126—Polyphenylene oxides modified by chemical after-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
-
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Abstract
The invention relates to a polyphenyl ether composite resin with excellent comprehensive performance, and a preparation method and application thereof. The benzoxazine functional polyphenyl ether/benzoxazine binary composite resin is obtained by curing a benzoxazine functional polyphenyl ether resin prepolymer, benzoxazine or/and hydrocarbon resin prepolymer, or the benzoxazine functional polyphenyl ether/hydrocarbon resin binary composite resin or the benzoxazine functional polyphenyl ether/benzoxazine/hydrocarbon resin ternary composite resin. The composite resin has low dielectric property, high heat resistance, flexibility and even self-flame-retardant performance.
Description
Technical Field
The invention relates to the technical field of organic high polymer materials, in particular to high-frequency low-dielectric polyphenyl ether composite resin with excellent comprehensive performance, and preparation and application thereof.
Background
The ultrahigh frequency communication technology is a great strategic requirement of China, and is a new opportunity for the economy of a plain entity, and a new engine of the network is built. The printed circuit board is an important carrier for carrying electronic components and realizing electric signal transmission, and a base material copper-clad plate is prepared by coating (or dipping) glass fiber cloth with polymer resin and then hot-pressing with copper foil. With the advent of the ultra-high frequency age, the requirements for dielectric, heat-resistant, flame-retardant properties and the like of polymer resins are increasing.
The polyphenyl ether resin is the fifth engineering plastic in the world and has the advantages of high tensile and bending strength, small thermal expansion coefficient, low water absorption, good dimensional stability and the like. In particular, excellent dielectric properties, i.e., low dielectric constant and low dielectric loss, have made their use in the field of electronic communications interesting. However, commercial high molecular weight polyphenylene ether resins have problems such as high melt viscosity, poor processability, poor solvent resistance, poor heat resistance and flame retardancy. Furthermore, when the thermoplastic polyphenylene ether resin is used as a base resin for a printed wiring board, it is necessary to carry out heat curing modification. The main modification method of the polyphenyl ether resin comprises the steps of preparing low molecular weight polyphenyl ether resin (the number average molecular weight is less than 4000 g/mol) by a monomer copolymerization and redistribution method; introducing active groups on the hydroxyl-terminated groups, the lateral methyl groups and the main chain of the polyphenyl ether resin to prepare the polyphenyl ether resin or hyperbranched polyphenyl ether resin which can be thermally cured by itself; forming a binary and ternary composite resin system with epoxy resin, cyanate resin, bismaleimide resin, polyolefin and the like; inorganic/organic compounding with inorganic micro/nano particles such as oligomeric silsesquioxane, nano silicon dioxide and the like. Thus, the low dielectric characteristics of the polyphenylene ether resin are maintained and further improved as much as possible while improving the processability, solvent resistance and heat resistance thereof.
Benzoxazine resins have been widely used in the fields of high frequency communications, aerospace, automotive industry, and the like. Benzoxazine is an intermediate with a nitrogenous oxygen heterocyclic structure, which is synthesized by taking phenols, aldehydes and primary amine compounds as raw materials through a Mannich condensation reaction, and benzoxazine resin can be obtained through thermal ring-opening polymerization. The benzoxazine resin has the advantages of good thermal performance, strong cohesiveness, high mechanical strength, low dielectric constant (3.4-3.6) and the like, and only the dielectric performance of the benzoxazine resin needs to be further improved to meet the requirement of high-frequency communication. Based on the respective advantages of the polyphenyl ether and the benzoxazine resin, the preparation of the benzoxazine modified polyphenyl ether resin is a new research method. In 2018, chen et al first introduced benzoxazine functionality into polyphenylene ether resins (Polymers, 2018,10 (4): 411-425) starting from a low molecular weight (number average molecular weight 1600) polyphenylene ether derivative SA90, i.e., phenol-terminated oligo (2, 6-dimethylphenylene oxide), by nucleophilic substitution with fluoronitrobenzene followed by catalytic hydrogenation to produce an amine-terminated SA90 (APPO). Then APPO is taken as an amine source, and is mixed with paraformaldehyde and phenol or bisphenol A to prepare telechelic benzoxazine functional polyphenyl ether prepolymer or main chain benzoxazine functional polyphenyl ether prepolymer, and finally, thermosetting resin with glass transition temperature (218-225 ℃) and lower dielectric property (k is 2.9,1 GHz) can be obtained through self-curing and epoxy resin curing. But the thermal performance of the device still has difficulty in meeting the use requirements of high-frequency, high-speed and high-performance communication equipment. In addition, the preparation method has complex procedures, requires multi-step chemical reactions such as nitration, amination, benzoxazine functionalization and the like, has complicated steps and a plurality of side reactions, and also causes purification after synthesis to be a big problem. In particular, the cost of selecting the derivative of polyphenylene ether resin (SA 90) as a reaction raw material is high.
In order to further meet the high requirements on the comprehensive performances such as low dielectric constant, low dielectric loss, high heat resistance, self-flame retardance, flexibility and the like, the design and research of the polyphenyl ether composite resin with excellent comprehensive performances are significant.
Disclosure of Invention
The invention aims to provide polyphenyl ether composite resin with excellent comprehensive performance, and preparation and application thereof. The composite resin has low dielectric property, high heat resistance, flexibility and even self-flame-retardant performance.
In order to achieve the above purpose, the invention adopts the following technical scheme:
Providing a polyphenyl ether composite resin with excellent comprehensive performance, wherein the polyphenyl ether composite resin is prepared by curing a benzoxazine functionalized polyphenyl ether resin prepolymer, benzoxazine or/and hydrocarbon resin prepolymer to obtain a benzoxazine functionalized polyphenyl ether/benzoxazine binary composite resin, or a benzoxazine functionalized polyphenyl ether/hydrocarbon resin binary composite resin, or a benzoxazine functionalized polyphenyl ether/benzoxazine/hydrocarbon resin ternary composite resin;
The benzoxazine functionalized polyphenyl ether resin prepolymer is one or a combination of more than one of benzoxazine functionalized polyphenyl ether compounds shown in the following structural formula, and the benzoxazine functionalized polyphenyl ether comprises monofunctional benzoxazine, difunctional benzoxazine and end-capped main chain benzoxazine functionalized polyphenyl ether, and the structural formula is shown in the formula 1:
R 1 -is
-R 2- is
-R 3- is
N is 15-30, and m is 1-5.
According to the scheme, the benzoxazine functionalized polyphenyl ether/benzoxazine binary composite resin comprises the following components: 55-95 parts by weight of benzoxazine functionalized polyphenyl ether resin prepolymer; 45-5 parts by weight of benzoxazine;
Benzoxazine functionalized polyphenylene ether/hydrocarbon resin binary composite resin: 55-95 parts by weight of benzoxazine functionalized polyphenyl ether resin prepolymer; 45-5 parts by weight of hydrocarbon resin prepolymer;
Benzoxazine-functionalized polyphenylene ether/benzoxazine/hydrocarbon resin ternary composite resin: 55-85 parts by weight of benzoxazine functionalized polyphenyl ether resin prepolymer; 15-5 parts of benzoxazine; 30-10 parts of hydrocarbon resin prepolymer.
The preparation method of the modified polyphenyl ether composite resin prepolymer comprises the following steps:
55-95 parts by weight of benzoxazine functionalized polyphenyl ether resin prepolymer is added into a reaction container; 45-5 parts by weight of benzoxazine, dispersing the benzoxazine in an organic solvent to obtain a composite resin prepolymer with the solid content of 20-90 wt%, pre-reacting for a period of time, and heating and curing the resin prepolymer obtained by pre-reacting to obtain the benzoxazine functionalized polyphenyl ether/benzoxazine binary composite resin;
55-95 parts by weight of benzoxazine functionalized polyphenyl ether resin prepolymer is added into a reaction container; 45-5 parts by weight of hydrocarbon resin prepolymer, dispersing the hydrocarbon resin prepolymer in an organic solvent to obtain a composite resin prepolymer with the solid content of 20-90 wt%, pre-reacting for a period of time, and heating and curing the resin prepolymer obtained by pre-reacting to obtain the benzoxazine functionalized polyphenyl ether/hydrocarbon resin binary composite resin.
Adding 55-85 parts by weight of benzoxazine functionalized polyphenyl ether resin prepolymer into a reaction container; 15-5 parts of benzoxazine; 30-10 parts by weight of hydrocarbon resin prepolymer, dispersing the hydrocarbon resin prepolymer in an organic solvent to obtain a composite resin prepolymer with the solid content of 20-90 wt%, pre-reacting for a period of time, and heating and curing the resin prepolymer obtained by pre-reacting to obtain the benzoxazine-functionalized polyphenyl ether/benzoxazine/hydrocarbon resin ternary composite resin after curing.
According to the scheme, the benzoxazine is one or a combination of the following components: polyfunctional degree of a benzoxazine is used as a base for the preparation of a benzoxazine, a multifunctional benzoxazine is used as a solvent, the main chain of the benzoxazine is a compound, end-capped backbone benzoxazines, naphthoxazines, and other organic compounds containing oxazine rings.
According to the scheme, the benzoxazine is intrinsic flame-retardant benzoxazine, specifically one or more of intrinsic flame-retardant benzoxazine compounds, and the chemical structural formula of the intrinsic flame-retardant benzoxazine is shown as formula 2:
According to the scheme, the hydrocarbon resin prepolymer is one or a combination of the following prepolymers: styrene-maleic anhydride copolymer, polybutadiene resin, hydrogenated diene-butadiene-styrene copolymer, styrene-butadiene resin, styrene-isoprene copolymer, styrene-butadiene copolymer, cyclic olefin copolymer, polyisoprene rubber, styrene-butadiene-divinylbenzene copolymer.
According to the scheme, the organic solvent is one or a combination of the following components: toluene, ethanol, methanol, xylene, diethyl ether, acetone, butanone, cyclohexanone, ethyl acetate, N '-dimethylformamide, N' -dimethylacetamide, ethylene glycol methyl ether, propylene glycol methyl ether, dioxane, chloroform.
According to the scheme, the pre-reaction is carried out at 60-120 ℃ for 1-12 h, and the curing condition of the polyphenyl ether composite resin is 100-220 ℃ for 2-24 h.
The preparation method of the benzoxazine functionalized polyphenyl ether resin prepolymer comprises the following steps:
Adding reactants which are a phenol source, an amine source and an aldehyde compound into a reaction container in a one-step or step-by-step multi-feeding mode, reacting for 5-60 hours at 70-120 ℃ in a nitrogen atmosphere, and performing post-treatment to obtain a benzoxazine functional polyphenyl ether resin prepolymer, wherein the one-step feeding mode is that all raw materials are simultaneously added into the reaction container, and then a polar/nonpolar mixed solvent is added for dissolution and reaction; the step-by-step and repeated feeding mode is that firstly aldehyde compounds and amine compounds are added into a reaction container, then a polar/nonpolar mixed solvent is added, and phenol source substances are added after stirring is complete;
Wherein:
the phenol source in the preparation of the monofunctional benzoxazine functional polyphenyl ether resin prepolymer (formula 1 (a)) is redistributed polyphenyl ether resin, and the amine source is aniline, furfuryl amine, allylamine and paravinylaniline;
The phenol source in the preparation of the difunctional benzoxazine functional polyphenyl ether resin prepolymer (formula 1 (b)) is redistributed polyphenyl ether resin, and the amine source is 4,4' -diaminodiphenylmethane and hexamethylenediamine;
In the preparation of the end-capped main chain benzoxazine functionalized polyphenyl ether resin prepolymer (formula 1 (c)), phenol sources are dihydric phenol and reassigned polyphenyl ether resin, wherein the dihydric phenol is bisphenol A, bisphenol F, bisphenol S, dicyclopentadiene bisphenol A, 4' -dihydroxybiphenyl, 4' -dihydroxydiphenyl ether, and the amine source is 4,4' -diaminodiphenylmethane and hexamethylenediamine.
According to the above scheme, the redistributed polyphenyl ether resin isN value range: 15-30.
According to the above scheme, the number average molecular weight of the redistributed polyphenylene ether resin is 2027 to 3827.
According to the scheme, the aldehyde compound is formaldehyde, paraformaldehyde and the like.
According to the scheme, the molar ratio of phenolic hydroxyl, amino and aldehyde functional groups of the reactants is 1: :1:2.
According to the scheme, the molar ratio of the functional groups of the dihydric phenol compound to the phenolic hydroxyl groups in the redistribution polyphenyl ether resin in the preparation of the polyphenyl ether resin prepolymer functionalized by the end-capped main chain benzoxazine is 1:1.
According to the scheme, the polar/nonpolar mixed solvent is a polar solvent and the volume ratio of the nonpolar solvent is 1: 5-5: 1, wherein the polar solvent is: cyclohexanone, acetone, ethyl acetate, methanol, diethyl ether, N' -dimethylformamide, dioxane, chloroform, ethanol, tetrahydrofuran and the like, wherein the nonpolar solvent is toluene, butanone, xylene and the like.
According to the scheme, the post-treatment is as follows: after the reaction is finished, the reaction solution is poured into a methanol solution to obtain a precipitate, the precipitate is washed for multiple times, and then the product is dissolved in a polar/nonpolar mixed solvent, and then the precipitate is precipitated by methanol for multiple times. Repeating the above process for multiple times to purify the prepared sample, and finally drying and grinding to obtain a pale yellow resin prepolymer of the benzoxazine-functionalized polyphenyl ether resin.
According to the above scheme, the redistribution polyphenyl ether resin is obtained by redistribution reaction of commercial high molecular weight polyphenyl ether.
According to the scheme, the preparation method of the redistribution polyphenyl ether resin comprises the following steps: commercial high molecular weight polyphenyl ether, bisphenol A and peroxide are taken as raw materials, dissolved in a polar/nonpolar mixed solvent, reacted for 4 to 50 hours at the temperature of 60 to 125 ℃, and post-treated to obtain a redistribution polyphenyl ether resin which is a low molecular weight polyphenyl ether resin after redistribution reaction, wherein the reaction formula is shown as follows:
According to the above scheme, the peroxide comprises benzoic acid peroxide, methyl ethyl ketone peroxide, tert-amyl peroctoate, dibenzoyl peroxide, benzoyl peroxide, 3', 5' -tetramethyl biphenyl di-quinone, tributyl phenoxy free radical, benzoyl peroxide and the like.
According to the scheme, the number average molecular weight of the commercial high molecular weight polyphenyl ether resin is 12000-24000, and the n' value is 100-200.
Preferably, the mass of the peroxide and bisphenol A is 25-30% and 20-25% of the mass of the polyphenylene ether resin, respectively.
According to the scheme, the polar/nonpolar mixed solvent is a polar solvent and the volume ratio of the nonpolar solvent is 1: 5-5: 1, wherein the polar solvent is cyclohexanone, acetone, ethyl acetate, methanol, diethyl ether, N' -dimethylformamide, dioxane, chloroform, ethanol, tetrahydrofuran, etc., and the nonpolar solvent is toluene, butanone, xylene, etc.
According to the scheme, the post-treatment process after redistribution reaction is to pour the reaction liquid into distilled water for precipitation, dissolve the product into a polar/nonpolar mixed solvent, then precipitate with distilled water, and repeat the precipitation and dissolution process for a plurality of times until the pH value of the solution is neutral.
Providing the application of the polyphenyl ether composite resin with excellent comprehensive performance in preparing resin varnish or prepreg or laminated board or multi-layer printed wiring board, wherein the resin varnish consists of the polyphenyl ether composite resin prepolymer as set forth in claim 1 and an organic solvent; the prepreg is prepared by adding inorganic filler and/or flame retardant into the resin varnish; the laminated board is formed by uniformly coating the prepreg on non-woven fabrics; the multilayer printed wiring board is made of the laminated board.
A multilayer printed wiring board is provided comprising a copper foil and a laminate made of a prepreg containing a polyphenylene ether compound resin supported on the copper foil.
The benzoxazine-functionalized polyphenyl ether resin prepolymer used in the invention can be prepared based on the reassigned polyphenyl ether resin by only one-step chemical reaction, and has low cost and simple preparation method. In addition, through the selection of amine compounds and phenolic compounds with different chemical structures, monofunctional benzoxazines, difunctional benzoxazines and end-capped main chain benzoxazine functionalized polyphenyl ether resin prepolymers with different chemical structures can be synthesized according to application requirements. The benzoxazine functionalized polyphenyl ether resin prepolymer prepared based on the redistribution polyphenyl ether with low molecular weight has low molecular weight and good processability, and the thermosetting resin obtained by curing the benzoxazine functionalized polyphenyl ether resin prepolymer has excellent solvent resistance, thermal performance (glass transition temperature: 238-269 ℃) and high-frequency dielectric performance (k value: 2.0-2.8).
Based on the benzoxazine functional polyphenyl ether resin prepolymer, the invention further cooperates with the benzoxazine and/or hydrocarbon resin prepolymer to construct a binary and ternary copolymer resin system with excellent comprehensive performance.
In a binary composite system constructed by benzoxazine functionalized polyphenyl ether and benzoxazine, the compatibility and the crosslinking density of the composite resin system can be improved by carrying out copolymerization reaction based on a shared oxazine ring. This is because the compatibility of the two resins is improved by the ring-opening polymerization reaction of the oxazine ring. And because of copolymerization reaction of two oxazine rings and winding and penetrating of polyphenyl ether long chains in a benzoxazine resin crosslinked network structure, the crosslinking density of the benzoxazine resin is increased. Notably, the introduction of the intrinsic flame retardant benzoxazine resin enables the composite resin system to achieve self-flame retardance without the need for external flame retardants.
In a binary composite system constructed by benzoxazine functionalized polyphenyl ether and hydrocarbon resin, the hydrocarbon resin has a regular structure and contains a low-polarity long carbon chain chemical structure, and the hydrocarbon resin is introduced into the polyphenyl ether composite resin, so that the dielectric property of the whole composite resin system can be improved. In addition, the hydrocarbon resin can complete self-polymerization in the polymerization and curing process of the benzoxazine resin, and forms an Interpenetrating Polymer Network (IPN) structure with the benzoxazine resin, so that the crosslinking density and the high temperature resistance of the composite resin are effectively improved. In addition, the double bond of the benzoxazine functionalized polyphenyl ether can form a chemical copolymerization reaction with the double bond structure contained in hydrocarbon resin, so that the compatibility of the benzoxazine functionalized polyphenyl ether and the hydrocarbon resin and the crosslinking density of the copolymer are effectively improved, and the thermal performance is improved. In addition, carbonyl functional groups contained in hydrocarbon resin can react with phenolic hydroxyl groups formed by benzoxazine ring opening to generate aromatic ester, so that a chemical crosslinking structure is formed, the crosslinking density of the copolymer resin is further improved, and the thermal property of the composite resin is greatly improved. Meanwhile, the reduction of polar phenolic hydroxyl functional groups formed by ring-opening curing of the benzoxazine functionalized polyphenyl ether is also beneficial to the improvement of the dielectric property of the composite resin. In addition, the hydrocarbon resin has a long carbon chain structure, so that the flexibility of the composite resin can be endowed, and the flexibility of the benzoxazine functional group polyphenyl ether tree/hydrocarbon resin binary composite resin body is remarkably improved.
In particular, each resin in the benzoxazine-functionalized polyphenylene ether/benzoxazine/hydrocarbon resin ternary composite resin has the properties, and the interaction and the mutual influence are realized. Besides the reaction of the benzoxazine functionalized polyphenyl ether with the benzoxazine resin and the hydrocarbon resin respectively, the small-molecular benzoxazine is equivalent to a diluent in the processing process of the binary and ternary composite resin, so that the viscosity of the composite resin system can be effectively reduced, and the technological properties of the binary and ternary composite resin system can be improved. The hydrocarbon resin is a catalyst for benzoxazine ring-opening reaction, so that the curing temperature of a composite resin system can be effectively reduced, the processing performance is improved, and the crosslinking density of the composite resin is improved, thereby further improving the thermal performance and the dielectric performance. And the hydrocarbon resin has a long carbon chain structure, so that the flexibility of the composite resin can be endowed, and the flexibility of the benzoxazine functionalized polyphenyl ether/benzoxazine/hydrocarbon resin ternary composite resin body is remarkably improved. In addition, the intrinsic flame-retardant benzoxazine resin is introduced, so that the ternary composite resin system can realize self flame retardance without adding flame retardant.
In addition, the benzoxazine functional polyphenyl ether resin has low dielectric constant and dielectric loss under the ultrahigh frequency condition, and copolymerization reaction with the benzoxazine resin and hydrocarbon resin respectively can effectively improve the crosslinking density to inhibit polarization orientation, so that the binary and ternary composite resin has lower dielectric constant (1.8-2.5) and dielectric loss (0.0007-0.005) under the ultrahigh frequency condition, thereby having application prospects in the emerging fields of ultrahigh frequency communication and the like. Can be applied to laminated boards, copper-clad plates, multilayer printed circuit boards, semiconductor packaging materials and other composite materials.
The invention has the beneficial effects that:
The preparation method is simple in preparation process, low in cost and easy to industrialize.
The polyphenyl ether composite resin provided by the invention has excellent heat resistance (glass transition temperature 253-394 ℃) and toughness (tensile strength 96-127 MPa); excellent dielectric performance under the ultra-high frequency condition (dielectric constant is between 1.8 and 2.5 at 10GHz, and dielectric loss is between 0.0007 and 0.005). The composite material can be widely applied to laminates, copper-clad plates, multilayer printed circuit boards, semiconductor packaging materials and other composite materials, and is particularly suitable for the emerging communication fields such as ultrahigh frequency communication and the like.
The binary and ternary resin containing intrinsic flame-retardant benzoxazine can achieve the flame-retardant effect without adding flame retardant.
Drawings
FIG. 1 is an infrared spectrum (FTIR) of the resin prepolymer products synthesized in examples 1-3 in the preparation of a redistributed low molecular weight polyphenylene ether resin and a benzoxazine-functionalized polyphenylene ether resin prepolymer.
Wherein:
FIG. 1a is a redistributed low molecular weight polyphenylene ether resin;
FIG. 1b example 1, aniline/bisphenol A-type benzoxazine-functionalized polyphenylene ether resin prepolymer;
FIG. 1c example 2, furfuryl amine/bisphenol A type benzoxazine functionalized polyphenylene ether resin prepolymer;
FIG. 1d example 3, 4' -diaminodiphenylmethane/bisphenol A-type benzoxazine-functionalized polyphenylene ether resin prepolymer.
Detailed Description
The following is a detailed description of embodiments of the present invention.
Example 1
95 Parts of a prepolymer (chemical structural formula shown as the following) of aniline/bisphenol A type benzoxazine functional polyphenyl ether resin and 5 parts of a styrene-butadiene-divinylbenzene copolymer prepolymer are taken, the solid content of the resin composition is regulated to 90wt% by using a butanone solvent, and the mixture is stirred for 1 hour at 60 ℃ and uniformly mixed. And then curing the obtained prepolymer at 220 ℃ for 2 hours to obtain the binary composite resin. The glass transition temperature (dynamic thermo-mechanical analyzer) is 253 ℃, the tensile strength (universal mechanical tester) is 96MPa, the dielectric constant (network vector analyzer) at 10GHz is 2.5, and the dielectric loss (network vector analyzer) is 0.005.
Example 2
55 Parts of a prepolymer (chemical structural formula shown as the following) of furfuryl amine/bisphenol A type benzoxazine functionalized polyphenyl ether is taken.
45 Parts of aniline/bisphenol A type benzoxazine is taken, and the chemical reaction formula is shown as follows.
The above resin raw materials were mixed with toluene/ethanol (2:1 v/v) mixed solvent to adjust the solid content of the resin composition to 20wt%, and stirred at 80℃for 12 hours, followed by uniform mixing. And then curing the obtained prepolymer at 100 ℃ for 24 hours to obtain the binary composite resin. The glass transition temperature (dynamic thermo-mechanical analyzer) is 297 ℃, the tensile strength (universal mechanical tester) is 101MPa, the dielectric constant (network vector analyzer) at 10GHz is 2.4, and the dielectric loss (network vector analyzer) is 0.004.
Example 3
30 Parts of a prepolymer (chemical structural formula shown as the following) of aniline/bisphenol A type benzoxazine functionalized polyphenyl ether is taken.
Then 30 parts of a prepolymer (chemical structural formula shown as the following) of 4,4' -diaminodiphenylmethane/bisphenol A type benzoxazine functionalized polyphenyl ether is taken.
Finally, 40 parts of styrene-maleic anhydride copolymer prepolymer is taken. The resin raw material was stirred at 120℃for 3 hours with the solid content of the resin composition adjusted to 80% by weight with an N, N' -dimethylformamide solvent, and the mixture was uniformly mixed. And then curing the obtained prepolymer at 200 ℃ for 4 hours to obtain the binary composite resin. The glass transition temperature (dynamic thermo-mechanical analyzer) is 299 ℃, the tensile strength (universal mechanical experiment machine) is 105MPa, the dielectric constant (network vector analyzer) at 10GHz is 2.3, and the dielectric loss (network vector analyzer) is 0.004.
Example 4
35 Parts of a prepolymer (chemical structural formula shown below) of furfuryl amine/bisphenol A type benzoxazine functionalized polyphenyl ether is taken.
30 Parts of a prepolymer (chemical structural formula shown as the following) of a terminal-end-capped main chain benzoxazine-functionalized polyphenyl ether resin is taken.
Wherein: r 2 isR 3 is
And then 35 parts of furfuryl amine/bisphenol A type benzoxazine is taken, and the chemical reaction formula is shown as follows.
The above resin raw materials were mixed with toluene/ethanol (2:1 v/v) mixed solvent to adjust the solid content of the resin composition to 50% by weight, and stirred at 80℃for 2 hours, followed by uniform mixing. And then curing the obtained prepolymer at 180 ℃ for 10 hours to obtain the binary composite resin. The glass transition temperature (dynamic thermo-mechanical analyzer) is 334 ℃, the tensile strength (universal mechanical experiment machine) is 126MPa, the dielectric constant (network vector analyzer) at 10GHz is 2.2, and the dielectric loss (network vector analyzer) is 0.003.
Example 5
10 Parts of furfuryl amine/bisphenol A type benzoxazine is taken, and the chemical reaction formula is shown as follows.
And 5 parts of end-capped main chain benzoxazine, wherein the chemical reaction formula is shown as follows.
Wherein: r 1 is
And taking 15 parts of furfuryl amine/bisphenol A type benzoxazine functionalized polyphenyl ether resin prepolymer (the chemical structural formula is shown as below).
50 Parts of a prepolymer (chemical structural formula shown as the following) of a blocked main chain benzoxazine functional polyphenyl ether resin is taken.
Wherein: r 2 isR 3 is
And finally, taking 20 parts of styrene-maleic anhydride copolymer prepolymer.
The solid content of the resin composition was adjusted to 45wt% by using dioxane solvent for the above resin raw materials, and stirred at 80℃for 4 hours, followed by uniform mixing. And then curing the obtained prepolymer at 160 ℃ for 20 hours to obtain the ternary composite resin. The glass transition temperature (dynamic thermo-mechanical analyzer) is 345 ℃, the tensile strength (universal mechanical experiment machine) is 127MPa, the dielectric constant (network vector analyzer) at 10GHz is 2.0, and the dielectric loss (network vector analyzer) is 0.002.
Example 6
5 Parts of furfuryl amine/bisphenol A type benzoxazine is taken, and the chemical reaction formula is shown as follows.
And 10 parts of end-capped main chain benzoxazine, wherein the chemical reaction formula is shown as follows.
Wherein: r 1 is
65 Parts of end-capped main chain benzoxazine functional polyphenyl ether resin prepolymer (the chemical structural formula is shown as below) is taken.
Wherein: r 2 isR 3 is
And finally taking 10 parts of styrene-maleic anhydride copolymer prepolymer and 10 parts of styrene-butadiene copolymer prepolymer. The above resin raw materials were mixed with toluene/ethanol (2:1 v/v) mixed solvent to adjust the solid content of the resin composition to 40% by weight, and stirred at 70℃for 12 hours, followed by uniform mixing. And then curing the obtained prepolymer at 190 ℃ for 6 hours to obtain the ternary composite resin. The glass transition temperature (dynamic thermo-mechanical analyzer) is 394 ℃, the tensile strength (universal mechanical experiment machine) is 121MPa, the dielectric constant (network vector analyzer) at 10GHz is 1.8, and the dielectric loss (network vector analyzer) is 0.0007.
100 Parts of the polyphenylene ether resin composition (solid content: 40% by weight, solvent: toluene/ethanol (2:1 v/v) mixed solvent) prepared in example 6 above was used. 70 parts of nanoscale magnesium hydroxide (the solid content is 70wt%, and the solvent is toluene/ethanol (2:1 v/v) mixed solvent), which is used as a reinforcing material and a flame retardant. Mixing the two, and performing ultrasonic treatment for 120min at the ultrasonic power of 500W to obtain the inorganic/organic nano composite resin solution with uniform dispersion. And (3) uniformly coating the inorganic/organic composite resin solution on a non-woven fabric (with the thickness of 0.05 mm), airing at room temperature, and transferring into a blast oven for pre-curing at 110 ℃ to obtain the prepreg. Cutting to obtain regularly shaped prepreg, stacking ten layers, applying copper foil on one side, pressing in a hot press at 170deg.C under 10.0MPa for 2 hr, and degassing every ten minutes. The inorganic/organic polyphenyl ether nano composite resin is easy to process and difficult to gummosis. Finally, the obtained plate is subjected to processing methods such as punching, metal plating, etching and the like to obtain the copper-clad plate.
The physical properties of the prepared copper-clad plate were tested as follows. The test result of the peel strength of the copper foil is 1.2N/mm, which shows that the polyphenyl ether composite resin has good adhesive property. Cutting the copper-clad plate etched with copper into small pieces with a certain size, placing the small pieces in an autoclave, and steaming and boiling the small pieces at 105kPa and 121 ℃ for 360 minutes, wherein the tin soldering heat resistance test (PCT, tin bath 288 ℃) is carried out for more than 5 minutes, the bubbling and layering are avoided, and the copper-clad plate shows good water steaming and boiling resistance. Thermal mechanical analysis tests that the Coefficient of Thermal Expansion (CTE) is 34 ppm/DEG C show that the copper-clad plate has good dimensional stability. The glass transition temperature of the dynamic thermo-mechanical analysis test copper-clad plate is 376 ℃, the carbon residue rate (thermogravimetric analyzer) at 800 ℃ is 65%, and excellent thermal performance is shown. When the test frequency is 10GHz, the dielectric constant and the dielectric loss are respectively 2.37 and 0.0031, and the result shows that the copper-clad plate has excellent ultrahigh-frequency dielectric property. The flame retardance of the copper-clad plate obtained by the UL-94 vertical test method is still V-0 grade.
Example 7
95 Parts of a prepolymer (chemical structural formula shown as the following) of furfuryl amine/bisphenol A type benzoxazine functionalized polyphenyl ether is taken.
And then 5 parts of intrinsic flame-retardant benzoxazine is taken, and the chemical structural formula is shown as follows.
The above resin raw materials were mixed with an ethanol/toluene (3:1 v/v) mixed solvent to adjust the solid content of the resin composition to 20% by weight, and stirred at 60℃for 4 hours, followed by uniform mixing. And then curing the obtained prepolymer at 100 ℃ for 24 hours to obtain the binary composite resin. The glass transition temperature (dynamic thermo-mechanical analyzer) is 296 ℃, the tensile strength (universal mechanical experiment machine) is 99MPa, the dielectric constant (network vector analyzer) at 10GHz is 2.4, and the dielectric loss (network vector analyzer) is 0.004. The carbon residue rate (thermogravimetric analyzer) at 800 ℃ can reach 50%, the limiting oxygen index (GB 2406-80) is as low as 43.5, the heat release capacity (micro combustion calorimeter) can reach 100J g -1K-1, and the flame retardant performance is V-0 grade (UL-94).
Example 8
30 Parts of a prepolymer (chemical structural formula shown as the following) of furfuryl amine/bisphenol A type benzoxazine functionalized polyphenyl ether is taken.
25 Parts of a prepolymer (chemical structural formula shown in the specification) of a terminal-end type main chain benzoxazine functional polyphenyl ether resin is taken.
Wherein: r 2 isR 3 is
45 Parts of intrinsic flame-retardant benzoxazine is taken, and the chemical structural formula is shown as follows.
The solid content of the resin composition was adjusted to 50wt% with butanone solvent for the above resin raw materials, and stirred at 85℃for 2 hours, and mixed uniformly. And then curing the obtained prepolymer at 180 ℃ for 12 hours to obtain the binary composite resin. The glass transition temperature (dynamic thermo-mechanical analyzer) is 334 ℃, the tensile strength (universal mechanical experiment machine) is 106MPa, the dielectric constant (network vector analyzer) at 10GHz is 2.2, and the dielectric loss (network vector analyzer) is 0.003. The carbon residue rate (thermogravimetric analyzer) at 800 ℃ can reach 55%, the limiting oxygen index (GB 2406-80) can reach 32.6, the heat release capacity (micro combustion calorimeter) can reach 57J g - 1K-1, and the flame retardant performance V-0 grade (UL-94).
Example 9
5 Parts of furfuryl amine/bisphenol A type benzoxazine functionalized polyphenyl ether prepolymer (the chemical structural formula is shown as the following) are taken.
50 Parts of a prepolymer (chemical structural formula shown as the following) of a blocked main chain benzoxazine functional polyphenyl ether resin is taken.
Wherein: r 2 isR 3 is
And then 10 parts of intrinsic flame-retardant benzoxazine is taken, and the chemical structural formula is shown as follows.
And 5 parts of intrinsic flame-retardant benzoxazine, wherein the chemical structural formula is shown as follows.
And finally, 30 parts of styrene-maleic anhydride copolymer prepolymer is taken. The solid content of the resin composition was adjusted to 45wt% by using dioxane solvent for the above resin raw materials, and stirred at 80℃for 4 hours, followed by uniform mixing. And then curing the obtained prepolymer at 160 ℃ for 8 hours to obtain the ternary composite resin. The glass transition temperature (dynamic thermo-mechanical analyzer) is 375 ℃, the tensile strength (universal mechanical experiment machine) is 127MPa, the dielectric constant (network vector analyzer) at 10GHz is 2.1, and the dielectric loss (network vector analyzer) is 0.002. The carbon residue rate (thermogravimetric analyzer) at 800 ℃ can reach 57%, the limiting oxygen index (GB 2406-80) can reach 35.2, the heat release capacity (micro combustion calorimeter) can reach 69J g -1K-1, and the flame retardant performance V-0 grade (UL-94).
Example 10
5 Parts of a prepolymer (chemical structural formula shown below) of 4,4' -diaminodiphenylmethane/bisphenol A-type benzoxazine-functionalized polyphenylene ether resin is taken.
50 Parts of a prepolymer (chemical structural formula shown as the following) of a blocked main chain benzoxazine functional polyphenyl ether resin is taken.
Wherein: r 2 isR 3 is
9 Parts of intrinsic flame-retardant benzoxazine is taken, and the chemical structural formula is shown as follows.
And 6 parts of another intrinsic flame-retardant benzoxazine, wherein the chemical structural formula is shown as follows.
Finally, 10 parts of styrene-maleic anhydride copolymer prepolymer and 20 parts of styrene-butadiene copolymer prepolymer are taken. The above resin raw materials were mixed with an ethanol/toluene (3:1 v/v) mixed solvent to adjust the solid content of the resin composition to 45wt%, and stirred at 60℃for 1 hour, followed by uniform mixing. And then curing the obtained prepolymer at 190 ℃ for 6 hours to obtain the ternary composite resin. The glass transition temperature (dynamic thermo-mechanical analyzer) is 379 ℃, the tensile strength (universal mechanical tester) is 125MPa, the dielectric constant (network vector analyzer) at 10GHz is 2.0, and the dielectric loss (network vector analyzer) is 0.001. The carbon residue rate (thermogravimetric analyzer) at 800 ℃ can reach 60%, the limiting oxygen index (GB 2406-80) can reach 35, the heat release capacity (micro combustion calorimeter) can reach 30.3J g -1K-1, and the flame retardant performance V-0 grade (UL-94).
Example 11
100 Parts of the polyphenylene ether resin composition prepared in example 10 (solid content: 45wt% solvent: ethanol/toluene (3:1 v/v) mixed solvent) and 80 parts of nanosilica (solid content: 70wt% solvent: ethanol/toluene (3:1 v/v) mixed solvent) were mixed, and the mixture was sonicated for 60 minutes at a sonication power of 500W to obtain a uniformly dispersed nanocomposite resin solution. And (3) uniformly coating the inorganic/organic composite resin solution on a non-woven fabric (with the thickness of 0.05 mm), airing at room temperature, and transferring into a blast oven for pre-curing at the temperature of 100-120 ℃ to obtain the prepreg. Cutting to obtain prepreg with regular shape, stacking six layers, adding copper foil on one side, pressing in a hot press at 160deg.C under 10.0MPa for 1 hr, and degassing every ten minutes. The composite resin has good processability, no gummosis and easy processing. Finally, the obtained plate is subjected to processing methods such as punching, metal plating, etching and the like to obtain the copper-clad plate.
The physical properties of the prepared copper-clad plate were tested as follows. The test result of the peel strength of the copper foil is 1.4N/mm, which shows that the polyphenyl ether composite resin has good adhesive property. Cutting the copper-clad plate etched with copper into small pieces with a certain size, placing the small pieces in an autoclave, and steaming and boiling the small pieces at 105kPa and 121 ℃ for 360 minutes, wherein the tin soldering heat resistance test (PCT, tin bath 288 ℃) is carried out for more than 5 minutes, the bubbling and layering are avoided, and the copper-clad plate shows good water steaming and boiling resistance. Thermal mechanical analysis tests show that the Coefficient of Thermal Expansion (CTE) is 40 ppm/DEG C, and the copper-clad plate has good dimensional stability. The glass transition temperature of the dynamic thermo-mechanical analysis test copper-clad plate is 365 ℃, the carbon residue rate (thermogravimetric analyzer) at 800 ℃ is 55%, and excellent thermal performance is shown. When the test frequency is 10GHz, the dielectric constant and the dielectric loss are respectively 2.35 and 0.0027, and the result shows that the copper-clad plate has excellent ultrahigh frequency dielectric property. Notably, the flame retardance of the copper-clad plate obtained by the UL-94 vertical test method is still V-0 grade.
Preparation of benzoxazine-functionalized polyphenylene ether:
Redistributed low molecular weight polyphenylene ether resins
100G of commercial high molecular weight polyphenyl ether resin (with the number average molecular weight of 12000 g/mol), 20g of bisphenol A and 30g of peroxybenzoic acid are mixed in a toluene/ethanol (5:1 v/v) solvent, reacted for 50 hours at 60 ℃, and after the reaction is finished, the mixture is subjected to multiple precipitation and washing by distilled water, and the low molecular weight polyphenyl ether resin (with the number average molecular weight of 2027 g/mol) is obtained after treatment.
Example 1
100G of commercial high molecular weight polyphenyl ether resin (with the number average molecular weight of 12000 g/mol), 25g of bisphenol A and 25g of peroxybenzoic acid are mixed in a toluene/ethanol (5:1 v/v) solvent, reacted for 50 hours at 60 ℃, and after the reaction is finished, the mixture is subjected to multiple precipitation and washing by distilled water, and the low molecular weight polyphenyl ether resin (with the number average molecular weight of 2027 g/mol) is obtained after treatment.
According to the mole ratio of phenolic hydroxyl, amino and aldehyde functional groups of 1:1:2, 0.025mol of the prepared low molecular weight polyphenyl ether resin, 0.025mol of aniline and 0.05mol of paraformaldehyde are added into a four-neck flask provided with a condenser tube, a magnetor stirrer, a thermometer and a temperature sensor, 70mL of toluene/ethanol (1:5 v/v) mixed solvent is added, and the mixture is slowly heated to 70 ℃ for reaction for 60 hours. After the completion of the reaction, the reaction mixture was poured into 200mL of methanol solution (99 wt% concentration) and allowed to stand for 24 hours to obtain a precipitate, which was washed several times. The precipitation and washing process was repeated several times. Finally, the obtained precipitate is dried in vacuum for 12 hours at 60 ℃, and the dried product is ground to obtain light yellow powder which is the prepolymer of the aniline/bisphenol A type benzoxazine functional polyphenyl ether resin (the chemical structural formula is shown as follows).
Example 2
100G of commercial high molecular weight polyphenyl ether resin (with the number average molecular weight of 24000 g/mol), 25g of bisphenol A and 30g of peroxybenzoic acid are mixed in a butanone/N, N' -dimethylformamide (1:5 v/v) solvent, reacted for 4 hours at 125 ℃, and after the reaction is finished, the mixture is subjected to multiple precipitation and washing by distilled water, and the low molecular weight polyphenyl ether resin (with the number average molecular weight of 3827 g/mol) is obtained after treatment.
According to the mole ratio of phenolic hydroxyl, amino and aldehyde functional groups of 1:1:2, 0.025mol of the prepared low molecular weight polyphenylene ether resin, 0.025mol of furfuryl amine and 0.05mol of paraformaldehyde are added into a four-neck flask equipped with a condenser tube, a magnetic stirrer, a thermometer and a temperature sensor, 70mL of toluene/N, N' -dimethylformamide (5:1 v/v) mixed solvent is added, and the mixture is slowly heated to 105 ℃ for reaction for 5 hours. After the completion of the reaction, the reaction mixture was poured into 200mL of methanol solution (95 wt%) and allowed to stand for 24 hours to obtain a precipitate, which was washed several times. The precipitation and washing process was repeated several times. Finally, the obtained precipitate is dried in vacuum for 12 hours at 60 ℃, and the light yellow powder obtained by grinding the dried product is furfuryl amine/bisphenol A type benzoxazine functional polyphenyl ether prepolymer (the chemical structural formula is shown as follows).
Example 3
100G of commercial high molecular weight polyphenyl ether resin (with the number average molecular weight of 20000 g/mol), 20g of bisphenol A and 25g of 3,3', 5' -tetramethyl biphenyl biquinone are mixed in butanone/dioxane (1:3 v/v) solvent, reacted for 24 hours at 100 ℃, and after the reaction is finished, distilled water is used for multiple precipitation and washing, and the low molecular weight polyphenyl ether resin (with the number average molecular weight of 2645 g/mol) is obtained after treatment.
According to the mole ratio of phenolic hydroxyl, amino and aldehyde functional groups of 1:1:2, 0.025mol of the prepared low molecular weight polyphenylene ether resin, 0.0125mol of 4,4 '-diaminodiphenylmethane and 0.05mol of paraformaldehyde are added into a four-necked flask equipped with a condenser, a magnetor stirrer, a thermometer and a temperature sensor, 70mL of a toluene/N, N' -dimethylformamide (1:1 v/v) mixed solvent is added, and the mixture is slowly heated to 120 ℃ for reaction for 25 hours. After the completion of the reaction, the reaction mixture was poured into 200mL of a methanol solution (concentration: 90 wt%) and allowed to stand for 24 hours to obtain a precipitate, which was washed several times. The precipitation and washing process was repeated several times. Finally, the obtained precipitate is dried in vacuum for 12 hours at 60 ℃, and the dried product is ground to obtain light yellow powder which is the 4,4' -diaminodiphenyl methane/bisphenol A type benzoxazine functional polyphenyl ether prepolymer (the chemical structural formula is shown as follows).
Example 4
100G of commercial high molecular weight polyphenyl ether resin (with the number average molecular weight of 12000 g/mol), 20g of bisphenol A and 30g of peroxybenzoic acid are mixed in a toluene/ethanol (5:1 v/v) solvent, reacted for 50 hours at 60 ℃, and after the reaction is finished, the mixture is subjected to multiple precipitation and washing by distilled water, and the low molecular weight polyphenyl ether resin (with the number average molecular weight of 2027 g/mol) is obtained after treatment.
According to the mole ratio of phenolic hydroxyl, amino and aldehyde functional groups of 1:1:2, and the molar ratio of bisphenol A to the phenolic hydroxyl groups in the reassigned polyphenylene ether resin is 1:1, adding 0.05mol of prepared low molecular weight polyphenyl ether resin, 0.025mol of bisphenol A, 0.05mol of 1, 6-hexamethylenediamine and 0.2mol of paraformaldehyde into a 250mL three-neck flask provided with a condenser tube, a magnetor stirrer and a thermometer, adding 51mL of toluene/ethanol mixed solvent (1:2v/v), uniformly mixing, heating to 90 ℃ for reaction for 48 hours, pouring the reaction solution into 100mL of methanol solution (with the concentration of 40 wt%) after the reaction is finished to obtain a suspension, standing for 24 hours, removing supernatant to obtain a precipitate, vacuum-drying the precipitate at 50 ℃ for 8 hours, and finally grinding the dried product to obtain powder, namely the end-capped main chain benzoxazine functional polyphenyl ether resin prepolymer (with the chemical structural formula shown as below).
Wherein: r 2 isR 3 is
The molecular structural formulas of the 1, 6-hexamethylenediamine, bisphenol A and the redistributed polyphenyl ether resin used in the example are respectively as follows:
The products synthesized in the comparative examples and examples were characterized by infrared spectroscopy (FTIR), which indicates that the present invention successfully synthesizes the three benzoxazine-functionalized polyphenylene ether resin prepolymers based on the reassigned polyphenylene ether resin.
Wherein: the products synthesized in the comparative examples and examples are shown in FIG. 1.
Wherein:
fig. 1 a: redistributed low molecular weight polyphenylene ether resin prepared in comparative example;
Fig. 1 b: the aniline/bisphenol a-type benzoxazine-functionalized polyphenylene ether resin prepolymer synthesized in example 1;
fig. 1 c: furfuryl amine/bisphenol a-type benzoxazine-functionalized polyphenylene ether resin prepolymer of example 2;
Fig. 1 d: 4,4' -diaminodiphenylmethane/bisphenol A-type benzoxazine-functionalized polyphenylene ether prepolymer of example 3).
As shown in FIG. 1a, 3460cm-1 is the telescopic vibration characteristic absorption peak of hydroxyl, 1306, 1189, 1020cm-1 is the vibration characteristic absorption peak of phenyl ether, and 857cm-1 is the C-H bending vibration characteristic absorption peak on benzene ring. The infrared spectrum of the low molecular weight polyphenylene ether resin was substantially identical to that of the high molecular weight polyphenylene ether resin, which indicated that the redistribution reaction only changed the length of the molecular chain, and did not change the chemical structure of the polyphenylene ether. Notably, the prepolymer of the polyphenyl ether resin synthesized by the embodiment of the invention contains benzoxazine functional groups, and the characteristic absorption peak of the oxazine ring of the prepolymer is at 935cm -1. Asymmetric telescopic vibration characteristic absorption peaks of C-O-C (1229 cm -1) and C-N-C (1180 cm -1) of the benzoxazine structure were also observed, corresponding to the C-C telescopic vibration characteristic absorption peak in the plane of the trisubstituted benzene ring at 1498cm -1. Characteristic absorption peaks ascribed to furan rings at 1605 and 988cm -1 can also be observed for the prepolymer of furfuryl amine/bisphenol a type benzoxazine functionalized polyphenylene ether resin (fig. 1 c). The above infrared spectral results demonstrate that the present invention successfully synthesizes a prepolymer of a benzoxazine-functionalized polyphenylene ether resin based on a reassigned polyphenylene ether resin.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (12)
1. The polyphenyl ether composite resin with excellent comprehensive performance is benzoxazine functional polyphenyl ether/benzoxazine binary composite resin or benzoxazine functional polyphenyl ether/hydrocarbon resin binary composite resin or benzoxazine functional polyphenyl ether/benzoxazine/hydrocarbon resin ternary composite resin which is obtained by curing a benzoxazine functional polyphenyl ether resin prepolymer and a benzoxazine or/and hydrocarbon resin prepolymer; 55-95 parts by weight of benzoxazine functionalized polyphenyl ether resin prepolymer in the benzoxazine functionalized polyphenyl ether/benzoxazine binary composite resin; 45-5 parts by weight of benzoxazine;
55-95 parts by weight of benzoxazine functionalized polyphenyl ether resin prepolymer in the benzoxazine functionalized polyphenyl ether/hydrocarbon resin binary composite resin; 45-5 parts by weight of hydrocarbon resin prepolymer;
55-85 parts by weight of benzoxazine functionalized polyphenyl ether resin prepolymer in the benzoxazine functionalized polyphenyl ether/benzoxazine/hydrocarbon resin ternary composite resin; 15-5 parts of benzoxazine; 30 to 10 weight portions of hydrocarbon resin prepolymer,
The benzoxazine functionalized polyphenyl ether resin prepolymer is more than one of benzoxazine functionalized polyphenyl ether compounds shown in the following structural formula, and the benzoxazine functionalized polyphenyl ether comprises monofunctional benzoxazine, difunctional benzoxazine and end-capped main chain benzoxazine functionalized polyphenyl ether, wherein the structural formula is shown in the formula 1:
R 1 -is
-R 2- is
-R 3- is
N is 15-30, and m is 1-5.
2. The polyphenylene ether composite resin excellent in combination properties according to claim 1, wherein: the benzoxazine is one or a combination of the following components: a monofunctional benzoxazine which is a compound of formula (i), a difunctional benzoxazine, a multifunctional benzoxazine is used as a solvent, backbone benzoxazines, end-capped backbone benzoxazines, naphthoxazines.
3. The polyphenylene ether composite resin excellent in combination properties according to claim 1, wherein: the benzoxazine is intrinsic flame-retardant benzoxazine.
4. The polyphenylene ether composite resin excellent in combination properties according to claim 3, wherein: the benzoxazine is more than one of intrinsic flame-retardant benzoxazine compounds, and the chemical structural formula of the intrinsic flame-retardant benzoxazine is shown as formula 2:
5. The polyphenylene ether composite resin excellent in combination properties according to claim 1, wherein: the hydrocarbon resin prepolymer is one or a combination of the following prepolymers: styrene-maleic anhydride copolymer, polybutadiene resin, hydrogenated diene-butadiene-styrene copolymer, styrene-butadiene resin, styrene-isoprene copolymer, styrene-butadiene copolymer, cyclic olefin copolymer, polyisoprene rubber, styrene-butadiene-divinylbenzene copolymer.
6. The method for producing a polyphenylene ether composite resin excellent in combination properties as set forth in claim 1, characterized in that:
55-95 parts by weight of benzoxazine functionalized polyphenyl ether resin prepolymer is added into a reaction container; 45-5 parts by weight of benzoxazine, dispersing the benzoxazine in an organic solvent to obtain a composite resin prepolymer with the solid content of 20-90 wt%, pre-reacting for a period of time, and heating and curing the resin prepolymer obtained by pre-reacting to obtain the benzoxazine functionalized polyphenyl ether/benzoxazine binary composite resin;
55-95 parts by weight of benzoxazine functionalized polyphenyl ether resin prepolymer is added into a reaction container; 45-5 parts by weight of hydrocarbon resin prepolymer, dispersing the hydrocarbon resin prepolymer in an organic solvent to obtain a composite resin prepolymer with 20-90 wt% of solid content, pre-reacting for a period of time, and heating and curing the resin prepolymer obtained by pre-reacting to obtain benzoxazine functionalized polyphenyl ether/hydrocarbon resin binary composite resin;
adding 55-85 parts by weight of benzoxazine functionalized polyphenyl ether resin prepolymer into a reaction container; 15-5 parts of benzoxazine; 30-10 parts by weight of hydrocarbon resin prepolymer, dispersing the hydrocarbon resin prepolymer in an organic solvent to obtain a composite resin prepolymer with the solid content of 20-90 wt%, pre-reacting for a period of time, and heating and curing the resin prepolymer obtained by pre-reacting to obtain the benzoxazine-functionalized polyphenyl ether/benzoxazine/hydrocarbon resin ternary composite resin after curing.
7. The method of manufacturing according to claim 6, wherein: the organic solvent is one or a combination of the following components: toluene, ethanol, methanol, xylene, diethyl ether, acetone, butanone, cyclohexanone, ethyl acetate, N '-dimethylformamide, N' -dimethylacetamide, ethylene glycol methyl ether, propylene glycol methyl ether, dioxane, chloroform.
8. The method of manufacturing according to claim 6, wherein: the pre-reaction is carried out for 1-12 hours at 60-120 ℃, and the curing condition of the polyphenyl ether composite resin is 100-220 ℃ for 2-24 hours.
9. The method of manufacturing according to claim 6, wherein: the preparation method of the benzoxazine functionalized polyphenyl ether resin prepolymer comprises the following steps: adding reactants which are a phenol source, an amine source and an aldehyde compound into a reaction container in a one-step or step-by-step multi-feeding mode, reacting for 5-60 hours at 70-120 ℃ in a nitrogen atmosphere, and performing post-treatment to obtain a benzoxazine functional polyphenyl ether resin prepolymer, wherein the one-step feeding mode is that all raw materials are simultaneously added into the reaction container, and then a polar/nonpolar mixed solvent is added for dissolution and reaction; the step-by-step and repeated feeding mode is that firstly aldehyde compounds and amine compounds are added into a reaction container, then a polar/nonpolar mixed solvent is added, and phenol source substances are added after stirring is complete;
Wherein:
the phenol source in the preparation of the monofunctional benzoxazine functional polyphenyl ether resin prepolymer (formula 1 (a)) is redistributed polyphenyl ether resin, and the amine source is aniline, furfuryl amine, allylamine and paravinylaniline;
The phenol source in the preparation of the difunctional benzoxazine functional polyphenyl ether resin prepolymer (formula 1 (b)) is redistributed polyphenyl ether resin, and the amine source is 4,4' -diaminodiphenylmethane and hexamethylenediamine;
In the preparation of the end-capped main chain benzoxazine functionalized polyphenyl ether resin prepolymer (formula 1 (c)), phenol sources are dihydric phenol and reassigned polyphenyl ether resin, wherein the dihydric phenol is bisphenol A, bisphenol F, bisphenol S, dicyclopentadiene bisphenol A, 4' -dihydroxybiphenyl, 4' -dihydroxydiphenyl ether, and the amine source is 4,4' -diaminodiphenylmethane and hexamethylenediamine.
10. The method of manufacturing according to claim 9, wherein: the redistribution polyphenyl ether resin is obtained by redistribution reaction of commercial high molecular weight polyphenyl ether, and the number average molecular weight of the redistribution polyphenyl ether resin is 2027-3827.
11. The use of the polyphenylene ether composite resin of claim 1 having excellent combination properties as a resin varnish or prepreg or laminate or multilayer printed wiring board, wherein the resin varnish is composed of the polyphenylene ether composite resin prepolymer of claim 1 and an organic solvent; the prepreg is prepared by adding inorganic filler and/or flame retardant into the resin varnish; the laminated board is formed by uniformly coating the prepreg on non-woven fabrics; the multilayer printed wiring board is made of the laminated board.
12. A multilayer printed wiring board comprising a copper foil and a laminate made of a prepreg containing the polyphenylene ether-based composite resin according to claim 1 supported on the copper foil.
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