CN110511360A - A kind of active ester resin and its preparation method and application - Google Patents
A kind of active ester resin and its preparation method and application Download PDFInfo
- Publication number
- CN110511360A CN110511360A CN201910811203.1A CN201910811203A CN110511360A CN 110511360 A CN110511360 A CN 110511360A CN 201910811203 A CN201910811203 A CN 201910811203A CN 110511360 A CN110511360 A CN 110511360A
- Authority
- CN
- China
- Prior art keywords
- chloride
- resin
- active ester
- naphthalene
- ester 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.)
- Granted
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 153
- 239000011347 resin Substances 0.000 title claims abstract description 153
- 150000002148 esters Chemical class 0.000 title claims abstract description 136
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 239000003822 epoxy resin Substances 0.000 claims abstract description 33
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 33
- 239000004305 biphenyl Substances 0.000 claims abstract description 28
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 10
- 235000010290 biphenyl Nutrition 0.000 claims abstract description 8
- -1 2,2'- dihydroxybiphenyl phenolic resin Chemical compound 0.000 claims description 135
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 129
- 229920001568 phenolic resin Polymers 0.000 claims description 88
- 239000005011 phenolic resin Substances 0.000 claims description 88
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 claims description 79
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 64
- IMHDGJOMLMDPJN-UHFFFAOYSA-N biphenyl-2,2'-diol Chemical group OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 claims description 53
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 claims description 41
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims description 40
- 235000010292 orthophenyl phenol Nutrition 0.000 claims description 40
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 35
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 34
- 239000003292 glue Substances 0.000 claims description 32
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 27
- 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 25
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical group CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 19
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- 150000004782 1-naphthols Chemical class 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 12
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 12
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000012779 reinforcing material Substances 0.000 claims description 7
- 229910015900 BF3 Inorganic materials 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 6
- 150000002790 naphthalenes Chemical class 0.000 claims description 6
- 150000001263 acyl chlorides Chemical class 0.000 claims description 5
- GFAUNYMRSKVDJL-UHFFFAOYSA-N formyl chloride Chemical compound ClC=O GFAUNYMRSKVDJL-UHFFFAOYSA-N 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 125000002619 bicyclic group Chemical group 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 3
- RCHKEJKUUXXBSM-UHFFFAOYSA-N n-benzyl-2-(3-formylindol-1-yl)acetamide Chemical compound C12=CC=CC=C2C(C=O)=CN1CC(=O)NCC1=CC=CC=C1 RCHKEJKUUXXBSM-UHFFFAOYSA-N 0.000 claims description 3
- NIXKBAZVOQAHGC-UHFFFAOYSA-N phenylmethanesulfonic acid Chemical compound OS(=O)(=O)CC1=CC=CC=C1 NIXKBAZVOQAHGC-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 claims description 2
- FYXKZNLBZKRYSS-UHFFFAOYSA-N benzene-1,2-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC=C1C(Cl)=O FYXKZNLBZKRYSS-UHFFFAOYSA-N 0.000 claims 2
- 229920003986 novolac Polymers 0.000 claims 1
- 238000004132 cross linking Methods 0.000 abstract description 13
- 230000009477 glass transition Effects 0.000 abstract description 10
- 239000003063 flame retardant Substances 0.000 abstract description 6
- 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 abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 135
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 46
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 45
- 238000003756 stirring Methods 0.000 description 39
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 26
- 239000004744 fabric Substances 0.000 description 26
- 239000011521 glass Substances 0.000 description 26
- 239000007788 liquid Substances 0.000 description 21
- 238000000926 separation method Methods 0.000 description 21
- 230000003068 static effect Effects 0.000 description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 13
- 230000006837 decompression Effects 0.000 description 13
- 230000018044 dehydration Effects 0.000 description 13
- 238000006297 dehydration reaction Methods 0.000 description 13
- 238000001035 drying Methods 0.000 description 13
- 238000003825 pressing Methods 0.000 description 13
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 13
- 235000017557 sodium bicarbonate Nutrition 0.000 description 13
- 238000010792 warming Methods 0.000 description 13
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 229910021529 ammonia Inorganic materials 0.000 description 8
- 239000003125 aqueous solvent Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 150000003222 pyridines Chemical class 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 7
- 238000005227 gel permeation chromatography Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- MDVUQSWBRKRIBG-UHFFFAOYSA-N [S]CC1=CC=CC=C1 Chemical compound [S]CC1=CC=CC=C1 MDVUQSWBRKRIBG-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 150000003927 aminopyridines Chemical class 0.000 description 4
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- XYHUIOCRXXWEAX-UHFFFAOYSA-N cyclopenta-1,3-diene;phenol Chemical group C1C=CC=C1.OC1=CC=CC=C1 XYHUIOCRXXWEAX-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- JBVCEGLZIMVTFE-UHFFFAOYSA-N formaldehyde;phenoxybenzene Chemical compound O=C.C=1C=CC=CC=1OC1=CC=CC=C1 JBVCEGLZIMVTFE-UHFFFAOYSA-N 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- XRQVVFIEYAHKBV-OGYJWPHRSA-N opp protocol Chemical compound CNNCC1=CC=C(C(=O)NC(C)C)C=C1.O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1.C([C@H](C[C@]1(C(=O)OC)C=2C(=C3C([C@]45[C@H]([C@@]([C@H](OC(C)=O)[C@]6(CC)C=CCN([C@H]56)CC4)(O)C(=O)OC)N3C=O)=CC=2)OC)C[C@@](C2)(O)CC)N2CCC2=C1NC1=CC=CC=C21 XRQVVFIEYAHKBV-OGYJWPHRSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 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
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical class CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- ANRCFKDSDRXMCZ-UHFFFAOYSA-N [Cl].C(C1=CC=C(C(=O)N)C=C1)(=O)N Chemical compound [Cl].C(C1=CC=C(C(=O)N)C=C1)(=O)N ANRCFKDSDRXMCZ-UHFFFAOYSA-N 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical class [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000007707 calorimetry Methods 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- LCDFWRDNEPDQBV-UHFFFAOYSA-N formaldehyde;phenol;urea Chemical compound O=C.NC(N)=O.OC1=CC=CC=C1 LCDFWRDNEPDQBV-UHFFFAOYSA-N 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 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
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- WSGCRAOTEDLMFQ-UHFFFAOYSA-N nonan-5-one Chemical compound CCCCC(=O)CCCC WSGCRAOTEDLMFQ-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- 238000009774 resonance method Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
Classifications
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/123—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/127—Acids containing aromatic rings
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/123—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/133—Hydroxy compounds containing aromatic rings
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- 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
- H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
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Abstract
The present invention provides a kind of active ester resin and its preparation method and application, by introducing biphenyl structural in active ester resin, biphenyl structural is as a kind of structure with more phenyl ring, higher glass transition temperature, dimensional stability and anti-flammability can be brought, to make the active ester resin that there is high glass-transition temperature, high flame retardant and excellent impact resistance；The active ester resin has multiple crosslinking points, to make the active ester resin be easy to generate cross-linking and curing reaction with epoxy resin, and since the active ester resin will not generate secondary hydroxyl when solidifying with cross linking of epoxy resin, therefore not only there are excellent dielectric properties by the curing system that crosslinking curing is formed, while also there is good heat resistance, moisture-proof, impact resistance and anti-flammability；So as to effectively meet electronic product high-frequency, the use demand of high speed instantly.
Description
Technical field
The present invention relates to polymeric material fields more particularly to a kind of active ester resin and its preparation method and application.
Background technique
It is shown using epoxy resin and its curing agent as the curing system of the composition epoxy resin of essential component excellent
Heat resistance and insulating properties, therefore be widely used in the electronic components such as semiconductor, multilayer printed board.
All kinds of electronic component-uses on the way, especially in the technical field of multilayer printed board insulating materials, in recent years
Come, the high speed of the signal in various electronic equipments, high-frequencyization are promoting.However, along with the high speed of signal, high frequency
Rate guarantees substantially low previous composition epoxy resin and its solidfied material while guaranteeing high-speed high frequency signal
Dielectric constant and substantially low dielectric loss angle tangent gradually become difficult.Therefore, for composition epoxy resin and its admittedly
Compound, while ensuring to have the signal of high speed, high-frequency, it is also desirable to substantially low dielectric constant can be shown simultaneously
Show substantially low dielectric loss angle tangent.
However, being also required to due to the high-frequency of electronic component, the tendency of miniaturization to multilayer printed board insulating materials
Higher dimensional stability and good heat resistance, higher glass transition temperature and anti-flammability.And in studying at present, for
Simultaneously there is the epoxy curing agent system of low-dielectric loss and above-mentioned characteristic to still have some deficits, thus is not able to satisfy material reality
Requirement in.
Summary of the invention
It is an object of the invention to overcome the deficiencies of existing technologies, a kind of active ester resin and preparation method thereof is provided and is answered
With.
In order to achieve the above object, first aspect present invention provides a kind of active ester resin, the active ester resin includes such as
At least one of resin shown in formula A and the resin as shown in formula B；Wherein, structural formula shown in formula A are as follows:
Wherein, Ar is any one of ortho position xenyl, para-biphenyl base and 1- naphthalene；Ph is appointing in phenyl ring and naphthalene nucleus
It is a kind of；R is any one of ortho position xenyl, para-biphenyl base；
X is methylene；N is 0~20；
Structural formula shown in formula B are as follows:
Wherein, R1For any one of ortho position xenyl, para-biphenyl base and 1- naphthalene；Ph is phenyl ring or naphthalene nucleus；
Work as R1When for any in ortho position xenyl, para-biphenyl base, R2For ortho position xenyl, para-biphenyl base and double
Any one of cyclopentadiene phenol structure；Work as R1When for 1- naphthalene, R2For ortho position xenyl and any in para-biphenyl base
Kind；
N is 0~20.
Second aspect of the present invention provides a kind of resin combination, including active ester resin as described above and epoxy resin,
Ester functional groups' equivalent proportion of the active ester resin and the epoxy resin is (1~1.5): 1.
Third aspect present invention provides a kind of prepreg, including resin combination as described above and reinforcing material, institute
It states the dissolution of resin combination solvent and glue is made, then the reinforcing material is immersed in the glue, shape after heat treatment
At the prepreg.
Fourth aspect present invention provides a kind of laminate, the solidfied material including prepreg as described above.
Fifth aspect present invention provides a kind of printed circuit board, the solidfied material including prepreg as described above.
Sixth aspect present invention provides a kind of preparation method of active ester resin, as the structural formula such as formula A of active ester resin
Shown, the preparation method of the active ester resin includes the following steps:
O-phenyl phenol/p-phenyl phenol/2,2'- dihydroxybiphenyl/4,4' dihydroxy diphenyl is reacted to obtain with formaldehyde
O-phenyl phenol phenolic resin/p-phenyl phenol phenolic resin/2,2'- dihydroxybiphenyl phenolic resin/4,4' dihydroxy diphenyl
Phenolic resin；
The structural formula of the o-phenyl phenol phenolic resin is as shown in formula C:
N is 0~5；
The structural formula of the p-phenyl phenol phenolic resin is as shown in formula D:
N is 0~5；
The structural formula of the 4,4' dihydroxy diphenyl phenolic resin is as shown in formula E:
N is 0~5；
The structural formula of the 2,2'- dihydroxybiphenyl phenolic resin is as shown in formula F:
N is 0~5；
The o-phenyl phenol phenolic resin/p-phenyl phenol phenolic resin/2,2'- dihydroxybiphenyl the phenol being prepared
In urea formaldehyde/4,4'- dihydroxybiphenyl phenolic resin, o-phenyl phenol/p-phenyl phenol/1- naphthols, phenyl-diformyl is added
Chlorine/paraphthaloyl chloride/o-phthaloyl chloride/1,5- naphthalene dimethyl chloride/1,6- naphthalene dimethyl chloride/1,7- naphthalene dimethyl chloride/1,
8- naphthalene dimethyl chloride/2,6- naphthalene dimethyl chloride/2,7- naphthalene dimethyl chloride, acid binding agent are reacted, and active ester resin is obtained；
Alternatively, when the structural formula of active ester resin is as shown in formula B, R2When for dicyclopentadiene phenol structure, the activity
The preparation method of ester resin includes the following steps:
Phenol, dicyclopentadiene and the first catalyst reaction are obtained into dicyclopentadiene phenolic resin, described bicyclic penta 2
The structural formula of alkene phenolic resin is as shown in formula G:
N is 0~5；
In the dicyclopentadiene phenolic resin being prepared, o-phenyl phenol/p-phenyl phenol, isophthalic two is added
Formyl chloride/paraphthaloyl chloride/o-phthaloyl chloride/1,5- naphthalene dimethyl chloride/1,6- naphthalene dimethyl chloride/two formyl of 1,7- naphthalene
Chlorine/1,8- naphthalene dimethyl chloride/2,6- naphthalene dimethyl chloride/2,7- naphthalene dimethyl chloride, acid binding agent are reacted, and active ester tree is obtained
Rouge；
Alternatively, when the structural formula of active ester resin is formula B, R2For any one of ortho position xenyl and para-biphenyl base
When, the preparation method of the active ester resin includes the following steps:
In 2,2'- dihydroxybiphenyl or 4,4'- dihydroxybiphenyl, o-phenyl phenol/p-phenyl phenol/1- naphthalene is added
Phenol, m-phthaloyl chloride/paraphthaloyl chloride/o-phthaloyl chloride/1,5- naphthalene dimethyl chloride/1,6- naphthalene dimethyl chloride/1,7-
Naphthalene dimethyl chloride/1,8- naphthalene dimethyl chloride/2,6- naphthalene dimethyl chloride/2,7- naphthalene dimethyl chloride, acid binding agent are reacted, and are lived
Property ester resin.
As a further improvement of the above technical scheme, the hydroxyl equivalent of the o-phenyl phenol phenolic resin is 175g/
Eq~190g/eq；The hydroxyl equivalent of the p-phenyl phenol phenolic resin is 175g/eq~190g/eq；The 2,2'- dihydroxy
The hydroxyl equivalent of base biphenyl phenolic resin is 96.5g/eq~115g/eq；The hydroxyl of the 4,4' dihydroxy diphenyl phenolic resin
Equivalent is 96.5g/eq~115g/eq；The hydroxyl equivalent of the dicyclopentadiene phenolic resin is 180g/eq~210g/eq.
As a further improvement of the above technical scheme, o-phenyl phenol/p-phenyl phenol/2,2'- dihydroxybiphenyl/
In the reacting of 4,4'- dihydroxybiphenyls and formaldehyde, o-phenyl phenol/p-phenyl phenol/2,2'- dihydroxybiphenyl/4 of addition,
The molar ratio of 4'- dihydroxybiphenyl and formaldehyde is (1~2): 1；
It preferably, further include that the second catalyst is added in the reaction system；
Preferably, second catalyst is acidic catalyst；
Preferably, reaction temperature is 90 DEG C~130 DEG C.
As a further improvement of the above technical scheme, in phenol, the reacting of dicyclopentadiene and the first catalyst, add
The molar ratio of the dicyclopentadiene and phenol that enter is (3~5): 1；
Preferably, first catalyst include boron trifluoride ether at least one of benzyl sulfonic acid；
Preferably, reaction temperature is 110 DEG C~120 DEG C.
As a further improvement of the above technical scheme, the o-phenyl phenol phenolic resin/p-phenyl phenol phenolic aldehyde tree
Rouge/2,2'- dihydroxybiphenyl phenolic resin/4,4' dihydroxy diphenyl phenolic resin, o-phenyl phenol/p-phenyl phenol/1- naphthalene
Phenol, m-phthaloyl chloride/paraphthaloyl chloride/o-phthaloyl chloride/1,5- naphthalene dimethyl chloride/1,6- naphthalene dimethyl chloride/1,7-
Naphthalene dimethyl chloride/1,8- naphthalene dimethyl chloride/2,6- naphthalene dimethyl chloride/2,7- naphthalene dimethyl chloride additional amount presses phenolic hydroxyl group and acyl chlorides
The ratio that the molar ratio of base is 1:1 is added；
The dicyclopentadiene phenolic resin, o-phenyl phenol/p-phenyl phenol, m-phthaloyl chloride/paraphenylene terephthalamide
Chlorine/o-phthaloyl chloride/1,5- naphthalene dimethyl chloride/1,6- naphthalene dimethyl chloride/1,7- naphthalene dimethyl chloride/1,8- naphthalene dimethyl chloride/
2,6- naphthalene dimethyl chloride/2,7- naphthalene dimethyl chloride additional amount is added in the ratio that the molar ratio of phenolic hydroxyl group and acid chloride group is 1:1；
2,2'- dihydroxybiphenyl/the 4,4' dihydroxy diphenyl, o-phenyl phenol/p-phenyl phenol/1- naphthols, isophthalic
Dimethyl chloride/paraphthaloyl chloride/o-phthaloyl chloride/1,5- naphthalene dimethyl chloride/1,6- naphthalene dimethyl chloride/two formyl of 1,7- naphthalene
Chlorine/1,8- naphthalene dimethyl chloride/2,6- naphthalene dimethyl chloride/2,7- naphthalene dimethyl chloride additional amount presses mole of phenolic hydroxyl group and acid chloride group
Than the ratio addition for 1:1.
Beneficial effects of the present invention:
The present invention provides a kind of active ester resin and its preparation method and application, by introducing biphenyl in active ester resin
Structure, biphenyl structural can bring higher glass transition temperature, size stable as a kind of structure with more phenyl ring
Property and anti-flammability, thus make the active ester resin have high glass-transition temperature, high flame retardant and excellent impact resistance；It should
Active ester resin has multiple crosslinking points, so that the active ester resin is made to be easy to generate cross-linking and curing reaction with epoxy resin, and
Since the active ester resin will not generate secondary hydroxyl when solidifying with cross linking of epoxy resin, consolidate by what crosslinking curing was formed
Change system not only has excellent dielectric properties, while also having good heat resistance, moisture-proof, impact resistance and anti-flammability；
So as to effectively meet electronic product high-frequency, the use demand of high speed instantly.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached
Figure is briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as pair
The restriction of the scope of the invention.
Fig. 1 is the GPC spectrogram of the active ester resin in the embodiment of the present invention 2；
Fig. 2 is the GPC spectrogram of the active ester resin in the embodiment of the present invention 4；
Fig. 3 is the GPC spectrogram of the active ester resin in the embodiment of the present invention 6.
Specific embodiment
Term as used herein:
" by ... preparation " it is synonymous with "comprising".Term "comprising" used herein, " comprising ", " having ", " containing "
Or its any other deformation, it is intended that cover non-exclusionism includes.For example, composition, step, method comprising listed elements,
Product or device are not necessarily limited to those elements, but may include not expressly listed other elements or such composition, step
Suddenly, method, product or the intrinsic element of device.
Conjunction " by ... form " exclude any element that do not point out, step or component.If in claim,
This phrase will make claim closed, so that it is not included the material in addition to the material of those descriptions, but relative
Except customary impurities.When phrase " by ... form " be rather than immediately following theme in the clause that appears in claim main body after
When, only it is limited to element described in the clause；Other elements be not excluded the claim as a whole it
Outside.
Equivalent, concentration or other values or parameter are excellent with range, preferred scope or a series of upper limit preferred values and lower limit
When the Range Representation that choosing value limits, this should be understood as specifically disclosing by any range limit or preferred value and any range
Any pairing of lower limit or preferred value is formed by all ranges, regardless of whether the range separately discloses.For example, when open
When range " 1~5 ", described range should be interpreted as including range " 1~4 ", " 1~3 ", " 1~2 ", " 1~2 and 4~
5 ", " 1~3 and 5 " etc..When numberical range is described herein, unless otherwise stated, otherwise the range is intended to include its end
Value and all integers and score in the range.
In these embodiments, unless otherwise specified, described part and percentage is by mass.
" mass parts " refer to the basic measurement unit for indicating the mass ratio relationship of multiple components, and 1 part can indicate arbitrary list
Position quality, can such as be expressed as 1g, may also indicate that 2.689g etc..If we say that the mass parts of component A are a parts, the matter of B component
Measuring part is b parts, then it represents that the quality of component A and the mass ratio a:b of B component.Alternatively, indicating that the quality of component A is aK, B group
The quality divided is bK (K is arbitrary number, indicates multiplying factor).It can not misread, unlike mass fraction, all components
The sum of mass parts be not limited to 100 parts of limitation.
"and/or" is used to indicate that one of illustrated situation or both may to occur, for example, A and/or B includes (A
And B) and (A or B).
As used herein, term " o-phenyl phenol " is identical as " OPP " meaning, term " o-phenyl phenol phenolic resin " with
" OPP phenolic resin " meaning is identical, and term " p-phenyl phenol " is identical as " PPP " meaning, term " p-phenyl phenol phenolic aldehyde tree
Rouge " is identical as " PPP phenolic resin " meaning, and term " dicyclopentadiene " is identical as " DCPD " meaning, term " dicyclopentadiene phenol
Urea formaldehyde " is identical as " DCPD phenolic resin " meaning.
The present invention provides a kind of active ester resin, including as in resin shown in formula A and the resin as shown in formula B at least
It is a kind of；Wherein, structural formula shown in formula A are as follows:
Wherein, Ar is any one of ortho position xenyl, para-biphenyl base and 1- naphthalene；Ph is appointing in phenyl ring and naphthalene nucleus
It is a kind of；R is any one of ortho position xenyl, para-biphenyl base；
X is methylene；N is 0~20；
Structural formula shown in formula B are as follows:
Wherein, R1For any one of ortho position xenyl, para-biphenyl base and 1- naphthalene；Ph is phenyl ring or naphthalene nucleus；
Work as R1When for any in ortho position xenyl, para-biphenyl base, R2For ortho position xenyl, para-biphenyl base and double
Any one of cyclopentadiene phenol structure；Work as R1When for 1- naphthalene, R2For ortho position xenyl and any in para-biphenyl base
Kind；
N is 0~20.
It is understood that biphenyl structural is as a kind of with more by introducing biphenyl structural in active ester resin
The structure of phenyl ring can bring higher glass transition temperature, dimensional stability and anti-flammability, to make the active ester resin
It with high glass-transition temperature, high flame retardant and excellent impact resistance, and can be dissolved in most of organic solvent, have excellent
Different dissolubility.
In addition, the active ester resin has multiple crosslinking points, so that the active ester resin be made to be easy to generate with epoxy resin
Cross-linking and curing reaction.It is to crosslink to react with the epoxy group of epoxy resin by hydroxyl compared to existing phenolic resin, makes
The shortcomings that being easy to produce secondary hydroxyl after cross-linking reaction, leading to occur higher composition water absorption rate, higher dielectric consume, this reality
The active ester resin in mode is applied due to being to pass through work when active ester resin is reacted with epoxy resin with the presence of ester group
The ester group of property ester resin is crosslinked with the epoxy group of epoxy resin to react, thus the active ester resin with cross linking of epoxy resin
Secondary hydroxyl will not be generated when solidification.Therefore the active ester resin in present embodiment and epoxy resin are formed by crosslinking curing
Curing system not only has excellent dielectric properties, while having good heat resistance, moisture-proof, impact resistance and anti-flammability；
So as to effectively meet electronic product high-frequency, the use demand of high speed instantly.
The present invention also provides a kind of resin combination, the resin combination includes active ester resin and ring as described above
Ester functional groups' equivalent proportion of oxygen resin, the active ester resin and the epoxy resin is (1~1.5): 1, such as can be
1:1、1.1:1、1.2:1、1.3:1、1.4:1、1.5:1。
Preferably, ester functional groups' equivalent proportion of the active ester resin and epoxy resin is (1~1.1): 1.
Above-mentioned resin combination can be used for manufacturing semiconductor-encapsulating material, lamination adhering film, binder, resin
Cast material, conductive paste etc..
Above-mentioned resin combination can add the one of inorganic filler, fire retardant and curing accelerator according to the actual situation
Kind is a variety of.
The inorganic filler includes but is not limited to aluminium hydroxide, boehmite, silica, talcum powder, mica, sulfuric acid
One of barium, lithopone, calcium carbonate, wollastonite, kaolin, shepardite, diatomite, bentonite and ground pumice are a variety of.
The fire retardant includes but is not limited to three (2,6- 3,5-dimethylphenyl) phosphines, 10- (2,5- dihydroxy phenyl) -9,10-
Miscellaneous -10- phosphine phenanthrene -10- the oxide of dihydro-9-oxy, 2,6- bis- (2,6- 3,5-dimethylphenyl) phosphino- benzene, 10- phenyl -9,10- dihydro -
9- oxa- -10- phosphine phenanthrene -10- oxide, phenoxyphosphazene compound, nitrogen phosphorus series expansion type organic fire-retardant, phosphorus-containing phenolic aldehyde tree
One of rouge, phosphorous bismaleimide, zinc borate, aluminium hydroxide, magnesium hydroxide and antimony oxide are a variety of.
The curing accelerator includes but is not limited to lutidines, 2-methylimidazole, 2- phenylimidazole, benzyl diformazan
One of amine, triethylamine, triethanolamine, dimethylethanolamine and triphenylphosphine are a variety of.
The present invention also provides a kind of prepreg, including resin combination as described above and reinforcing material, the resins
Glue is made in the dissolution of composition solvent, and then the reinforcing material is immersed in the glue, after heat treatment described in formation
Prepreg.
Optionally, the solvent includes but is not limited to that toluene, dimethylbenzene, trimethylbenzene, acetone, butanone, cyclohexanone, methyl are different
One of butyl ketone, N,N-dimethylformamide, tetrahydrofuran, butyl acetate, petroleum ether are a variety of.
The reinforcing material includes carbon fiber, glass fibre, any one in aramid fibre.
The present invention also provides a kind of laminate, the solidfied material including prepreg as described above.
The present invention also provides a kind of printed circuit board, the solidfied material including prepreg as described above.
The present invention provides a kind of preparation method of active ester resin, described when the structural formula of active ester resin is as shown in formula A
The preparation method of active ester resin includes the following steps:
O-phenyl phenol/p-phenyl phenol/2,2'- dihydroxybiphenyl/4,4' dihydroxy diphenyl is reacted to obtain with formaldehyde
O-phenyl phenol phenolic resin/p-phenyl phenol phenolic resin/2,2'- dihydroxybiphenyl phenolic resin/4,4' dihydroxy diphenyl
Phenolic resin；
The structural formula of the o-phenyl phenol phenolic resin is as shown in formula C:
N is 0~5；
The structural formula of the p-phenyl phenol phenolic resin is as shown in formula D:
N is 0~5；
The structural formula of the 4,4' dihydroxy diphenyl phenolic resin is as shown in formula E:
N is 0~5；
The structural formula of the 2,2'- dihydroxybiphenyl phenolic resin is as shown in formula F:
N is 0~5；
In the o-phenyl phenol phenolic resin/p-phenyl phenol phenolic resin/2,2'- dihydroxybiphenyl being prepared
In phenolic resin/4,4'- dihydroxybiphenyl phenolic resin, o-phenyl phenol/p-phenyl phenol/1- naphthols, isophthalic diformazan is added
Acyl chlorides/paraphthaloyl chloride/o-phthaloyl chloride/1,5- naphthalene dimethyl chloride/1,6- naphthalene dimethyl chloride/1,7- naphthalene dimethyl chloride/
1,8- naphthalene dimethyl chloride/2,6- naphthalene dimethyl chloride/2,7- naphthalene dimethyl chloride, acid binding agent are reacted, and active ester resin is obtained.
Specifically, the hydroxyl equivalent of the o-phenyl phenol phenolic resin is 175g/eq~190g/eq, such as can be
175g/eq, 178g/eq, 180g/eq, 185g/eq, 190g/eq etc..
Specifically, the hydroxyl equivalent of the p-phenyl phenol phenolic resin is 175g/eq~190g/eq, such as can be
175g/eq, 178g/eq, 180g/eq, 185g/eq, 190g/eq etc..
Specifically, the hydroxyl equivalent of 2, the 2'- dihydroxybiphenyl phenolic resin is 96.5g/eq~115g/eq, such as
It can be 96.5g/eq, 99g/eq, 100g/eq, 105g/eq, 115g/eq etc..
Specifically, the hydroxyl equivalent of 4, the 4'- dihydroxybiphenyl phenolic resin is 96.5g/eq~115g/eq, such as
It can be 96.5g/eq, 99g/eq, 100g/eq, 105g/eq, 115g/eq etc..
Specifically, be added o-phenyl phenol/p-phenyl phenol/2,2'- dihydroxybiphenyl/4,4'- dihydroxybiphenyl with
The molar ratio of formaldehyde is (1~2): 1, such as can be 1:1,1.2:1,1.5:1,2:1 etc..
Preferably, in order to further speed up reaction rate, in o-phenyl phenol/p-phenyl phenol/2,2'- dihydroxy connection
It further include that the second catalyst is added in the reaction system in the reacting of benzene/4,4'- dihydroxybiphenyl and formaldehyde, and reaction temperature
Between 90 DEG C~130 DEG C, such as it can be 90 DEG C, 100 DEG C, 110 DEG C, 120 DEG C, 130 DEG C etc..
Above-mentioned, second catalyst includes acidic catalyst, including but not limited to hydrochloric acid, oxalic acid, p-methyl benzenesulfonic acid
It is one or more.
Specifically, the o-phenyl phenol phenolic resin/p-phenyl phenol phenolic resin/2,2'- dihydroxybiphenyl phenolic aldehyde
Resin/4,4' dihydroxy diphenyl phenolic resin, o-phenyl phenol/p-phenyl phenol/1- naphthols, m-phthaloyl chloride/to benzene two
Formyl chloride/o-phthaloyl chloride/1,5- naphthalene dimethyl chloride/1,6- naphthalene dimethyl chloride/1,7- naphthalene dimethyl chloride/two formyl of 1,8- naphthalene
Chlorine/2,6- naphthalene dimethyl chloride/2,7- naphthalene dimethyl chloride additional amount is added in the ratio that the molar ratio of phenolic hydroxyl group and acid chloride group is 1:1
Enter.
The present invention also provides a kind of preparation method of active ester resin, when the structural formula of active ester resin is as shown in formula B, R2
When for dicyclopentadiene phenol structure, the preparation method of the active ester resin includes the following steps:
Phenol, dicyclopentadiene and the first catalyst reaction are obtained into dicyclopentadiene phenolic resin, described bicyclic penta 2
The structural formula of alkene phenolic resin is as shown in formula G:
N is 0~5；
In the dicyclopentadiene phenolic resin being prepared, o-phenyl phenol/p-phenyl phenol, isophthalic two is added
Formyl chloride/paraphthaloyl chloride/o-phthaloyl chloride/1,5- naphthalene dimethyl chloride/1,6- naphthalene dimethyl chloride/two formyl of 1,7- naphthalene
Chlorine/1,8- naphthalene dimethyl chloride/2,6- naphthalene dimethyl chloride/2,7- naphthalene dimethyl chloride, acid binding agent are reacted, and active ester tree is obtained
Rouge.
Specifically, the hydroxyl equivalent of the dicyclopentadiene phenolic resin is 180g/eq~210g/eq, such as can be
180g/eq, 185g/eq, 190g/eq, 195g/eq, 200g/eq, 205g/eq, 210g/eq etc..
Specifically, the softening point of the dicyclopentadiene phenolic resin be 105 DEG C~120 DEG C, such as can be 105 DEG C,
110 DEG C, 115 DEG C, 120 DEG C etc..
Specifically, the molar ratio of the dicyclopentadiene and phenol that are added is (3~5): 1, such as can be 3:1,4:1,5:1
Deng.
Specifically, first catalyst include boron trifluoride ether at least one of benzyl sulfonic acid.
Specifically, the reaction temperature of the phenol, dicyclopentadiene and the first catalyst reaction is 110 DEG C~120 DEG C, example
It such as can be 110 DEG C, 115 DEG C, 120 DEG C.
Specifically, the dicyclopentadiene phenolic resin, o-phenyl phenol/p-phenyl phenol, m-phthaloyl chloride/to benzene
Dimethyl chloride/o-phthaloyl chloride/1,5- naphthalene dimethyl chloride/1,6- naphthalene dimethyl chloride/1,7- naphthalene dimethyl chloride/1,8- naphthalene diformazan
The ratio that acyl chlorides/2,6- naphthalene dimethyl chloride/2,7- naphthalene dimethyl chloride additional amount is 1:1 in the molar ratio of phenolic hydroxyl group and acid chloride group
It is added.
The present invention also provides a kind of preparation method of active ester resin, when the structural formula of active ester resin is as shown in formula B, R2
When for any in ortho position xenyl and para-biphenyl base, the preparation method of the active ester resin includes the following steps:
In 2,2'- dihydroxybiphenyl or 4,4'- dihydroxybiphenyl, o-phenyl phenol/p-phenyl phenol/1- naphthalene is added
Phenol, m-phthaloyl chloride/paraphthaloyl chloride/o-phthaloyl chloride/1,5- naphthalene dimethyl chloride/1,6- naphthalene dimethyl chloride/1,7-
Naphthalene dimethyl chloride/1,8- naphthalene dimethyl chloride/2,6- naphthalene dimethyl chloride/2,7- naphthalene dimethyl chloride, acid binding agent are reacted, and are lived
Property ester resin；
The structural formula of the 2,2'- dihydroxybiphenyl is as shown in formula H:
The structural formula of the 4,4' dihydroxy diphenyl is shown in formula I:
Specifically, 2,2'- dihydroxybiphenyl/4,4'- dihydroxybiphenyl, o-phenyl phenol/p-phenyl phenol/1- naphthalene
Phenol, m-phthaloyl chloride/paraphthaloyl chloride/o-phthaloyl chloride/1,5- naphthalene dimethyl chloride/1,6- naphthalene dimethyl chloride/1,7-
Naphthalene dimethyl chloride/1,8- naphthalene dimethyl chloride/2,6- naphthalene dimethyl chloride/2,7- naphthalene dimethyl chloride additional amount presses phenolic hydroxyl group and acyl chlorides
The ratio that the molar ratio of base is 1:1 is added.
Preferably, the acid binding agent includes any one of pyridine and triethylamine, and the acid binding agent can accelerate phenolic hydroxyl group
With the esterification of acid chloride group.
Embodiment of the present invention is described in detail below in conjunction with specific embodiment, but those skilled in the art
It will be understood that the following example is merely to illustrate the present invention, and it is not construed as limiting the scope of the invention.It is not specified in embodiment
Actual conditions person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer,
It is the conventional products that can be obtained by commercially available purchase.
Embodiment 1
The preparation method for present embodiments providing a kind of active ester resin, includes the following steps:
In ready three-necked flask addition 1020g OPP (6mol), 150g formaldehyde (5mol) and 5.85g to benzyl sulphur
Acid is warming up to temperature and stablizes at 95 DEG C, and stirring carries out reaction 4h, is warming up to 120 DEG C later and reacts 4h again after being dehydrated, with
It is dissolved afterwards with 3900g toluene solvant, is subsequently added into 1000ml water stirring 10min, static liquid separation removes water layer, repeats the operation
It is in 6~7 to aqueous pH values, then primary with the washing of 1000ml, obtains solid OPP phenolic resin after finally removing aqueous solvent
(hydroxyl equivalent: 180g/eq).
In ready three-necked flask investment 540g above-mentioned OPP phenolic resin (hydroxyl equivalent are as follows: 180g/eq), 170g
OPP (1mol), 965g toluene and 152g triethylamine (1.5mol), stirring and dissolving at room temperature, and maintain the temperature at 25 DEG C~34 DEG C.
406g m-phthaloyl chloride (acid chloride group molal quantity is 4mol) is dissolved in 609g toluene solvant, it will be molten with 5h~6h
It is instilled in three-necked flask in the m-phthaloyl chloride of toluene solvant, then proceedes to be stirred to react 1h~2h.
After reaction, sodium bicarbonate aqueous solution is added and stirs 10min, then static liquid separation removes water layer, repeats the behaviour
Make to aqueous pH values to be in 6~7, then cleaned twice with 500ml water respectively, the first that mass fraction is 60% is added after decompression dehydration
Benzole soln obtains the active ester resin of structure shown in formula A.
The functional equivalent of above-mentioned active ester resin is 227g/eq according to feed ratio, wherein functional equivalent is according to feeding intake
The meaning of ratio refers to reacted completely according to feed ratio after functional equivalent theoretical value.
Embodiment 2
The preparation method for present embodiments providing a kind of active ester resin, includes the following steps:
After 1974g phenol (21mol) is added in ready three-necked flask, it is warming up to temperature stabilization and is added after 115 DEG C
The boron trifluoride ether solution that 61.7g mass concentration is 47% starts after 5min that 924g DCPD is added dropwise, process used time 4h is added dropwise,
And continue insulated and stirred and carry out reaction 4h, heating later sloughs phenol to after 170 DEG C, continues to keep the temperature de- phenol 1.5h.Then use
5000g toluene solvant dissolution, be subsequently added into 1000ml water stirring 10min, static liquid separation and remove water layer, repeat the operation to water
Phase pH value is in 6~7, then primary with the washing of 1000ml.Solid DCPD phenolic resin (hydroxyl is obtained after finally taking off aqueous solvent
Equivalent: 196g/eq).
The above-mentioned DCPD phenolic resin (hydroxyl equivalent are as follows: 196g/eq) of ready three-necked flask investment 88.2g,
25.5g OPP (0.15mol), 170g toluene and 25.3g triethylamine (0.25mol), stirring and dissolving at room temperature, and maintain the temperature at
25 DEG C~34 DEG C.
60.9g m-phthaloyl chloride (acid chloride group molal quantity is 0.6mol) is dissolved in 92g toluene solvant, it will with 2h~3h
The m-phthaloyl chloride for being dissolved in toluene solvant instills in three-necked flask, then proceedes to be stirred to react 1h~2h.
After reaction, sodium bicarbonate aqueous solution is added and stirs 10min, then static liquid separation removes water layer, repeats the behaviour
Make to aqueous pH values to be in 6~7, then cleaned twice with 200ml water respectively, the first that mass fraction is 60% is added after decompression dehydration
Benzole soln obtains the active ester resin of structure shown in formula B.
The functional equivalent of above-mentioned active ester resin is 254g/eq according to feed ratio.
The GPC spectrogram (gel permeation chromatography spectrogram) for the active ester resin being prepared is referring to FIG. 1, measure active ester tree
The average number-average molecular weight (Mn) of rouge is 910, and average weight-average molecular weight (Mw) is 3630；It can thus be appreciated that DCPD phenolic resin is (flat
Equal number-average molecular weight 663, average weight-average molecular weight 961), OPP and m-phthaloyl chloride be able to carry out chain extending reaction, obtain activity
Ester resin.
Embodiment 3
The preparation method for present embodiments providing a kind of active ester resin, includes the following steps:
After 1974g phenol (21mol) is added in ready three-necked flask, it is warming up to temperature stabilization and is added after 115 DEG C
The boron trifluoride ether solution that 61.7g mass concentration is 47% starts after 5min that 924g DCPD is added dropwise, process used time 4h is added dropwise,
And continue insulated and stirred and carry out reaction 4h, heating later sloughs phenol to after 170 DEG C, continues to keep the temperature de- phenol 1.5h.Then use
5000g toluene solvant dissolution, be subsequently added into 1000ml water stirring 10min, static liquid separation and remove water layer, repeat the operation to water
Phase pH value is in 6~7, then primary with the washing of 1000ml.Solid DCPD phenolic resin (hydroxyl is obtained after finally taking off aqueous solvent
Equivalent: 196g/eq).
In ready three-necked flask investment 88.2g above-mentioned DCPD phenolic resin (hydroxyl equivalent are as follows: 196g/eq), 51g
OPP (0.3mol), 209g hexone (MIBK) and 30.3g triethylamine (0.3mol), stirring and dissolving at room temperature, and protect
Temperature is held at 25 DEG C~34 DEG C.
76.2g m-phthaloyl chloride (acid chloride group molal quantity is 0.75mol) is dissolved in 115g hexone
(MIBK) in solvent, the m-phthaloyl chloride for being dissolved in hexone solvent is instilled in three-necked flask with 2h~3h, so
After continue to be stirred to react 1h~2h.
After reaction, sodium bicarbonate aqueous solution is added and stirs 10min, then static liquid separation removes water layer, repeats the behaviour
Make to aqueous pH values to be in 6~7, then cleaned twice with the water of 200ml respectively, it is 60% that mass fraction is added after decompression dehydration
Hexone (MIBK) solution obtains the active ester resin of structure shown in formula B.
The functional equivalent of above-mentioned active ester resin is 250.7g/eq according to feed ratio.
Embodiment 4
The preparation method for present embodiments providing a kind of active ester resin, includes the following steps:
In ready three-necked flask addition 1020g OPP (6mol), 150g formaldehyde (5mol) and 5.85g to benzyl sulphur
Acid is warming up to temperature and stablizes at 95 DEG C, and stirring carries out reaction 4h, is warming up to 120 DEG C later and reacts 4h again after being dehydrated, with
It is dissolved afterwards with 3900g toluene solvant, is subsequently added into 1000ml water stirring 10min, static liquid separation removes water layer, repeats the operation
It is in 6~7 to aqueous pH values, then primary with the washing of 1000ml, obtains solid OPP phenolic resin after finally removing aqueous solvent
(hydroxyl equivalent: 180g/eq).
The above-mentioned OPP phenolic resin (hydroxyl equivalent are as follows: 180g/eq) of ready three-necked flask investment 86.4g,
40.8g OPP (1mol), 190g toluene and 25.3g triethylamine (1.5mol), stirring and dissolving at room temperature, and maintain the temperature at 25 DEG C
~34 DEG C.
73.1g m-phthaloyl chloride (acid chloride group molal quantity is 0.72mol) is dissolved in 110g toluene solvant, with 2h~3h
The m-phthaloyl chloride for being dissolved in toluene solvant is instilled in three-necked flask, then proceedes to be stirred to react 1h~2h.
After reaction, sodium bicarbonate aqueous solution is added and stirs 10min, then static liquid separation removes water layer, repeats the behaviour
Make to aqueous pH values to be in 6~7, then cleaned twice with 200ml water respectively, the first that mass fraction is 60% is added after decompression dehydration
Benzole soln obtains the active ester resin of structure shown in formula A.
The functional equivalent of above-mentioned active ester resin is 241.7g/eq according to feed ratio.
The GPC spectrogram for the active ester resin being prepared is referring to FIG. 2, measure the average number-average molecular weight of active ester resin
It (Mn) is 953, average weight-average molecular weight (Mw) is 3537；It can thus be appreciated that (average number-average molecular weight 1052, puts down OPP phenolic resin
Equal weight average molecular weight 1052), OPP and m-phthaloyl chloride be able to carry out chain extending reaction, obtain active ester resin.
Embodiment 5
The preparation method for present embodiments providing a kind of active ester resin, includes the following steps:
In ready three-necked flask addition 1020g PPP (6mol), 150g formaldehyde (5mol) and 5.85g to benzyl sulphur
Acid solution is warming up to temperature and stablizes at 95 DEG C, and stirring carries out reaction 4h, is warming up to 120 DEG C later and reacts again after being dehydrated
4h is then dissolved with 3900g toluene solvant, is subsequently added into 1000ml water stirring 10min, and static liquid separation removes water layer, and repeating should
Operation to aqueous pH values are in 6~7, then primary with the washing of 1000ml, obtain solid PPP phenolic aldehyde tree after finally removing aqueous solvent
Rouge (hydroxyl equivalent: 180g/eq).
In ready three-necked flask investment 144g above-mentioned PPP phenolic resin (hydroxyl equivalent are as follows: 180g/eq), 68g
PPP (0.4mol), 636g toluene and 121.2g triethylamine (1.2mol), stirring and dissolving at room temperature, and maintain the temperature at 25 DEG C~
34℃。
121.8g m-phthaloyl chloride (acid chloride group molal quantity is 1.2mol) is dissolved in 365g toluene solvant, with 2h~3h
The m-phthaloyl chloride for being dissolved in toluene solvant is instilled in three-necked flask, then proceedes to be stirred to react 1h~2h.
After reaction, sodium bicarbonate aqueous solution is added and stirs 10min, static liquid separation and water layer of going out repeat the operation
It is in 6~7 to aqueous pH values, then is cleaned twice with the water of 200ml respectively, the first that mass fraction is 60% is added after decompression dehydration
Benzole soln obtains the active ester resin of structure shown in formula A.
The functional equivalent of above-mentioned active ester resin is 241.7g/eq according to feed ratio.
Embodiment 6
The preparation method for present embodiments providing a kind of active ester resin, includes the following steps:
In ready three-necked flask addition 1020g OPP (6mol), 150g formaldehyde (5mol) and 5.85g to benzyl sulphur
Acid solution is warming up to temperature and stablizes at 95 DEG C, and stirring carries out reaction 4h, is warming up to 120 DEG C later and reacts again after being dehydrated
4h is then dissolved with 3900g toluene solvant, is subsequently added into 1000ml water stirring 10min, and static liquid separation removes water layer, and repeating should
Operation to aqueous pH values are in 6~7, then primary with the washing of 1000ml, obtain solid OPP phenolic aldehyde tree after finally removing aqueous solvent
Rouge (hydroxyl equivalent: 180g/eq).
In ready three-necked flask investment 144g above-mentioned OPP phenolic resin (hydroxyl equivalent are as follows: 180g/eq), 57.6g
1- naphthols (0.4mol), 605g toluene and 121.2g triethylamine (1.2mol), stirring and dissolving at room temperature, and maintain the temperature at 25 DEG C
~34 DEG C.
121.8g m-phthaloyl chloride (acid chloride group molal quantity is 1.2mol) is dissolved in 365g toluene solvant, with 2h~3h
The m-phthaloyl chloride for being dissolved in toluene solvant is instilled in three-necked flask, then proceedes to be stirred to react 1h~2h.
After reaction, sodium bicarbonate aqueous solution is added and stirs 10min, static liquid separation and water layer of going out repeat the operation
It is in 6~7 to aqueous pH values, then is cleaned twice with the water of 200ml respectively, the first that mass fraction is 60% is added after decompression dehydration
Benzole soln obtains the active ester resin of structure shown in formula A.
The functional equivalent of above-mentioned active ester resin is 233g/eq according to feed ratio.
The GPC spectrogram for the active ester resin being prepared is referring to FIG. 3, measure the average number-average molecular weight of active ester resin
It (Mn) is 1072, average weight-average molecular weight (Mw) is 5475；It can thus be appreciated that (average number-average molecular weight 1052, puts down OPP phenolic resin
Equal weight average molecular weight 1502), 1- naphthols and m-phthaloyl chloride be able to carry out chain extending reaction, obtain active ester resin.
Embodiment 7
The preparation method for present embodiments providing a kind of active ester resin, includes the following steps:
In ready three-necked flask addition 1020g PPP (6mol), 150g formaldehyde (5mol) and 5.85g to benzyl sulphur
Acid solution is warming up to temperature and stablizes at 95 DEG C, and stirring carries out reaction 4h, is warming up to 120 DEG C later and reacts again after being dehydrated
4h is then dissolved with 3900g toluene solvant, is subsequently added into 1000ml water stirring 10min, and static liquid separation removes water layer, and repeating should
Operation to aqueous pH values are in 6~7, then primary with the washing of 1000ml, obtain solid PPP phenolic aldehyde tree after finally removing aqueous solvent
Rouge (hydroxyl equivalent: 180g/eq).
The above-mentioned PPP phenolic resin (hydroxyl equivalent are as follows: 180g/eq) of ready three-necked flask investment 144g,
57.6g1- naphthols (0.4mol), 605g toluene and 121.2g triethylamine (1.2mol), stirring and dissolving at room temperature, and keep temperature
At 25 DEG C~34 DEG C.
121.8g m-phthaloyl chloride (acid chloride group molal quantity is 1.2mol) is dissolved in 365g toluene solvant, with 2h~3h
The m-phthaloyl chloride for being dissolved in toluene solvant is instilled in three-necked flask, then proceedes to be stirred to react 1h~2h.
After reaction, sodium bicarbonate aqueous solution is added and stirs 10min, static liquid separation and water layer of going out repeat the operation
It is in 6~7 to aqueous pH values, then is cleaned twice with the water of 200ml respectively, the first that mass fraction is 60% is added after decompression dehydration
Benzole soln obtains the active ester resin of structure shown in formula A.
The functional equivalent of above-mentioned active ester resin is 233g/eq according to feed ratio.
Embodiment 8
The preparation method for present embodiments providing a kind of active ester resin, includes the following steps:
After 1974g phenol (21mol) is added in ready three-necked flask, it is warming up to temperature stabilization and is added after 115 DEG C
The boron trifluoride ether solution that 61.7g mass concentration is 47% starts after 5min that 924g DCPD is added dropwise, process used time 4h is added dropwise,
And continue insulated and stirred and carry out reaction 4h, heating later sloughs phenol to after 170 DEG C, continues to keep the temperature de- phenol 1.5h.Then use
5000g toluene solvant dissolution, be subsequently added into 1000ml water stirring 10min, static liquid separation and remove water layer, repeat the operation to water
Phase pH value is in 6~7, then primary with the washing of 1000ml.Solid DCPD phenolic resin (hydroxyl is obtained after finally taking off aqueous solvent
Equivalent: 196g/eq).
The above-mentioned DCPD phenolic resin (hydroxyl equivalent are as follows: 196g/eq) of ready three-necked flask investment 156.8g,
68g PPP (0.15mol), 675g toluene and 121.2g triethylamine (0.25mol), stirring and dissolving at room temperature, and maintain the temperature at
25 DEG C~34 DEG C.
121.8g m-phthaloyl chloride (acid chloride group molal quantity is 0.6mol) is dissolved in 365g toluene solvant, with 2h~3h
The m-phthaloyl chloride for being dissolved in toluene solvant is instilled in three-necked flask, then proceedes to be stirred to react 1h~2h.
After reaction, sodium bicarbonate aqueous solution is added and stirs 10min, then static liquid separation removes water layer, repeats the behaviour
Make to aqueous pH values to be in 6~7, then cleaned twice with 200ml water respectively, the first that mass fraction is 60% is added after decompression dehydration
Benzole soln obtains the active ester resin of structure shown in formula B.
The functional equivalent of above-mentioned active ester resin is 252.3g/eq according to feed ratio.
Embodiment 9
The preparation method for present embodiments providing a kind of active ester resin, includes the following steps:
Ready three-necked flask put into 55.8g 4,4' dihydroxy diphenyl (0.3mol), 102g PPP (0.6mol),
474g toluene and 121.2g triethylamine (1.2mol), stirring and dissolving at room temperature, and maintain the temperature at 25 DEG C~34 DEG C.
121.8g m-phthaloyl chloride (acid chloride group molal quantity is 1.2mol) is dissolved in 365g toluene solvant, with 2h~3h
The m-phthaloyl chloride for being dissolved in toluene solvant is instilled in three-necked flask, then proceedes to be stirred to react 1h~2h.
After reaction, sodium bicarbonate aqueous solution is added and stirs 10min, then static liquid separation removes water layer, repeats the behaviour
Make to aqueous pH values to be in 6~7, then cleaned twice with 200ml water respectively, the first that mass fraction is 60% is added after decompression dehydration
Benzole soln obtains the active ester resin of structure shown in formula B.
The functional equivalent of above-mentioned active ester resin is 196.5g/eq according to feed ratio.
Embodiment 10
The preparation method for present embodiments providing a kind of active ester resin, includes the following steps:
Ready three-necked flask put into 55.8g 4,4' dihydroxy diphenyl (0.3mol), 102g OPP (0.6mol),
474g toluene and 121.2g triethylamine (1.2mol), stirring and dissolving at room temperature, and maintain the temperature at 25 DEG C~34 DEG C.
121.8g m-phthaloyl chloride (acid chloride group molal quantity is 1.2mol) is dissolved in 365g toluene solvant, with 2h~3h
The m-phthaloyl chloride for being dissolved in toluene solvant is instilled in three-necked flask, then proceedes to be stirred to react 1h~2h.
After reaction, sodium bicarbonate aqueous solution is added and stirs 10min, then static liquid separation removes water layer, repeats the behaviour
Make to aqueous pH values to be in 6~7, then cleaned twice with 200ml water respectively, the first that mass fraction is 60% is added after decompression dehydration
Benzole soln obtains the active ester resin of structure shown in formula B.
The functional equivalent of above-mentioned active ester resin is 196.5g/eq according to feed ratio.
Embodiment 11
The preparation method for present embodiments providing a kind of active ester resin, includes the following steps:
55.8g 4,4' dihydroxy diphenyl (0.3mol), 86.4g 1- naphthols are put into ready three-necked flask
(0.6mol), 427g toluene and 121.2g triethylamine (1.2mol), stirring and dissolving at room temperature, and maintain the temperature at 25 DEG C~34
℃。
121.8g m-phthaloyl chloride (acid chloride group molal quantity is 1.2mol) is dissolved in 365g toluene solvant, with 2h~3h
The m-phthaloyl chloride for being dissolved in toluene solvant is instilled in three-necked flask, then proceedes to be stirred to react 1h~2h.
After reaction, sodium bicarbonate aqueous solution is added and stirs 10min, then static liquid separation removes water layer, repeats the behaviour
Make to aqueous pH values to be in 6~7, then cleaned twice with 200ml water respectively, the first that mass fraction is 60% is added after decompression dehydration
Benzole soln obtains the active ester resin of structure shown in formula B.
The functional equivalent of above-mentioned active ester resin is 183.5g/eq according to feed ratio.
Embodiment 12
The preparation method for present embodiments providing a kind of active ester resin, includes the following steps:
55.8g 2,2'- dihydroxybiphenyl (0.3mol), 86.4g 1- naphthols are put into ready three-necked flask
(0.6mol), 427g toluene and 121.2g triethylamine (1.2mol), stirring and dissolving at room temperature, and maintain the temperature at 25 DEG C~34
℃。
121.8g m-phthaloyl chloride (acid chloride group molal quantity is 1.2mol) is dissolved in 365g toluene solvant, with 2h~3h
The m-phthaloyl chloride for being dissolved in toluene solvant is instilled in three-necked flask, then proceedes to be stirred to react 1h~2h.
After reaction, sodium bicarbonate aqueous solution is added and stirs 10min, then static liquid separation removes water layer, repeats the behaviour
Make to aqueous pH values to be in 6~7, then cleaned twice with 200ml water respectively, the first that mass fraction is 60% is added after decompression dehydration
Benzole soln obtains the active ester resin of structure shown in formula B.
The functional equivalent of above-mentioned active ester resin is 183.5g/eq according to feed ratio.
Embodiment 13
The preparation method for present embodiments providing a kind of active ester resin, includes the following steps:
Ready three-necked flask put into 55.8g 2,2'- dihydroxybiphenyl (0.3mol), 102g OPP (0.6mol),
474g toluene and 121.2g triethylamine (1.2mol), stirring and dissolving at room temperature, and maintain the temperature at 25 DEG C~34 DEG C.
121.8g m-phthaloyl chloride (acid chloride group molal quantity is 1.2mol) is dissolved in 365g toluene solvant, with 2h~3h
The m-phthaloyl chloride for being dissolved in toluene solvant is instilled in three-necked flask, then proceedes to be stirred to react 1h~2h.
After reaction, sodium bicarbonate aqueous solution is added and stirs 10min, then static liquid separation removes water layer, repeats the behaviour
Make to aqueous pH values to be in 6~7, then cleaned twice with 200ml water respectively, the first that mass fraction is 60% is added after decompression dehydration
Benzole soln obtains the active ester resin of structure shown in formula B.The functional equivalent of above-mentioned active ester resin is according to feed ratio
196.5g/eq。
Application examples 1
Active ester resin 175.8g, epoxy resin HP-7200H 209.1g, the 4- diformazan provided by embodiment 1 is provided respectively
Aminopyridine (DMAP) 0.77g, is dissolved in butanone solvent, is then uniformly mixed and is adjusted to suitable viscosity formation glue.
The glass cloth that specification is 2116 is infiltrated in above-mentioned glue, is obtained after then carrying out drying removal butanone to glass cloth
To prepreg, 8 layers of prepreg are solidified into 90min through 200 DEG C of pressings, obtain the laminate of thickness 1.0mm, performance is shown in Table
One.
Application examples 2
Active ester resin 142.0g, epoxy resin HP-7200H 154.0g, the 4- diformazan provided by embodiment 2 is provided respectively
Aminopyridine (DMAP) 0.60g, is dissolved in butanone solvent, is then uniformly mixed and is adjusted to suitable viscosity formation glue.
The glass cloth that specification is 2116 is infiltrated in above-mentioned glue, is obtained after then carrying out drying removal butanone to glass cloth
To prepreg, 8 layers of prepreg are solidified into 90min through 200 DEG C of pressings, obtain the laminate of thickness 1.0mm, performance is shown in Table
One.
Application examples 3
Active ester resin 160.0g, epoxy resin HP-7200H 172.0g, the 4- diformazan provided by embodiment 3 is provided respectively
Aminopyridine (DMAP) 0.67g, is dissolved in butanone solvent, is then uniformly mixed and is adjusted to suitable viscosity formation glue.
The glass cloth that specification is 2116 is infiltrated in above-mentioned glue, is obtained after then carrying out drying removal butanone to glass cloth
To prepreg, 8 layers of prepreg are solidified into 90min through 200 DEG C of pressings, obtain the laminate of thickness 1.0mm, performance is shown in Table
One.
Application examples 4
Active ester resin 155.0g, epoxy resin HP-7200H 173.2g, the 4- diformazan provided by embodiment 3 is provided respectively
Aminopyridine (DMAP) 0.67g, is dissolved in butanone solvent, is then uniformly mixed and is adjusted to suitable viscosity formation glue.
The glass cloth that specification is 2116 is infiltrated in above-mentioned glue, is obtained after then carrying out drying removal butanone to glass cloth
To prepreg, 8 layers of prepreg are solidified into 90min through 200 DEG C of pressings, obtain the laminate of thickness 1.0mm, performance is shown in Table
One.
Application examples 5
Active ester resin 200g, epoxy resin HP-7200H 223.4g, 4- the diformazan ammonia provided by embodiment 5 is provided respectively
Yl pyridines (DMAP) 2.12g, is dissolved in butanone solvent, is then uniformly mixed and is adjusted to suitable viscosity formation glue.
The glass cloth that specification is 2116 is infiltrated in above-mentioned glue, is obtained after then carrying out drying removal butanone to glass cloth
To prepreg, 8 layers of prepreg are solidified into 90min through 200 DEG C of pressings, obtain the laminate of thickness 1.0mm, performance is shown in Table
One.
Application examples 6
Active ester resin 200g, epoxy resin HP-7200H 231.8g, 4- the diformazan ammonia provided by embodiment 6 is provided respectively
Yl pyridines (DMAP) 2.16g, is dissolved in butanone solvent, is then uniformly mixed and is adjusted to suitable viscosity formation glue.
The glass cloth that specification is 2116 is infiltrated in above-mentioned glue, is obtained after then carrying out drying removal butanone to glass cloth
To prepreg, 8 layers of prepreg are solidified into 90min through 200 DEG C of pressings, obtain the laminate of thickness 1.0mm, performance is shown in Table
One.
Application examples 7
Active ester resin 200g, epoxy resin HP-7200H 231.8g, 4- the diformazan ammonia provided by embodiment 7 is provided respectively
Yl pyridines (DMAP) 2.16g, is dissolved in butanone solvent, is then uniformly mixed and is adjusted to suitable viscosity formation glue.
The glass cloth that specification is 2116 is infiltrated in above-mentioned glue, is obtained after then carrying out drying removal butanone to glass cloth
To prepreg, 8 layers of prepreg are solidified into 90min through 200 DEG C of pressings, obtain the laminate of thickness 1.0mm, performance is shown in Table
One.
Application examples 8
Active ester resin 200g, epoxy resin HP-7200H 214g, the 4- dimethylamino provided by embodiment 8 is provided respectively
Pyridine (DMAP) 2.07g, is dissolved in butanone solvent, is then uniformly mixed and is adjusted to suitable viscosity formation glue.
The glass cloth that specification is 2116 is infiltrated in above-mentioned glue, is obtained after then carrying out drying removal butanone to glass cloth
To prepreg, 8 layers of prepreg are solidified into 90min through 200 DEG C of pressings, obtain the laminate of thickness 1.0mm, performance is shown in Table
One.
Application examples 9
Active ester resin 150g, epoxy resin HP-7200H 206.1g, 4- the diformazan ammonia provided by embodiment 9 is provided respectively
Yl pyridines (DMAP) 1.78g, is dissolved in butanone solvent, is then uniformly mixed and is adjusted to suitable viscosity formation glue.
The glass cloth that specification is 2116 is infiltrated in above-mentioned glue, is obtained after then carrying out drying removal butanone to glass cloth
To prepreg, 8 layers of prepreg are solidified into 90min through 200 DEG C of pressings, obtain the laminate of thickness 1.0mm, performance is shown in Table
One.
Application examples 10
Active ester resin 150g, epoxy resin HP-7200H 206.1g, 4- the diformazan ammonia provided by embodiment 10 is provided respectively
Yl pyridines (DMAP) 1.78g, is dissolved in butanone solvent, is then uniformly mixed and is adjusted to suitable viscosity formation glue.
The glass cloth that specification is 2116 is infiltrated in above-mentioned glue, is obtained after then carrying out drying removal butanone to glass cloth
To prepreg, 8 layers of prepreg are solidified into 90min through 200 DEG C of pressings, obtain the laminate of thickness 1.0mm, performance is shown in Table
One.
Application examples 11
Active ester resin 150g, epoxy resin HP-7200H 220.7g, 4- the diformazan ammonia provided by embodiment 11 is provided respectively
Yl pyridines (DMAP) 1.86g, is dissolved in butanone solvent, is then uniformly mixed and is adjusted to suitable viscosity formation glue.
The glass cloth that specification is 2116 is infiltrated in above-mentioned glue, is obtained after then carrying out drying removal butanone to glass cloth
To prepreg, 8 layers of prepreg are solidified into 90min through 200 DEG C of pressings, obtain the laminate of thickness 1.0mm, performance is shown in Table
One.
Application examples 12
Active ester resin 150g, epoxy resin HP-7200H 220.7g, 4- the diformazan ammonia provided by embodiment 12 is provided respectively
Yl pyridines (DMAP) 1.86g, is dissolved in butanone solvent, is then uniformly mixed and is adjusted to suitable viscosity formation glue.
The glass cloth that specification is 2116 is infiltrated in above-mentioned glue, is obtained after then carrying out drying removal butanone to glass cloth
To prepreg, 8 layers of prepreg are solidified into 90min through 200 DEG C of pressings, obtain the laminate of thickness 1.0mm, performance is shown in Table
One.
Application examples 13
Active ester resin 150g, epoxy resin HP-7200H 206.1g, 4- the diformazan ammonia provided by embodiment 13 is provided respectively
Yl pyridines (DMAP) 1.78g, is dissolved in butanone solvent, is then uniformly mixed and is adjusted to suitable viscosity formation glue.
The glass cloth that specification is 2116 is infiltrated in above-mentioned glue, is obtained after then carrying out drying removal butanone to glass cloth
To prepreg, 8 layers of prepreg are solidified into 90min through 200 DEG C of pressings, obtain the laminate of thickness 1.0mm, performance is shown in Table
One.
Performance test
The laminate of above application examples 1-13 is tested for the property, test item include glass transition temperature (Tg),
Dielectric constant, dielectric loss angle tangent, testing result are as shown in Table 1；
The detection method of each detection project is as follows:
Glass transition temperature (Tg): according to GB/T19466.2-2004/ISO11357-2:1999, differential scanning is used
Calorimetry (DSC), 10 DEG C/min of heating rate measure the specific heat capacity variation with temperature of laminate, and are determined by resulting curve
Glass transition characteristics temperature.
Dielectric constant and dielectric loss angle tangent: according to JIS-C-6481, Agilent Technologies Inc is used
The Network Analyzer " E8362C " of manufacture, by empty resonance method measurement solidify after 23 DEG C, the interior of humidity 50%
Laminate dielectric constant at 1 GHz and dielectric loss angle tangent after saving 24 hours.
The performance test results of the laminate of one application examples 1-13 of table
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
In addition, it will be appreciated by those of skill in the art that although some embodiments in this include institute in other embodiments
Including certain features rather than other feature, but the combination of the feature of different embodiment means in the scope of the present invention
Within and form different embodiments.For example, in claims above, embodiment claimed it is any it
One can in any combination mode come using.The information disclosed in the background technology section is intended only to deepen to the present invention
General background technology understanding, and be not construed as recognizing or imply that information composition has been this field skill in any form
The prior art well known to art personnel.
Claims (10)
1. a kind of active ester resin, which is characterized in that including as in resin shown in formula A and the resin as shown in formula B at least
It is a kind of；Wherein, structural formula shown in formula A are as follows:
Wherein, Ar is any one of ortho position xenyl, para-biphenyl base and 1- naphthalene；Ph is phenyl ring and any in naphthalene nucleus
Kind；R is any one of ortho position xenyl, para-biphenyl base；
X is methylene；N is 0~20；
Structural formula shown in formula B are as follows:
Wherein, R1For any one of ortho position xenyl, para-biphenyl base and 1- naphthalene；Ph is phenyl ring or naphthalene nucleus；
Work as R1When for any in ortho position xenyl, para-biphenyl base, R2For ortho position xenyl, para-biphenyl base and bicyclic penta
Any one of diene phenol structure；Work as R1When for 1- naphthalene, R2For any one of ortho position xenyl and para-biphenyl base；
N is 0~20.
2. a kind of resin combination, which is characterized in that including active ester resin as described in claim 1 and epoxy resin, institute
The ester functional groups' equivalent proportion for stating active ester resin and the epoxy resin is (1~1.5): 1.
3. a kind of prepreg, which is characterized in that described including resin combination as claimed in claim 2 and reinforcing material
Glue is made in the dissolution of resin combination solvent, and then the reinforcing material is immersed in the glue, is formed after heat treatment
The prepreg.
4. a kind of laminate, which is characterized in that the solidfied material including prepreg as claimed in claim 3.
5. a kind of printed circuit board, which is characterized in that the solidfied material including prepreg as claimed in claim 3.
6. a kind of preparation method of active ester resin as described in claim 1, which is characterized in that when the structure of active ester resin
As shown in formula A, the preparation method of the active ester resin includes the following steps: formula
It reacts o-phenyl phenol/p-phenyl phenol/2,2'- dihydroxybiphenyl/4,4' dihydroxy diphenyl to obtain adjacent benzene with formaldehyde
Base phenol novolacs/p-phenyl phenol phenolic resin/2,2'- dihydroxybiphenyl phenolic resin/4,4' dihydroxy diphenyl phenolic aldehyde
Resin；
The structural formula of the o-phenyl phenol phenolic resin is as shown in formula C:
N is 0~5；
The structural formula of the p-phenyl phenol phenolic resin is as shown in formula D:
N is 0~5；
The structural formula of the 4,4' dihydroxy diphenyl phenolic resin is as shown in formula E:
N is 0~5；
The structural formula of the 2,2'- dihydroxybiphenyl phenolic resin is as shown in formula F:
N is 0~5；
The o-phenyl phenol phenolic resin/p-phenyl phenol the phenolic resin being prepared/2,2'- dihydroxybiphenyl phenolic aldehyde tree
In rouge/4,4'- dihydroxybiphenyl phenolic resin, o-phenyl phenol/p-phenyl phenol/1- naphthols, m-phthaloyl chloride/right is added
Phthalyl chloride/o-phthaloyl chloride/1,5- naphthalene dimethyl chloride/1,6- naphthalene dimethyl chloride/1,7- naphthalene dimethyl chloride/1,8- naphthalene two
Formyl chloride/2,6- naphthalene dimethyl chloride/2,7- naphthalene dimethyl chloride, acid binding agent are reacted, and active ester resin is obtained；
Alternatively, when the structural formula of active ester resin is as shown in formula B, R2When for dicyclopentadiene phenol structure, the active ester resin
Preparation method include the following steps:
Phenol, dicyclopentadiene and the first catalyst reaction are obtained into dicyclopentadiene phenolic resin, the dicyclopentadiene phenol
The structural formula of urea formaldehyde is as shown in formula G:
N is 0~5；
In the dicyclopentadiene phenolic resin being prepared, o-phenyl phenol/p-phenyl phenol, phenyl-diformyl is added
Chlorine/paraphthaloyl chloride/o-phthaloyl chloride/1,5- naphthalene dimethyl chloride/1,6- naphthalene dimethyl chloride/1,7- naphthalene dimethyl chloride/1,
8- naphthalene dimethyl chloride/2,6- naphthalene dimethyl chloride/2,7- naphthalene dimethyl chloride, acid binding agent are reacted, and active ester resin is obtained；
Alternatively, when the structural formula of active ester resin is formula B, R2When for any in ortho position xenyl and para-biphenyl base, institute
The preparation method for stating active ester resin includes the following steps:
In 2,2'- dihydroxybiphenyl or 4,4'- dihydroxybiphenyl, addition o-phenyl phenol/p-phenyl phenol/1- naphthols,
M-phthaloyl chloride/paraphthaloyl chloride/o-phthaloyl chloride/1,5- naphthalene dimethyl chloride/1,6- naphthalene dimethyl chloride/1,7- naphthalene two
Formyl chloride/1,8- naphthalene dimethyl chloride/2,6- naphthalene dimethyl chloride/2,7- naphthalene dimethyl chloride, acid binding agent are reacted, and active ester is obtained
Resin.
7. the preparation method of active ester resin as claimed in claim 6, which is characterized in that the o-phenyl phenol phenolic resin
Hydroxyl equivalent be 175g/eq~190g/eq；The hydroxyl equivalent of the p-phenyl phenol phenolic resin is 175g/eq~190g/
eq；The hydroxyl equivalent of the 2,2'- dihydroxybiphenyl phenolic resin is 96.5g/eq~115g/eq；The 4,4'- dihydroxy connection
The hydroxyl equivalent of phenol aldehyde resin is 96.5g/eq~115g/eq；The hydroxyl equivalent of the dicyclopentadiene phenolic resin is
180g/eq~210g/eq.
8. the preparation method of active ester resin as claimed in claim 6, which is characterized in that in o-phenyl phenol/to phenyl benzene
In the reacting of phenol/2,2'- dihydroxybiphenyl/4,4'- dihydroxybiphenyl and formaldehyde, o-phenyl phenol/p-phenyl phenol of addition/
The molar ratio of 2,2'- dihydroxybiphenyl/4,4' dihydroxy diphenyl and formaldehyde is (1~2): 1；
It preferably, further include that the second catalyst is added in the reaction system；
Preferably, second catalyst is acidic catalyst；
Preferably, reaction temperature is 90 DEG C~130 DEG C.
9. the preparation method of active ester resin as claimed in claim 6, which is characterized in that in phenol, dicyclopentadiene and
In the reaction of one catalyst, the dicyclopentadiene of addition and the molar ratio of phenol are (3~5): 1；
Preferably, first catalyst include boron trifluoride ether at least one of benzyl sulfonic acid；
Preferably, reaction temperature is 110 DEG C~120 DEG C.
10. the preparation method of active ester resin as claimed in claim 6, which is characterized in that the o-phenyl phenol phenolic aldehyde tree
Rouge/p-phenyl phenol phenolic resin/2,2'- dihydroxybiphenyl phenolic resin/4,4' dihydroxy diphenyl phenolic resin, adjacent phenyl
Phenol/p-phenyl phenol/1- naphthols, m-phthaloyl chloride/paraphthaloyl chloride/o-phthaloyl chloride/1,5- naphthalene dimethyl chloride/
1,6- naphthalene dimethyl chloride/1,7- naphthalene dimethyl chloride/1,8- naphthalene dimethyl chloride/2,6- naphthalene dimethyl chloride/2,7- naphthalene dimethyl chloride
Additional amount is added in the ratio that the molar ratio of phenolic hydroxyl group and acid chloride group is 1:1；
The dicyclopentadiene phenolic resin, o-phenyl phenol/p-phenyl phenol, m-phthaloyl chloride/paraphthaloyl chloride/neighbour
Phthalyl chloride/1,5- naphthalene dimethyl chloride/1,6- naphthalene dimethyl chloride/1,7- naphthalene dimethyl chloride/1,8- naphthalene dimethyl chloride/2,6- naphthalene
Dimethyl chloride/2,7- naphthalene dimethyl chloride additional amount is added in the ratio that the molar ratio of phenolic hydroxyl group and acid chloride group is 1:1；
2,2'- dihydroxybiphenyl/the 4,4' dihydroxy diphenyl, o-phenyl phenol/p-phenyl phenol/1- naphthols, isophthalic diformazan
Acyl chlorides/paraphthaloyl chloride/o-phthaloyl chloride/1,5- naphthalene dimethyl chloride/1,6- naphthalene dimethyl chloride/1,7- naphthalene dimethyl chloride/
1,8- naphthalene dimethyl chloride/2,6- naphthalene dimethyl chloride/2,7- naphthalene dimethyl chloride additional amount presses the molar ratio of phenolic hydroxyl group and acid chloride group
It is added for the ratio of 1:1.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113999191A (en) * | 2021-11-25 | 2022-02-01 | 大连理工大学 | Novel bio-based epoxy resin containing active ester side group and preparation method thereof |
| JP7615933B2 (en) | 2021-07-09 | 2025-01-17 | 味の素株式会社 | Resin composition |
| JP7625816B2 (en) | 2020-10-01 | 2025-02-04 | Dic株式会社 | Reactive liquid crystal polyester, polyester composition, polyester solution, and cured product |
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| JP2002012650A (en) * | 2000-06-30 | 2002-01-15 | Dainippon Ink & Chem Inc | Epoxy resin composition for low dielectric materials |
| CN102227415A (en) * | 2008-09-29 | 2011-10-26 | 沙伯基础创新塑料知识产权有限公司 | Catalytic method for producing phenolphthalein compounds |
| CN102985485A (en) * | 2010-07-02 | 2013-03-20 | Dic株式会社 | Thermosetting resin composition, cured product thereof, active ester resin, semiconductor sealing material, prepreg, printed circuit board, and build-up film |
| CN109651763A (en) * | 2018-12-25 | 2019-04-19 | 广东生益科技股份有限公司 | A kind of compositions of thermosetting resin and prepreg, laminate and metal-clad laminate using it |
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Patent Citations (4)
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| JP2002012650A (en) * | 2000-06-30 | 2002-01-15 | Dainippon Ink & Chem Inc | Epoxy resin composition for low dielectric materials |
| CN102227415A (en) * | 2008-09-29 | 2011-10-26 | 沙伯基础创新塑料知识产权有限公司 | Catalytic method for producing phenolphthalein compounds |
| CN102985485A (en) * | 2010-07-02 | 2013-03-20 | Dic株式会社 | Thermosetting resin composition, cured product thereof, active ester resin, semiconductor sealing material, prepreg, printed circuit board, and build-up film |
| CN109651763A (en) * | 2018-12-25 | 2019-04-19 | 广东生益科技股份有限公司 | A kind of compositions of thermosetting resin and prepreg, laminate and metal-clad laminate using it |
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| JP7625816B2 (en) | 2020-10-01 | 2025-02-04 | Dic株式会社 | Reactive liquid crystal polyester, polyester composition, polyester solution, and cured product |
| JP7615933B2 (en) | 2021-07-09 | 2025-01-17 | 味の素株式会社 | Resin composition |
| CN113999191A (en) * | 2021-11-25 | 2022-02-01 | 大连理工大学 | Novel bio-based epoxy resin containing active ester side group and preparation method thereof |
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