CN107540816B - Preparation and application of epoxy resin copolymer of dicyclopentadiene-phenol and 2,6-dimethylphenol - Google Patents
Preparation and application of epoxy resin copolymer of dicyclopentadiene-phenol and 2,6-dimethylphenol Download PDFInfo
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- CN107540816B CN107540816B CN201610464112.1A CN201610464112A CN107540816B CN 107540816 B CN107540816 B CN 107540816B CN 201610464112 A CN201610464112 A CN 201610464112A CN 107540816 B CN107540816 B CN 107540816B
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- Prior art keywords
- resin
- phenol
- dicyclopentadiene
- dimethylphenol
- epoxy resin
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- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 title claims abstract description 201
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 84
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 105
- 239000005011 phenolic resin Substances 0.000 claims abstract description 93
- 229920001577 copolymer Polymers 0.000 claims abstract description 79
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 35
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 33
- -1 aldehyde compound Chemical class 0.000 claims abstract description 32
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 239000003365 glass fiber Substances 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 230000002378 acidificating effect Effects 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 4
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims abstract description 3
- 125000004464 hydroxyphenyl group Chemical group 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 52
- 229920005989 resin Polymers 0.000 claims description 41
- 239000011347 resin Substances 0.000 claims description 41
- 239000002904 solvent Substances 0.000 claims description 33
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 25
- 239000004843 novolac epoxy resin Substances 0.000 claims description 20
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical group COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 19
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 16
- 239000002966 varnish Substances 0.000 claims description 16
- 239000004848 polyfunctional curative Substances 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- 238000009835 boiling Methods 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 238000003786 synthesis reaction Methods 0.000 claims description 10
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 10
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 claims description 9
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 9
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 9
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 9
- 229920001955 polyphenylene ether Polymers 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 238000007670 refining Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 7
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 7
- 238000006735 epoxidation reaction Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000003063 flame retardant Substances 0.000 claims 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 claims description 5
- 229920000147 Styrene maleic anhydride Polymers 0.000 claims description 5
- 230000001588 bifunctional effect Effects 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003377 acid catalyst Substances 0.000 claims description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- 229920003986 novolac Polymers 0.000 claims description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims description 4
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 claims description 3
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 claims description 3
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 3
- 238000007259 addition reaction Methods 0.000 claims description 3
- UFZOLVFGAOAEHD-UHFFFAOYSA-N benzaldehyde;phenol Chemical compound OC1=CC=CC=C1.O=CC1=CC=CC=C1 UFZOLVFGAOAEHD-UHFFFAOYSA-N 0.000 claims description 3
- 239000006184 cosolvent Substances 0.000 claims description 3
- 238000010612 desalination reaction Methods 0.000 claims description 3
- 229940015043 glyoxal Drugs 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- ABFQGXBZQWZNKI-UHFFFAOYSA-N 1,1-dimethoxyethanol Chemical compound COC(C)(O)OC ABFQGXBZQWZNKI-UHFFFAOYSA-N 0.000 claims description 2
- LJBWJFWNFUKAGS-UHFFFAOYSA-N 2-[bis(2-hydroxyphenyl)methyl]phenol Chemical compound OC1=CC=CC=C1C(C=1C(=CC=CC=1)O)C1=CC=CC=C1O LJBWJFWNFUKAGS-UHFFFAOYSA-N 0.000 claims description 2
- HZEOUPCNUWSUFL-UHFFFAOYSA-N 4,5,5-trimethyl-4-pentan-3-yl-1H-imidazole Chemical compound C(C)C(C1(N=CNC1(C)C)C)CC HZEOUPCNUWSUFL-UHFFFAOYSA-N 0.000 claims description 2
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims description 2
- CPHGOBGXZQKCKI-UHFFFAOYSA-N 4,5-diphenyl-1h-imidazole Chemical compound N1C=NC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 CPHGOBGXZQKCKI-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 238000004807 desolvation Methods 0.000 claims description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims 3
- 125000002619 bicyclic group Chemical group 0.000 claims 1
- 230000035800 maturation Effects 0.000 claims 1
- XZVCKKPHOJCWME-UHFFFAOYSA-N penta-1,3-diene phenol Chemical compound CC=CC=C.Oc1ccccc1 XZVCKKPHOJCWME-UHFFFAOYSA-N 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract 2
- 229910000679 solder Inorganic materials 0.000 abstract 1
- 235000013824 polyphenols Nutrition 0.000 description 24
- 238000012360 testing method Methods 0.000 description 18
- 238000003756 stirring Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical group C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 125000000524 functional group Chemical group 0.000 description 8
- 238000005191 phase separation Methods 0.000 description 8
- 238000006297 dehydration reaction Methods 0.000 description 7
- 230000009477 glass transition Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 230000018044 dehydration Effects 0.000 description 6
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 239000011889 copper foil Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 238000010998 test method Methods 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 4
- 239000012267 brine Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- LLJVQTJFFWIRJN-UHFFFAOYSA-N 2,6-dimethylphenol;formaldehyde Chemical compound O=C.CC1=CC=CC(C)=C1O LLJVQTJFFWIRJN-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 230000000930 thermomechanical effect Effects 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229920006026 co-polymeric resin Polymers 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000008098 formaldehyde solution Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 235000019799 monosodium phosphate Nutrition 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- JYIZNFVTKLARKT-UHFFFAOYSA-N phenol;1,3,5-triazine-2,4,6-triamine Chemical compound OC1=CC=CC=C1.NC1=NC(N)=NC(N)=N1 JYIZNFVTKLARKT-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 description 2
- 238000013517 stratification Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- JIDWXFRXHGRFGY-UHFFFAOYSA-N 2,6-dimethylidenecyclohex-3-en-1-ol Chemical compound OC1C(=C)CC=CC1=C JIDWXFRXHGRFGY-UHFFFAOYSA-N 0.000 description 1
- VJXIZXJHJXDYGJ-UHFFFAOYSA-N 2,6-dimethylphenol;phenol Chemical compound OC1=CC=CC=C1.CC1=CC=CC(C)=C1O VJXIZXJHJXDYGJ-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- BULOCEWDRJUMEL-UHFFFAOYSA-N benzene formaldehyde Chemical compound C=O.C1=CC=CC=C1.C=O BULOCEWDRJUMEL-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- XYHUIOCRXXWEAX-UHFFFAOYSA-N cyclopenta-1,3-diene;phenol Chemical compound C1C=CC=C1.OC1=CC=CC=C1 XYHUIOCRXXWEAX-UHFFFAOYSA-N 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000013022 formulation composition Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
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- Epoxy Resins (AREA)
Abstract
本发明提供一种具有优异耐热性与低介电常数Dk、低损耗因子Df的新型二环戊二烯‑酚与2,6‑二甲基苯酚的共聚物环氧树脂(分子结构见式1)，其制备分两步骤，步骤一：由(a1)二环戊二烯‑酚树脂(式2)与(a2)2,6‑二甲基苯酚，于酸性催化剂存在下通过(a3)醛类化合物反应形成二环戊二烯‑酚与2,6‑二甲基苯酚的共聚物酚醛树脂，步骤二：将该共聚物酚醛树脂与过量环氧氯丙烷于NaOH条件下制备二环戊二烯‑酚与2,6‑二甲基苯酚的共聚物环氧树脂，将本发明的共聚物环氧树脂代入玻纤层合板配方组合物，经压力锅PCT 2hr吸水后，288℃浸焊锡耐热性10分钟以上不爆板。其中x为0～5整数，y为0～5整数；R代表：氢，C1～C10烷基，苯基，羟苯基等。
Description
技术领域technical field
本发明涉及二环戊二烯-酚与2,6-二甲基苯酚的共聚物环氧树脂及其制备方法，并将此二环戊二烯-酚与2,6-二甲基苯酚的共聚物环氧树脂代入玻纤层合板配方组成物，其硬化物呈现良好耐热性、高玻璃转移温度Tg、低介电常数Dk及低损耗因子Df，适用于高性能印刷电路板、半导体封装材料等高信赖性要求电子组件的绝缘材料。The invention relates to a copolymer epoxy resin of dicyclopentadiene-phenol and 2,6-dimethylphenol and a preparation method thereof. Copolymer epoxy resin is substituted into the formulation composition of glass fiber laminate, and its hardened product exhibits good heat resistance, high glass transition temperature Tg, low dielectric constant Dk and low loss factor Df, suitable for high-performance printed circuit boards, semiconductor packaging High reliability such as materials requires insulating materials for electronic components.
背景技术Background technique
在专利TW216439说明二环戊二烯-酚环氧树脂(Dicyclopentadiene-phenolepoxyresin)，是一种特殊骨架构造环氧树脂，结构中含有脂环族六元环，五元环与芳香族苯环，含有二环戊二烯结构而具优异耐热性，低极性，与硬化剂硬化产物具有低吸水性，优异电性质(低介电常数Dk，低损耗因子Df)，且二环戊二烯的结构具有减低固化物内应力的功能，优良机械特性，因此二环戊二烯-酚环氧树脂一直为玻纤层合板与印刷电路板业界所使用，并将二环戊二烯-酚树脂的酚羟基(phenolic OH group)进一步反应延伸合成为苯并噁嗪树脂(Benzoxazine)、活性酯树脂(active ester)、苯烯基结构等高性能树脂具有极佳的电性质，更低介电常数与损耗因子，以符合高频、高速电子产品趋势要求。但长期以来我们对二环戊二烯-酚环氧树脂的电性质研究其对于介电常数Dk降低效果较佳而对损耗因子Df降低效果较小。In patent TW216439, Dicyclopentadiene-phenol epoxy resin (Dicyclopentadiene-phenolepoxyresin) is described, which is a special skeleton structure epoxy resin. The structure contains alicyclic six-membered ring, five-membered ring and aromatic benzene ring, containing Dicyclopentadiene structure and excellent heat resistance, low polarity, low water absorption with hardener hardening products, excellent electrical properties (low dielectric constant Dk, low dissipation factor Df), and dicyclopentadiene The structure has the function of reducing the internal stress of the cured product and has excellent mechanical properties. Therefore, dicyclopentadiene-phenol epoxy resin has always been used in the glass fiber laminate and printed circuit board industry. The phenolic OH group is further reacted and extended to synthesize high-performance resins such as Benzoxazine, active ester, phenylene structure, etc. It has excellent electrical properties, lower dielectric constant and Loss factor to comply with high frequency, high speed electronics trends. However, for a long time, we have studied the electrical properties of dicyclopentadiene-phenol epoxy resin, which has a better effect on reducing the dielectric constant Dk and a lesser effect on reducing the dissipation factor Df.
在专利TW201038151揭露2,6-二甲基苯酚与醛类，于酸性催化剂下反应合成双官能2,6-二甲基苯酚醛树脂，此双官能2,6-二甲基苯酚醛树脂与环氧氯丙烷(epichlorhydrion，ECH)在氢氧化钠NaOH存在下合成双官能2,6-二甲基苯酚醛环氧树脂，2,6-二甲基苯酚醛树脂因具有高度对称性化学结构，低分子偶极距的特性，可有效降低介电常数(Dk)与损号因子(Df)，2,6-二甲基苯酚亦是合成低介电常数(Dk)与低损耗因子(Df)材料-聚苯醚树脂(PPE)的原料，聚苯醚PPE材料具极低损耗因子(Df)特色，损耗因子愈小，代表讯号传输损失愈小，而前述专利TW201038151中合成的双官能2,6-二甲基苯酚醛环氧树脂虽可有效降低介电常数(Dk)与损号因子(Df)，但双官能2,6-二甲基苯酚醛环氧树脂结构硬化物，其架桥密度较低，玻璃转移温度Tg较低与耐热性较差。Patent TW201038151 discloses that 2,6-dimethylphenol and aldehydes are reacted under acidic catalyst to synthesize bifunctional 2,6-dimethylphenol novolac resin. Oxychloropropane (epichlorhydrion, ECH) in the presence of sodium hydroxide NaOH synthesis of bifunctional 2,6-dimethylphenol novolac epoxy resin, 2,6-dimethylphenol novolac resin has a highly symmetrical chemical structure, low The characteristics of molecular dipole moment can effectively reduce the dielectric constant (Dk) and loss factor (Df), 2,6-dimethylphenol is also a low dielectric constant (Dk) and low loss factor (Df) material. - The raw material of polyphenylene ether resin (PPE). The polyphenylene ether PPE material has the characteristics of extremely low loss factor (Df). The smaller the loss factor, the smaller the signal transmission loss. -Although dimethylphenol novolac epoxy resin can effectively reduce the dielectric constant (Dk) and loss factor (Df), the bridging density of the bifunctional 2,6-dimethylphenol novolac epoxy resin structure hardened product lower, the glass transition temperature Tg is lower and the heat resistance is lower.
为满足电子通讯产品的高速传输，电子设备的讯号高速化、高频化是刻不容缓持续发展趋势，亦然电子零件朝轻、薄、短、小化，提供一种可兼具低的介电常数(Dk)、低损耗因子(Df)与要求极高耐热性、高玻璃转移温度Tg的树脂是印刷电路板业界所期盼课题。In order to meet the high-speed transmission of electronic communication products, the high-speed and high-frequency signals of electronic equipment are an urgent and sustainable development trend. Also, electronic components are becoming lighter, thinner, shorter, and smaller, providing a low dielectric constant. (Dk), low dissipation factor (Df), and resins that require extremely high heat resistance and high glass transition temperature Tg are the issues expected by the printed circuit board industry.
发明内容SUMMARY OF THE INVENTION
因此为解决上述课题，本发明在于提供一种二环戊二烯-酚树脂与2,6-二甲基苯酚共聚物环氧树脂，此共聚物环氧树脂不仅兼具二环戊二烯酚环氧树脂与2,6-二甲基苯酚醛环氧树脂此两种树脂的优异电性质(低介电常数Dk、低损耗因子Df)且耐热性较前述两者树脂更佳，由于兼具二环戊二烯酚环氧树脂与2,6-二甲基苯酚醛环氧树脂此两种树脂的优异电性质，特别具有2,6-二甲基苯酚醛环氧树脂的低损耗因子Df性质，本发明二环戊二烯-酚树脂与2,6-二甲基苯酚共聚物环氧树脂其电性质较二环戊二烯-酚环氧树脂更优异，并且此共聚物系将二环戊二烯-酚树脂与2,6-二甲基苯酚醛树脂两者反应加成连结在一起并与环氧氯丙烷反应形成二环戊二烯-酚树脂与2,6-二甲基苯酚醛树脂共聚物环氧树脂，较二环戊二烯-酚环氧树脂与2,6-二甲基苯酚醛环氧树脂具有更高官能团数的反应环氧基团，硬化架桥密度更高，耐热性质与机械性质更加提升，此新颖环氧树脂代入玻纤层合板配方，其硬化物亦具有低介电常数(Dk)、低损耗因子(Df)，优良机械性能，高玻璃转移温度Tg，同时兼备优良耐热性的热硬化性树脂组成硬化物，适合应用于铜箔玻纤层合板、印刷电路板、半导体封装材料，满足电子通讯产品的高速传输，电子设备的讯号高速化、高频化的需求。Therefore, in order to solve the above-mentioned problems, the present invention is to provide a copolymer epoxy resin of dicyclopentadiene-phenol resin and 2,6-dimethylphenol, and the copolymer epoxy resin not only has dicyclopentadienol The excellent electrical properties (low dielectric constant Dk, low dissipation factor Df) and heat resistance of epoxy resin and 2,6-dimethylphenol novolac epoxy resin are better than those of the aforementioned two resins. It has the excellent electrical properties of dicyclopentadienol epoxy resin and 2,6-dimethylphenol novolac epoxy resin, especially the low dissipation factor of 2,6-dimethylphenol novolac epoxy resin Df property, the dicyclopentadiene-phenol resin and 2,6-dimethylphenol copolymer epoxy resin of the present invention has better electrical properties than the dicyclopentadiene-phenol epoxy resin, and the copolymer will be Dicyclopentadiene-phenol resin and 2,6-dimethylphenol-formaldehyde resin react and join together and react with epichlorohydrin to form dicyclopentadiene-phenol resin and 2,6-dimethylphenol Phenol-based phenolic resin copolymer epoxy resin, which has a higher number of reactive epoxy groups than dicyclopentadiene-phenol epoxy resin and 2,6-dimethylphenol novolac epoxy resin, hardening bridging density Higher, the heat resistance and mechanical properties are further improved. This novel epoxy resin is substituted into the glass fiber laminate formulation, and its hardened product also has low dielectric constant (Dk), low loss factor (Df), excellent mechanical properties, high glass Transition temperature Tg, thermosetting resin with excellent heat resistance at the same time to form a cured product, suitable for copper foil glass fiber laminates, printed circuit boards, semiconductor packaging materials, to meet the high-speed transmission of electronic communication products, high-speed signal of electronic equipment demand for high frequency and high frequency.
制备本发明二环戊二烯-酚树脂与2,6-二甲基苯酚的共聚物环氧树脂的方法是以具有低介电常数(Dk)、低损耗因子(Df)的二环戊二烯-酚树脂与2,6-二甲基苯酚在酸性催化剂存在下与醛化合物进行缩合反应，得到更高平均官能团数(6～12)的二环戊二烯-酚树脂与2,6-二甲基苯酚的共聚物酚醛树脂，并将此二环戊二烯-酚树脂与2,6-二甲基苯酚的共聚物酚醛树脂与过量环氧氯丙烷于NaOH条件下合成二环戊二烯-酚树脂与2,6-二甲基苯酚共聚物环氧树脂，此二环戊二烯-酚树脂与2,6-二甲基苯酚的共聚物环氧树脂，与常用环氧树脂硬化剂如双氰胺Dicy、酚醛树脂PN硬化剂，苯乙烯-马来酸酐共聚物SMA，苯并嗪树脂(Benzoxazine)，聚苯醚树脂(PPE)，活性酯树脂(active ester)所得环氧树脂硬化物具有低介电常数(Dk)，低损耗因子(Df)并兼备优良耐热性与高Tg。The method for preparing the copolymer epoxy resin of dicyclopentadiene-phenol resin and 2,6-dimethylphenol of the present invention is to use dicyclopentadiene with low dielectric constant (Dk) and low dissipation factor (Df) The condensation reaction of ene-phenol resin and 2,6-dimethylphenol with aldehyde compound in the presence of acid catalyst to obtain dicyclopentadiene-phenol resin with higher average number of functional groups (6-12) and 2,6- The copolymer phenolic resin of dimethylphenol, and the copolymer phenolic resin of dicyclopentadiene-phenol resin and 2,6-dimethylphenol and excess epichlorohydrin were used to synthesize dicyclopentadiene under the condition of NaOH Dicyclopentadiene-phenol resin and 2,6-dimethylphenol copolymer epoxy resin, this copolymer epoxy resin of dicyclopentadiene-phenol resin and 2,6-dimethylphenol, hardened with common epoxy Agents such as dicyandiamide Dicy, phenolic resin PN hardener, styrene-maleic anhydride copolymer SMA, Benzoxazine resin (Benzoxazine), polyphenylene ether resin (PPE), epoxy resin obtained from active ester resin (active ester) The hardened product has low dielectric constant (Dk), low dissipation factor (Df), excellent heat resistance and high Tg.
本发明关于一种新颖二环戊二烯-酚树脂与2,6-二甲基苯酚的共聚物环氧树脂，分子结构如下列结构式1：The present invention relates to a novel copolymer epoxy resin of dicyclopentadiene-phenol resin and 2,6-dimethylphenol, and the molecular structure is shown in the following structural formula 1:
式1Formula 1
其中X为0～5整数，Y为0～5整数；where X is an integer from 0 to 5, and Y is an integer from 0 to 5;
R代表：氢，C1～C10烷基，苯基，羟苯基等。R represents: hydrogen, C1-C10 alkyl, phenyl, hydroxyphenyl, etc.
此新型二环戊二烯-酚与2,6-二甲基苯酚的共聚物环氧树脂的制备分两步骤，步骤一：由(a1)二环戊二烯-酚树脂(如下式2)与(a2)2,6-二甲基苯酚，于酸性催化剂存在下通过(a3)醛类化合物反应形成二环戊二烯-酚树脂与2,6-二甲基苯酚的共聚物酚醛树脂；The preparation of the novel copolymer epoxy resin of dicyclopentadiene-phenol and 2,6-dimethylphenol is divided into two steps. Step 1: from (a1) dicyclopentadiene-phenol resin (the following formula 2) With (a2) 2,6-dimethylphenol, in the presence of an acidic catalyst, through (a3) aldehyde compound reaction to form a copolymer phenolic resin of dicyclopentadiene-phenol resin and 2,6-dimethylphenol;
式2：
x＝0-5整数x=0-5 integer
以相对于(a1)二环戊二烯-酚树脂中1摩尔的酚性羟基(酚基OH)，(a2)2,6-二甲基苯酚为1～2.5摩尔，(a3)醛化合物为0.8～1.5摩尔的比例反应。步骤二：将二环戊二烯-酚与2,6-二甲基苯酚共聚物与过量环氧氯丙烷于NaOH条件下制备二环戊二烯-酚与2,6-二甲基苯酚的共聚物环氧树脂，二环戊二烯-酚与2,6-二甲基苯酚的共聚物与环氧氯丙烷(Epichlorohydrin，ECH)当量比为1:1～8，二环戊二烯-酚与2,6-二甲基苯酚共聚物与碱NaOH的当量比为1:0.95～1.1。With respect to (a1) 1 mole of phenolic hydroxyl group (phenolic OH) in the dicyclopentadiene-phenol resin, (a2) 2,6-dimethylphenol is 1 to 2.5 moles, and (a3) aldehyde compound is The ratio of 0.8 to 1.5 moles is reacted. Step 2: Prepare a mixture of dicyclopentadiene-phenol and 2,6-dimethylphenol by combining dicyclopentadiene-phenol and 2,6-dimethylphenol copolymer with excess epichlorohydrin under NaOH conditions. Copolymer epoxy resin, the equivalent ratio of dicyclopentadiene-phenol and 2,6-dimethylphenol to epichlorohydrin (ECH) is 1:1～8, dicyclopentadiene- The equivalent ratio of phenol and 2,6-dimethylphenol copolymer to alkali NaOH is 1:0.95-1.1.
本发明二环戊二烯-酚树脂与2,6-二甲基苯酚的共聚物环氧树脂的特性效果，是将二环戊二烯-酚树脂与2,6-二甲基苯酚此两种优异电性(低介电常数Dk、低损耗因子Df)树脂反应结合再予与环氧化，不但具有二环戊二烯酚环氧树脂的优异低介电常数Dk、低吸水率特性，且具有2,6-二甲基苯酚环氧树脂优异低介电常数Dk、低损耗因子Df，故此新颖二环戊二烯-酚树脂与2,6-二甲基苯酚的共聚物环氧树脂电性(低介电常数Dk、低损耗因子Df)更优于二环戊二烯酚环氧树脂，合成制备方法是将二环戊二烯-酚树脂与2,6-二甲基苯酚在酸性催化剂下与醛化合物进行缩合脱水反应而使两种树脂相接合，即利用醛化合物搭桥将二环戊二烯-酚树脂中多个反应点与2,6-二甲基苯酚相结合为共聚物(如下反应式)，The characteristic effect of the copolymer epoxy resin of dicyclopentadiene-phenol resin and 2,6-dimethylphenol of the present invention is the combination of dicyclopentadiene-phenol resin and 2,6-dimethylphenol. A resin with excellent electrical properties (low dielectric constant Dk, low loss factor Df) is reacted and combined with epoxidation, which not only has the excellent low dielectric constant Dk and low water absorption characteristics of dicyclopentadienyl phenol epoxy resin, And 2,6-dimethylphenol epoxy resin has excellent low dielectric constant Dk, low loss factor Df, so the novel copolymer epoxy resin of dicyclopentadiene-phenol resin and 2,6-dimethylphenol The electrical properties (low dielectric constant Dk, low loss factor Df) are better than dicyclopentadiene phenol epoxy resin. The synthesis method is to mix dicyclopentadiene-phenol resin and 2,6-dimethylphenol in Condensation and dehydration reaction with an aldehyde compound under an acidic catalyst to join the two resins, that is, the use of an aldehyde compound bridge to combine multiple reaction points in the dicyclopentadiene-phenol resin with 2,6-dimethylphenol to form a copolymerization (the following reaction formula),
n,x,y＝0～5整数n,x,y=0～5 integer
共聚物结构上的酚羟基(酚基OH)官能团数f等于二环戊二烯-酚树脂的酚羟基数(n+2)加上与二环戊二烯-酚树脂接合的2,6-二甲基苯酚数x+y+2，然而x+y＝n，即f＝2n+4，共聚物较二环戊二烯-酚树脂或2,6-二甲基苯酚醛树脂具有更高官能团数的酚羟基，此酚羟基的官能团数与合成入料醛化合物的当量数成正比，醛化合物当量数愈大，表示搭桥相结合愈多，则二环戊二烯-酚树脂与2,6-二甲基苯酚共聚物的酚羟基官能团数愈高，以凝胶色谱仪GPC分析数均分子量Mn与酚羟基当量150g/eq，依理论公式：官能团数＝Mn÷酚羟基当量，计算理论官能团数平均值为6～10，将二环戊二烯-酚树脂与2,6-二甲基苯酚的共聚物的酚羟基环氧化形成二环戊二烯-酚树脂与2,6-二甲基苯酚的共聚物环氧树脂，具有高官能基特性，硬化后耐热性佳，玻璃转移温度Tg高，得到预期功效佳的Low Dk、Df，高耐热，高Tg的二环戊二烯-酚树脂与2,6-二甲基苯酚共聚物环氧树脂。The number f of phenolic hydroxyl (phenolic OH) functional groups on the copolymer structure is equal to the number of phenolic hydroxyl groups (n+2) of the dicyclopentadiene-phenol resin plus the 2,6- The number of dimethylphenol x+y+2, however x+y=n, ie f=2n+4, the copolymer has higher than dicyclopentadiene-phenol resin or 2,6-dimethylphenol formaldehyde resin The number of phenolic hydroxyl groups of functional groups, the number of functional groups of this phenolic hydroxyl group is proportional to the equivalent number of the aldehyde compound in the synthesis feed, the larger the equivalent number of the aldehyde compound, the more the bridging combination, the dicyclopentadiene-phenol resin and 2, The higher the number of phenolic hydroxyl functional groups of 6-dimethylphenol copolymer, the number average molecular weight Mn and the phenolic hydroxyl equivalent of 150g/eq were analyzed by GPC by gel chromatography. According to the theoretical formula: number of functional groups = Mn÷phenolic hydroxyl equivalent, calculation theory The average number of functional groups is 6 to 10. The phenolic hydroxyl group of the copolymer of dicyclopentadiene-phenol resin and 2,6-dimethylphenol is epoxidized to form dicyclopentadiene-phenol resin and 2,6-dimethylphenol. The copolymer epoxy resin of dimethylphenol has the characteristics of high functional group, good heat resistance after hardening, high glass transition temperature Tg, low Dk, Df with good expected efficacy, high heat resistance, high Tg dicyclopentane Diene-phenol resin and 2,6-dimethylphenol copolymer epoxy resin.
本发明进一步涉及二环戊二烯-酚树脂与2,6-二甲基苯酚的共聚物环氧树脂的制备方法，共分二步骤，步骤一：由(a1)二环戊二烯-酚树脂中1摩尔酚羟基(酚基OH)与(a2)2,6-二甲基苯酚1～2.5摩尔，加入酸性催化剂，并将0.8～1.5摩尔醛化合物溶于水，滴加于前述反应混合物中，反应温度95～115℃，醛化合物水溶液滴加反应时间1～6小时，常用酸性催化剂有甲基磺酸(MSA)、对甲苯磺酸(PTSA)、草酸、盐酸等，酸性催化剂用量以相对二环戊二烯-酚树脂用量0.5～5％，醛化合物使用有甲醛，乙醛，乙二醛，苯甲醛等，反应毕再经中和，脱2,6-二甲基苯酚，水洗，脱溶剂即得二环戊二烯-酚树脂与2,6-二甲基苯酚共聚物酚醛树脂。步骤二：将步骤一所得二环戊二烯-酚树脂与2,6-二甲基苯酚的共聚物酚醛树脂以常用环氧化条件方式与过量环氧氯丙烷与NaOH制备二环戊二烯-酚与2,6-二甲基苯酚的共聚物环氧树脂，二环戊二烯-酚树脂与2,6-二甲基苯酚的共聚物酚醛树脂与环氧氯丙烷(Epichlorohydrin，ECH)当量比为1:1～8，二环戊二烯-酚与2,6-二甲基苯酚的共聚物与碱NaOH的当量比为1:0.95～1.1，环氧化的预，主反应温度50～100℃，再经脱环氧氯丙烷，精制反应，脱盐，中和，水洗，溶液过滤，脱溶剂即得本发明二环戊二烯-酚树脂与2,6-二甲基苯酚的共聚物环氧树脂。The present invention further relates to a method for preparing a copolymer epoxy resin of dicyclopentadiene-phenol resin and 2,6-dimethylphenol, which is divided into two steps. 1 mole of phenolic hydroxyl group (phenolic OH) and (a2) 1-2.5 moles of 2,6-dimethylphenol in the resin, add an acidic catalyst, dissolve 0.8-1.5 moles of aldehyde compounds in water, and add dropwise to the aforementioned reaction mixture , the reaction temperature is 95～115℃, and the reaction time is 1～6 hours for the dropwise addition of the aldehyde compound aqueous solution. Commonly used acidic catalysts are methanesulfonic acid (MSA), p-toluenesulfonic acid (PTSA), oxalic acid, hydrochloric acid, etc. The relative amount of dicyclopentadiene-phenol resin is 0.5-5%, and the aldehyde compounds are formaldehyde, acetaldehyde, glyoxal, benzaldehyde, etc. After the reaction is completed, neutralize, remove 2,6-dimethylphenol, and wash with water , and the solvent is removed to obtain dicyclopentadiene-phenol resin and 2,6-dimethylphenol copolymer phenolic resin. Step 2: Prepare dicyclopentadiene by using the copolymer phenolic resin of dicyclopentadiene-phenol resin and 2,6-dimethylphenol obtained in step 1 with excess epichlorohydrin and NaOH under common epoxidation conditions - Copolymer epoxy resin of phenol and 2,6-dimethylphenol, copolymer of dicyclopentadiene-phenol resin and 2,6-dimethylphenol phenolic resin and epichlorohydrin (ECH) The equivalent ratio is 1:1~8, the equivalent ratio of the copolymer of dicyclopentadiene-phenol and 2,6-dimethylphenol to the alkali NaOH is 1:0.95~1.1, the pre-epoxidation, the main reaction temperature 50 to 100°C, and then subjected to epichlorohydrin removal, purification reaction, desalination, neutralization, water washing, solution filtration, and solvent removal to obtain the mixture of dicyclopentadiene-phenol resin and 2,6-dimethylphenol of the present invention. Copolymer epoxy resin.
本发明进一步公开一种用于玻纤层合板的环氧树脂清漆组合物，包含：成份(一)本发明二环戊二烯-酚树脂与2,6-二甲基苯酚的共聚物环氧树脂，使用量占树脂总量比例30～80％(树脂总量等于成份一至成份四总和)。成份(二)多官能或双官能或改性型环氧树脂，使用量占树脂总量0～25％，是选自邻甲酚型酚醛环氧树脂，酚醛环氧树脂，苯甲醛-酚多官能环氧树脂，二环戊二烯-酚环氧树脂，双酚A型酚醛环氧树脂，四酚基乙烷酚醛环氧树脂，三(羟基苯基)甲烷酚醛环氧树脂，含磷环氧树脂，2,6-二甲基苯酚酚醛环氧树脂，溴化环氧树脂，四溴双酚A型环氧树脂，双酚A型环氧树脂，环氧化物与异氰酸酯共聚物。成份(三)硬化剂，使用量占树脂总量15～60％，是选自酚醛树脂，双酚A型酚醛树脂，二环戊二烯-酚树脂，苯甲醛-酚酚醛树脂，三聚氰胺-酚酚醛树脂(melamine-phenol novolac)，活性酯类硬化剂，苯乙烯-马来酸酐共聚物(SMA)，双酚A型苯并噁嗪(BPABenzoxazine)，双酚F型苯并噁嗪(BPF Benzoxazine)，二环戊二烯-酚苯并噁嗪(Dicyclopentadiene-phenolBenzoxazine)，聚苯醚(PPE)。或前述硬化剂中任何两种(含)以上组成。成份(四)阻燃剂，使用量占树脂总量10～40％，包含反应型阻燃剂与添加型阻燃剂，是选自含磷双酚A型酚醛硬化剂(磷含量5～10％)，六苯氧环三磷腈(磷含量13.4％，氮含量8％)，四溴双酚A(溴含量58.5％)。成份(五)填充剂，使用量占总配方清漆组成物0～45％(固态计算，固态配方清漆组成等于成份一至成份五总和)，是选自二氧化硅，氢氧化铝。成份(六)硬化促进剂，使用量为0.01～0.2％(相对于环氧树脂+硬化剂量，即成份一至成份三总和)，是选自二甲基咪唑，二苯基咪唑，二乙基四甲基咪唑，苄基二甲胺。成份(七)溶剂，用量为调整配方清漆组成物固形份50～70％，是选自丙酮，丁酮，环己酮，二甲氧基乙醇(MCS)，丙二醇甲醚(PM)，甲苯。The present invention further discloses an epoxy resin varnish composition for a glass fiber laminate, comprising: component (1) a copolymer epoxy resin of the present invention's dicyclopentadiene-phenol resin and 2,6-dimethylphenol The amount of resin used accounts for 30-80% of the total resin (the total amount of resin is equal to the sum of components 1 to 4). Ingredient (2) Multifunctional or bifunctional or modified epoxy resin, the usage amount accounts for 0-25% of the total resin, and is selected from o-cresol type novolac epoxy resin, novolac epoxy resin, benzaldehyde-phenol polyphenol Functional epoxy resin, dicyclopentadiene-phenol epoxy resin, bisphenol A novolac epoxy resin, tetraphenolic ethane novolac epoxy resin, tris(hydroxyphenyl)methane novolac epoxy resin, phosphorus ring Oxygen resin, 2,6-dimethylphenol novolac epoxy resin, brominated epoxy resin, tetrabromobisphenol A epoxy resin, bisphenol A epoxy resin, epoxide and isocyanate copolymer. Component (3) Hardener, used in an amount of 15-60% of the total resin, selected from phenolic resin, bisphenol A phenolic resin, dicyclopentadiene-phenolic resin, benzaldehyde-phenolic phenolic resin, melamine-phenol Phenolic resin (melamine-phenol novolac), active ester hardener, styrene-maleic anhydride copolymer (SMA), bisphenol A benzoxazine (BPABenzoxazine), bisphenol F benzoxazine (BPF Benzoxazine) ), dicyclopentadiene-phenolBenzoxazine (Dicyclopentadiene-phenolBenzoxazine), polyphenylene ether (PPE). Or any two (inclusive) or more of the aforementioned hardeners. Ingredient (4) flame retardant, the amount used accounts for 10-40% of the total resin, including reactive flame retardant and additive flame retardant, which is selected from phosphorus-containing bisphenol A type phenolic hardener (phosphorus content 5-10%). %), hexaphenoxycyclotriphosphazene (phosphorus content 13.4%, nitrogen content 8%), tetrabromobisphenol A (bromine content 58.5%). Component (5) filler, the usage amount accounts for 0～45% of the total formula varnish composition (in solid state, the solid formula varnish composition is equal to the sum of components 1 to 5), and is selected from silicon dioxide and aluminum hydroxide. Component (6) Hardening accelerator, the usage amount is 0.01-0.2% (relative to epoxy resin + hardener, i.e. the sum of components 1 to 3), which is selected from dimethyl imidazole, diphenyl imidazole, diethyl tetra Methylimidazole, benzyldimethylamine. Component (7) Solvent, the dosage is 50-70% of the solid content of the varnish composition to adjust the formula, and is selected from acetone, butanone, cyclohexanone, dimethoxyethanol (MCS), propylene glycol methyl ether (PM), and toluene.
本发明的二环戊二烯-酚树脂与2,6-二甲基苯酚的共聚物环氧树脂，与其清漆组合物经热硬化所得硬化物可使用于不同应用，包括用于例如PCB印刷电路板，EMC半导体封装等高可靠性电机/电子组件的绝缘材料，及需要优异电性特性及热稳定的涂料、粘着剂。The copolymer epoxy resin of dicyclopentadiene-phenol resin and 2,6-dimethylphenol of the present invention, and the hardened product obtained by thermal hardening of its varnish composition can be used in various applications, including for example, PCB printed circuits boards, insulating materials for high-reliability motor/electronic components such as EMC semiconductor packaging, and coatings and adhesives that require excellent electrical properties and thermal stability.
发明效果：根据本发明提供一种二环戊二烯-酚树脂与2,6-二甲基苯酚的共聚物环氧树脂的制备方法与应用，其清漆组合物经热硬化反应所得硬化物展现优异耐热性、低介电常数、低损耗因素、高Tg等性能，符合未来电子产业高速，高频发展趋势。Effects of the Invention: According to the present invention, a preparation method and application of a copolymer epoxy resin of dicyclopentadiene-phenol resin and 2,6-dimethylphenol are provided, and the cured product obtained by the thermal hardening reaction of the varnish composition exhibits Excellent heat resistance, low dielectric constant, low loss factor, high Tg and other properties are in line with the future high-speed and high-frequency development trend of the electronic industry.
具体实施方式Detailed ways
由下列详细说明将更清楚地理解本发明。The present invention will be more clearly understood from the following detailed description.
本发明二环戊二烯-酚树脂与2,6-二甲基苯酚的共聚物环氧树脂的最显著特点为以反应接枝方式结合二环戊二烯酚环氧树脂与2,6-二甲基苯酚醛环氧树脂两种优异电性结构树脂，结果本发明共聚物环氧树脂其电性(低介电常数Dk、低损耗因素Df)与耐热性，Tg特性更优于前述两种树脂，在于将二环戊二烯-酚树脂与2,6-二甲基苯酚醛树脂以醛化合物于酸性催化剂下反应接枝结合，后与环氧氯丙烷进行环氧化反应形成环氧树脂，由于采取反应接枝结合，其环氧基官能团数更多，硬化架桥密度更高，致使电性(低介电常数Dk、低损耗因素Df)与耐热性，Tg特性更优于前述两种树脂。The most notable feature of the copolymer epoxy resin of dicyclopentadiene-phenol resin and 2,6-dimethylphenol of the present invention is that the dicyclopentadiene phenol epoxy resin and 2,6-dimethylphenol are combined by reaction grafting mode. Dimethyl phenol novolac epoxy resin is two excellent electrical structural resins. As a result, the electrical properties (low dielectric constant Dk, low loss factor Df), heat resistance and Tg properties of the copolymer epoxy resin of the present invention are better than those mentioned above. The two resins are that the dicyclopentadiene-phenol resin and the 2,6-dimethylphenol-formaldehyde resin are reacted and grafted together with an aldehyde compound under an acidic catalyst, and then subjected to an epoxidation reaction with epichlorohydrin to form a ring. Oxygen resin, due to the use of reactive grafting, has more epoxy functional groups and higher hardening bridging density, resulting in better electrical properties (low dielectric constant Dk, low loss factor Df) and heat resistance, Tg characteristics are better in the above two resins.
明确而言，制备本发明的二环戊二烯-酚树脂与2,6-二甲基苯酚的共聚物环氧树脂制备方法包含两步骤，步骤一(二环戊二烯-酚树脂与2,6-二甲基苯酚共聚物酚醛树脂合成)：由(a1)二环戊二烯-酚树脂中1摩尔酚羟基(酚基OH)与(a2)2,6-二甲基苯酚1～2.5摩尔，加入中沸点低容水率溶剂(沸点>110℃)，再加入酸性催化剂，升温至95～115℃，并将0.8～1.5摩尔醛化合物溶于水，配成20～50％醛化物水溶液(若醛化物为液态，则无需配制水溶液)滴加于前述反应混合物中，滴加反应温度95～115℃，醛化合物水溶液滴加反应时间1～6小时，常用酸性催化剂有甲基磺酸(MSA)、对甲苯磺酸(PTSA)、草酸、盐酸等，酸性催化剂用量以相对二环戊二烯-酚树脂用量0.5～5％，醛化合物使用有甲醛，乙醛，乙二醛，苯甲醛等，反应过程需将水移除，可使醛化物反应完全，加入溶剂的目的是与水共沸将水带出并与水产生分相而移除水相，溶剂选择有甲基异丁基酮(MIBK)、甲苯等中沸点低容水率溶剂。溶剂用量以相对二环戊二烯-酚树脂用量5～20％。滴加反应毕后，进行熟成反应30分钟～2小时。反应结束后以碱中和酸性催化剂，碱无任何限制为工业常用碱如氢氧化钠，氢氧化钾，胺类等。中和至PH值6～7即进行升温脱除溶剂与2,6-二甲基苯酚，温度175～185℃，达温度175～185℃后慢慢降低真空度以不发生突沸，最终至真空度<5torr。真空度<5torr条件下维持温度175～185℃1小时。续加入溶剂如甲基异丁基酮(MIBK)，甲苯等溶解，加入水进行脱盐、水洗、过滤与脱溶剂步骤，脱溶剂后即得二环戊二烯-酚树脂与2,6-二甲基苯酚的共聚物酚醛树脂。Specifically, the preparation method of the copolymer epoxy resin of the dicyclopentadiene-phenol resin and 2,6-dimethylphenol of the present invention comprises two steps, step 1 (dicyclopentadiene-phenol resin and 2 ,6-dimethylphenol copolymer phenolic resin synthesis): from (a1) dicyclopentadiene-phenol resin in 1 mole of phenolic hydroxyl (phenolic OH) and (a2) 2,6-dimethylphenol 1 ~ 2.5 moles, add a medium boiling point low water volume solvent (boiling point>110°C), then add an acidic catalyst, heat up to 95-115°C, and dissolve 0.8-1.5 moles of aldehyde compounds in water to prepare 20-50% aldehyde compounds The aqueous solution (if the aldehyde compound is liquid, there is no need to prepare an aqueous solution) is added dropwise to the aforementioned reaction mixture, the dropwise addition reaction temperature is 95 to 115 ° C, and the dropwise reaction time of the aldehyde compound aqueous solution is 1 to 6 hours. Commonly used acidic catalysts are methanesulfonic acid. (MSA), p-toluenesulfonic acid (PTSA), oxalic acid, hydrochloric acid, etc., the amount of acid catalyst is 0.5-5% relative to the amount of dicyclopentadiene-phenol resin, and the aldehyde compounds are formaldehyde, acetaldehyde, glyoxal, benzene Formaldehyde, etc., the water needs to be removed in the reaction process, so that the reaction of the aldehyde compound can be completed. The purpose of adding a solvent is to azeotrope with water to bring out the water and to separate phases with water to remove the water phase. The solvent is selected from methyl isobutyl Base ketone (MIBK), toluene and other medium boiling point low water volume solvents. The amount of solvent is 5-20% relative to the amount of dicyclopentadiene-phenol resin. After the dropwise addition reaction is completed, the aging reaction is performed for 30 minutes to 2 hours. After the reaction is completed, the acidic catalyst is neutralized with an alkali, and the alkali is not limited to industrial common alkalis such as sodium hydroxide, potassium hydroxide, amines, etc. Neutralize to PH value of 6～7, then heat up to remove the solvent and 2,6-dimethylphenol, the temperature is 175～185℃, after reaching the temperature of 175～185℃, the vacuum degree is slowly reduced to prevent sudden boiling, and finally the vacuum is reached Degree < 5torr. Keep the temperature at 175-185℃ for 1 hour under the condition of vacuum degree <5torr. Continue to add solvent such as methyl isobutyl ketone (MIBK), toluene, etc. to dissolve, add water to carry out desalination, water washing, filtration and desolvation steps, after desolventizing, dicyclopentadiene-phenol resin and 2,6-dicyclopentadiene-phenol resin and 2,6-dicyclopentadiene-phenol resin are obtained. Copolymer phenolic resin of methyl phenol.
步骤二(二环戊二烯-酚与2,6-二甲基苯酚的共聚物环氧树脂合成)：将步骤一所得二环戊二烯-酚与2,6-二甲基苯酚的共聚物以常用环氧化条件方式与过量环氧氯丙烷与氢氧化钠(NaOH)制备二环戊二烯-酚与2,6-二甲基苯酚的共聚物环氧树脂，如步骤(1)～(5)。(1)预反应：将二环戊二烯-酚树脂与2,6-二甲基苯酚的共聚物酚醛树脂与环氧氯丙烷(Epichlorohydrin，ECH)当量比为1:1～8，并加入以相对二环戊二烯-酚树脂与2,6-二甲基苯酚的共聚物酚醛树脂用量10～40％共溶剂，共溶剂选择如丙二醇单甲醚(PM)或醇类等，再加入49.5％氢氧化钠NaOH，二环戊二烯-酚树脂与2,6-二甲基苯酚共聚物酚醛树脂与碱NaOH的当量比为1:0.1～0.2，预反应温度50～100℃，预反应时间2～4小时。(2)主反应：以49.5％NaOH 0.77～0.97当量比相对二环戊二烯-酚树脂与2,6-二甲基苯酚的共聚物酚醛树脂1当量滴加于反应物中，反应温度60～65℃，真空度160～190torr，主反应滴加时间2～5小时，主反应过程通过ECH与水共沸将系内水分带出并经由分相桶分相下层ECH回流至系内，上层水层排出。(3)脱环氧氯丙烷：以温度160℃，真空度<5torr脱除过量环氧氯丙烷ECH。(4)精制反应：加入溶剂配制30～50％固形份树脂溶液，加入20％氢氧化钠NaOH进行精制反应，20％氢氧化钠NaOH加入量＝所测可水解氯值÷35.5×40×精制系数1.5×树脂重÷0.2，精制温度70～90℃，精制反应时间1～3小时，反应结束进行加水脱盐分液，中和、水洗分液，树脂溶液过滤，脱溶剂后即得本发明二环戊二烯-酚与2,6-二甲基苯酚的共聚物环氧树脂。Step 2 (synthesis of epoxy resin copolymer of dicyclopentadiene-phenol and 2,6-dimethylphenol): copolymerization of dicyclopentadiene-phenol and 2,6-dimethylphenol obtained in step 1 The copolymer epoxy resin of dicyclopentadiene-phenol and 2,6-dimethylphenol was prepared with excess epichlorohydrin and sodium hydroxide (NaOH) under common epoxidation conditions, as in step (1) ~(5). (1) Pre-reaction: The equivalent ratio of the copolymer phenolic resin of dicyclopentadiene-phenol resin and 2,6-dimethylphenol to epichlorohydrin (ECH) is 1:1-8, and adding Use 10-40% co-solvent relative to the copolymer phenolic resin of dicyclopentadiene-phenol resin and 2,6-dimethylphenol, such as propylene glycol monomethyl ether (PM) or alcohol, etc., and then add 49.5% sodium hydroxide NaOH, the equivalent ratio of dicyclopentadiene-phenol resin and 2,6-dimethylphenol copolymer phenolic resin and alkali NaOH is 1:0.1～0.2, the pre-reaction temperature is 50～100℃, and the pre-reaction temperature is 50～100℃. The reaction time is 2 to 4 hours. (2) Main reaction: 49.5%NaOH 0.77～0.97 equivalent ratio was added dropwise to the reactant with 1 equivalent of the copolymer phenolic resin of dicyclopentadiene-phenol resin and 2,6-dimethylphenol, and the reaction temperature was 60 ℃ ～65℃, vacuum degree 160～190torr, main reaction dropping time is 2～5 hours, the main reaction process brings out the water in the system through azeotropy of ECH and water, and returns to the system through the phase-separating barrel and the lower layer ECH returns to the system, the upper layer is The water layer is drained. (3) Removal of epichlorohydrin: remove excess epichlorohydrin ECH at a temperature of 160°C and a vacuum degree of <5torr. (4) Refining reaction: add solvent to prepare 30-50% solid resin solution, add 20% sodium hydroxide NaOH to carry out refining reaction, the amount of 20% sodium hydroxide NaOH added = measured hydrolyzable chlorine value ÷ 35.5×40×refining Coefficient 1.5×resin weight ÷ 0.2, refining temperature 70～90 ℃, refining reaction time 1～3 hours, after the reaction is over, add water, desalinate and separate liquids, neutralize, wash and separate liquids, filter the resin solution, and remove the solvent to obtain the second method of the present invention. A copolymer epoxy resin of cyclopentadiene-phenol and 2,6-dimethylphenol.
关于制备本发明二环戊二烯-酚与2,6-二甲基苯酚的共聚物环氧树脂的方法更详细说明，采取如上述步骤一～二方式，步骤一将(a1)二环戊二烯-酚树脂中1摩尔酚羟基(酚基OH)与(a2)2,6-二甲基苯酚1～2.5摩尔，加入中沸点低容水率溶剂(沸点>110℃)，再加入酸性催化剂，升温至95～115℃，并将0.8～1.5摩尔醛化合物溶于水，配成20～50％醛化物水溶液(若醛化物为液态，则无需配制水溶液)滴加于前述反应混合物中，为使反应达高转化率、高反应率，反应过程需将水移除，通过中沸点低容水率溶剂将水带出，于分相桶分相将下层水层排除，上层溶剂回流至反应系统内，醛化合物水溶液以滴加方式，可使醛化合物反应效率更佳，反应更为完全。此步骤反应的进行有二种可能性，一为二环戊二烯-酚树脂不仅通过醛与自身二环戊二烯-酚反应相接合且通过醛与2,6-二甲基苯酚反应相接合，二为2,6-二甲基苯酚通过醛与自身2,6-二甲基苯酚反应相接合。所得产物重量平均分子量与醛化合物入料量成正相关，醛化合物入料当量不超过二环戊二烯-酚树脂与2,6-二甲基苯酚当量数总和，醛化合物入料当量以0.8至1.2为较佳范围。The method for preparing the copolymer epoxy resin of dicyclopentadiene-phenol and 2,6-dimethylphenol of the present invention is described in more detail, and the methods of steps 1 and 2 above are adopted. In step 1, (a1) dicyclopenta 1 mole of phenolic hydroxyl (phenolic OH) and (a2) 1-2.5 moles of 2,6-dimethylphenol in diene-phenol resin, add medium boiling point low water content solvent (boiling point>110℃), then add acid The catalyst is heated to 95-115°C, and 0.8-1.5 moles of aldehyde compounds are dissolved in water, and the 20-50% aldehyde compound aqueous solution (if the aldehyde compound is liquid, then there is no need to prepare an aqueous solution) is added dropwise to the aforementioned reaction mixture, In order to make the reaction reach high conversion rate and high reaction rate, the water needs to be removed during the reaction process. In the system, the aqueous solution of the aldehyde compound is added dropwise, so that the reaction efficiency of the aldehyde compound is better and the reaction is more complete. There are two possibilities for the reaction in this step. One is that the dicyclopentadiene-phenol resin not only joins with its own dicyclopentadiene-phenol through the reaction of aldehyde, but also reacts with 2,6-dimethylphenol through the aldehyde. Conjugation, the second is that 2,6-dimethylphenol reacts with itself 2,6-dimethylphenol through aldehyde. The weight-average molecular weight of the obtained product is positively correlated with the input amount of aldehyde compound, the input equivalent of aldehyde compound does not exceed the sum of the equivalents of dicyclopentadiene-phenol resin and 2,6-dimethylphenol, and the input equivalent of aldehyde compound is 0.8 to 1.2 is the preferred range.
步骤二：将步骤一所得二环戊二烯-酚与2,6-二甲基苯酚的共聚物酚醛树脂以常见环氧化条件合成二环戊二烯-酚与2,6-二甲基苯酚的共聚物环氧树脂，即以过量环氧氯丙烷在氢氧化钠存在下将二环戊二烯-酚与2,6-二甲基苯酚共聚物酚醛树脂进行环氧化合成。Step 2: Synthesize dicyclopentadiene-phenol and 2,6-dimethylphenol from the copolymer phenolic resin of dicyclopentadiene-phenol and 2,6-dimethylphenol obtained in step 1 under common epoxidation conditions The copolymer epoxy resin of phenol is synthesized by epoxidizing dicyclopentadiene-phenol and 2,6-dimethylphenol copolymer phenolic resin with excess epichlorohydrin in the presence of sodium hydroxide.
本发明的较佳具体实施例将根据下列实施例详细叙明。Preferred embodiments of the present invention will be described in detail based on the following examples.
合成例A：(二环戊二烯-酚与2,6-二甲基苯酚的共聚物环氧树脂A合成)Synthesis Example A: (Synthesis of epoxy resin A, a copolymer of dicyclopentadiene-phenol and 2,6-dimethylphenol)
将二环戊二烯-酚树脂(南亚塑料公司品名NPEH-772L，软化点85℃)170g(1摩尔酚羟基)，2,6-二甲基苯酚170g，溶剂甲基异丁基酮(MIBK)30g，催化剂甲基磺酸MSA1.7g混合升温至107℃，再将23％甲醛溶液130g于107℃滴加反应3.5小时，续于107℃熟成反应1Hr，反应结束后，加入49.5％NaOH水溶液0.8g，中和至PH值＝6～7，升温至140℃脱水，升温至185℃，慢慢降低真空度至5torr。温度与真空度达设定值185℃×5torr维持1小时。降温与破真空后加溶剂甲基异丁基酮550g，于80℃搅拌60分钟溶解，加水50g，80℃静置分层，将下层盐水层排掉，再加入水50g水洗，80℃静置分层，将下层水层排掉，再重复水洗步骤1次。溶液过滤后，于120℃脱水，续升温至180℃，降低真空度至5torr下，脱除溶剂甲基异丁基酮(MIBK)，得二环戊二烯-酚与2,6-二甲基苯酚的共聚物酚醛树脂A，收率99.5％，质量状况：平均分子量Mw2500，软化点126℃，酚羟基当量150g/eq。Dicyclopentadiene-phenol resin (NPEH-772L of Nan Ya Plastics Co., Ltd., softening point 85°C) 170g (1 mole of phenolic hydroxyl group), 170g of 2,6-dimethylphenol, solvent methyl isobutyl ketone (MIBK) ) 30g, 1.7g of catalyst methanesulfonic acid MSA was mixed and heated to 107°C, then 130g of 23% formaldehyde solution was added dropwise at 107°C to react for 3.5 hours, and the reaction was continued for 1Hr at 107°C. After the reaction, 49.5% NaOH aqueous solution was added. 0.8g, neutralize to PH value=6～7, heat up to 140°C for dehydration, heat up to 185°C, and slowly reduce the degree of vacuum to 5torr. The temperature and vacuum degree reached the set value of 185℃×5torr and maintained for 1 hour. After cooling and breaking the vacuum, add 550 g of solvent methyl isobutyl ketone, stir at 80 °C for 60 minutes to dissolve, add 50 g of water, let stand at 80 °C for stratification, drain the lower brine layer, add 50 g of water to wash, and let stand at 80 °C The layers were separated, the lower water layer was drained, and the water washing step was repeated once. After the solution was filtered, dehydrated at 120 °C, continued to heat up to 180 °C, reduced the vacuum to 5 torr, and removed the solvent methyl isobutyl ketone (MIBK) to obtain dicyclopentadiene-phenol and 2,6-dimethylene Phenol-based copolymer phenolic resin A, yield 99.5%, quality condition: average molecular weight Mw2500, softening point 126°C, phenolic hydroxyl equivalent 150g/eq.
将二环戊二烯-酚与2,6-二甲基苯酚共聚物树脂酚醛树脂A 150g，环氧氯丙烷555g，丙二醇单甲醚PM 166g，混合溶解后升温至60℃，加入49.5％氢氧化钠NaOH 12.1g进行预反应，预反应时间3小时；再将49.5％氢氧化钠66g滴加至混合溶液进行主反应，主反应温度62℃，真空度180torr，主反应时间4小时，主反应结束于150℃，10torr，维持1小时进行脱水与脱ECH；加入溶剂甲基异丙酮207g于80℃溶解30分钟，加入纯水196g，80℃搅拌15分钟静置分相，将下层盐水层排掉；分析树脂的可水解氯值为2500ppm，于80℃进行精制反应，加入49.5％氢氧化钠1.75g与2g纯水，反应2小时。续加入溶剂MIBK 276g，与加入50g纯水，80℃搅拌15分钟静置分相，将下层水层排掉，加入纯水30g，20g的10％NaH2PO4，80℃搅拌15分钟静置分相，分析PH值为6～7，将下层水层排掉，加入纯水40g，80℃搅拌15分钟静置分相，将下层水层排掉，升温至117℃进行环流脱水1小时，后经溶液过滤，升温至150℃，逐渐降低真空度至5torr，于150℃，5torr条件下维持1小时即得本发明二环戊二烯-酚与2,6-二甲基苯酚的共聚物环氧树脂A。Dicyclopentadiene-phenol and 2,6-dimethylphenol copolymer resin phenolic resin A 150g, epichlorohydrin 555g, propylene glycol monomethyl ether PM 166g, mixed and dissolved, heated to 60°C, added 49.5% hydrogen Sodium oxide NaOH 12.1g was pre-reacted, and the pre-reaction time was 3 hours; then 49.5% sodium hydroxide 66g was added dropwise to the mixed solution to carry out the main reaction, the main reaction temperature was 62°C, the vacuum degree was 180torr, the main reaction time was 4 hours, and the main reaction was carried out. Finished at 150°C, 10torr, maintained for 1 hour for dehydration and de-ECH; add solvent methyl isoacetone 207g, dissolve at 80°C for 30 minutes, add 196g of pure water, stir at 80°C for 15 minutes, let stand for phase separation, and drain the lower brine layer. The hydrolyzable chlorine value of the analysis resin was 2500 ppm, and the purification reaction was carried out at 80° C., 1.75 g of 49.5% sodium hydroxide and 2 g of pure water were added, and the reaction was carried out for 2 hours. Continue to add solvent MIBK 276g, add 50g pure water, stir at 80°C for 15 minutes and let stand for phase separation, drain the lower water layer, add 30g pure water, 20g of 10% NaH2PO4, stir at 80°C for 15 minutes and let stand for phase separation, Analyze the pH value to be 6 to 7, drain the lower water layer, add 40 g of pure water, stir at 80°C for 15 minutes, let stand for phase separation, drain the lower water layer, heat up to 117°C for loop dehydration for 1 hour, and then pass through the solution Filtration, warming up to 150° C., gradually reducing the degree of vacuum to 5torr, maintaining at 150° C. under the condition of 5torr for 1 hour to obtain the copolymer epoxy resin of dicyclopentadiene-phenol and 2,6-dimethylphenol of the present invention A.
质量状况：环氧当量228g/eq，可水解氯240ppm，重量平均分子量Mw3500。Quality status: epoxy equivalent 228g/eq, hydrolyzable chlorine 240ppm, weight average molecular weight Mw3500.
合成例B：(二环戊二烯-酚与2,6-二甲基苯酚的共聚物环氧树脂B合成)Synthesis Example B: (Synthesis of epoxy resin B, a copolymer of dicyclopentadiene-phenol and 2,6-dimethylphenol)
将二环戊二烯-酚树脂(南亚塑料公司品名NPEH-772H，软化点110℃)180g(1摩尔酚羟基)，2,6-二甲基苯酚170g，溶剂甲基异丁基酮(MIBK)30g，催化剂甲基磺酸MSA1.7g混合升温至107℃，再将23％甲醛溶液130g于107℃滴加反应3.5小时，续于107℃熟成反应1Hr，反应结束后，加入49.5％NaOH水溶液0.8g，中和至PH值＝6～7，升温至140℃脱水，升温至185℃，慢慢降低真空度至5torr。温度与真空度达设定值185℃×5torr维持1小时。降温与破真空后加溶剂甲基异丁基酮550g，于80℃搅拌60分钟溶解，加水50g，80℃静置分层，将下层盐水层排掉，再加入水50g水洗，80℃静置分层，将下层水层排掉，再重复水洗步骤1次。溶液过滤后，于120℃脱水，续升温至180℃，降低真空度至5torr下，脱除溶剂甲基异丁基酮(MIBK)，得二环戊二烯-酚与2,6-二甲基苯酚共聚物酚醛树脂B，收率99.5％，质量状况：平均分子量Mw2800，软化点129℃，酚羟基当量154g/eq。Dicyclopentadiene-phenol resin (named NPEH-772H of Nanya Plastics Co., Ltd., softening point 110°C) 180g (1 mole of phenolic hydroxyl group), 170g of 2,6-dimethylphenol, solvent methyl isobutyl ketone (MIBK) ) 30g, 1.7g of catalyst methanesulfonic acid MSA was mixed and heated to 107°C, then 130g of 23% formaldehyde solution was added dropwise at 107°C to react for 3.5 hours, and the reaction was continued for 1Hr at 107°C. After the reaction, 49.5% NaOH aqueous solution was added. 0.8g, neutralize to PH value=6～7, heat up to 140°C for dehydration, heat up to 185°C, and slowly reduce the degree of vacuum to 5torr. The temperature and vacuum degree reached the set value of 185℃×5torr and maintained for 1 hour. After cooling and breaking the vacuum, add 550 g of solvent methyl isobutyl ketone, stir at 80 °C for 60 minutes to dissolve, add 50 g of water, let stand at 80 °C for stratification, drain the lower brine layer, add 50 g of water to wash, and let stand at 80 °C The layers were separated, the lower water layer was drained, and the water washing step was repeated once. After the solution was filtered, dehydrated at 120 °C, continued to heat up to 180 °C, reduced the vacuum to 5 torr, and removed the solvent methyl isobutyl ketone (MIBK) to obtain dicyclopentadiene-phenol and 2,6-dimethylene Base phenol copolymer phenolic resin B, yield 99.5%, quality condition: average molecular weight Mw2800, softening point 129°C, phenolic hydroxyl equivalent weight 154g/eq.
将二环戊二烯-酚与2,6-二甲基苯酚共聚物树脂B 154g，环氧氯丙烷555g，丙二醇单甲醚PM 166g，混合溶解后升温至60℃，加入49.5％氢氧化钠NaOH 12.1g进行预反应，预反应时间3小时；再将49.5％氢氧化钠66g滴加至混合溶液进行主反应，主反应温度62℃，真空度180torr，主反应时间4小时，主反应结束于150℃，10torr，维持1小时进行脱水与脱ECH；加入溶剂甲基异丙酮207g于80℃溶解30分钟，加入纯水196g，80℃搅拌15分钟静置分相，将下层盐水层排掉；分析树脂的可水解氯值为2200ppm，于80℃进行精制反应，加入49.5％氢氧化钠1.70g与2g纯水，反应2小时。续加入溶剂MIBK 276g，与加入50g纯水，80℃搅拌15分钟静置分相，将下层水层排掉，加入纯水30g，20g的10％NaH2PO4，80℃搅拌15分钟静置分相，分析PH值为6～7，将下层水层排掉，加入纯水40g，80℃搅拌15分钟静置分相，将下层水层排掉，升温至117℃进行环流脱水1小时，后经溶液过滤，升温至150℃，逐渐降低真空度至5torr，于150℃，5torr条件下维持1小时即得本发明二环戊二烯-酚与2,6-二甲基苯酚的共聚物环氧树脂B。Dicyclopentadiene-phenol and 2,6-dimethylphenol copolymer resin B 154g, epichlorohydrin 555g, propylene glycol monomethyl ether PM 166g, mixed and dissolved, heated to 60°C, added 49.5% sodium hydroxide NaOH 12.1g was pre-reacted, and the pre-reaction time was 3 hours; then 49.5% sodium hydroxide 66g was added dropwise to the mixed solution to carry out the main reaction. 150°C, 10torr, maintained for 1 hour for dehydration and de-ECH; add solvent methyl isoacetone 207g, dissolve at 80°C for 30 minutes, add 196g pure water, stir at 80°C for 15 minutes, let stand for phase separation, and drain the lower brine layer; The hydrolyzable chlorine value of the analytical resin was 2200 ppm, and the purification reaction was carried out at 80° C., 1.70 g of 49.5% sodium hydroxide and 2 g of pure water were added, and the reaction was carried out for 2 hours. Continue to add solvent MIBK 276g, add 50g pure water, stir at 80°C for 15 minutes and let stand for phase separation, drain the lower water layer, add 30g pure water, 20g of 10% NaH2PO4, stir at 80°C for 15 minutes and let stand for phase separation, Analyze the pH value to be 6 to 7, drain the lower water layer, add 40 g of pure water, stir at 80°C for 15 minutes, let stand for phase separation, drain the lower water layer, heat up to 117°C for loop dehydration for 1 hour, and then pass through the solution Filtration, warming up to 150° C., gradually reducing the degree of vacuum to 5torr, maintaining at 150° C. under the condition of 5torr for 1 hour to obtain the copolymer epoxy resin of dicyclopentadiene-phenol and 2,6-dimethylphenol of the present invention B.
质量状况：环氧当量232g/eq，可水解氯210ppm，重量平均分子量Mw3800。Quality status: epoxy equivalent 232g/eq, hydrolyzable chlorine 210ppm, weight average molecular weight Mw3800.
实施例1～5覆铜板配方物性如表一The physical properties of the copper clad laminates in Examples 1 to 5 are shown in Table 1
实施例1～5使用本发明二环戊二烯-酚与2,6-二甲基苯酚的共聚物环氧树脂应用于玻纤层合板，具有优良耐热性与低介电常数的树脂清漆(Varnish)配方组成物，其配方组成详于表一，采用溶剂如丙二醇单甲醚(PM)或丁酮或丙酮调整固形份为65％的树脂清漆(Varnish)配方组成物，以公知方法制备玻纤层合板，将7628玻璃纤维布含浸上述树脂液，然后于170℃(含浸机温度)，干燥数分钟，借着调整控制干燥时间可调整干燥后预浸渍体的最低熔融粘度为4000～10000poise间，最后将8片预浸渍体层层相迭于两片35-um厚之铜箔间，在25kg/cm2压力下，控制升温程序：Examples 1-5 Use the copolymer epoxy resin of dicyclopentadiene-phenol and 2,6-dimethylphenol of the present invention to be applied to glass fiber laminates, resin varnish with excellent heat resistance and low dielectric constant (Varnish) formula composition, its formula composition is detailed in table 1, adopts solvent such as propylene glycol monomethyl ether (PM) or methyl ethyl ketone or acetone to adjust the resin varnish (Varnish) formula composition with solid content of 65%, prepared by known method For glass fiber laminate, 7628 glass fiber cloth is impregnated with the above resin solution, and then dried at 170°C (impregnation machine temperature) for several minutes. By adjusting and controlling the drying time, the minimum melt viscosity of the prepreg after drying can be adjusted to 4000～10000poise Finally, 8 pieces of prepreg are stacked between two pieces of 35-um thick copper foil layer by layer, under the pressure of 25kg/cm 2 , control the heating program:
85℃→85℃→200℃→200℃→130℃85℃→85℃→200℃→200℃→130℃
20min 30min 120min慢慢冷却20min 30min 120min Cool slowly
经热压后而得到1.6mm厚的铜箔基板。After hot pressing, a copper foil substrate with a thickness of 1.6 mm was obtained.
表一实施例清漆组合物与玻纤层合板物性Table 1 Example varnish composition and physical properties of glass fiber laminate
比较例1～3Comparative Examples 1 to 3
在不使用本发明二环戊二烯-酚与2,6-二甲基苯酚的共聚物环氧树脂，以其它低介电环氧树脂作为比较例，其配方组成详于表二，比较例1为使用苯甲醛-酚环氧树脂(南亚塑料公司型号NPPN-433)，比较例2为使用2,6-二甲基苯酚酚醛环氧树脂(南亚塑料公司型号NPPN-260)，比较例3为使用二环戊二烯-酚环氧树脂(南亚塑料公司型号NPPN-272H)。Without using the copolymer epoxy resin of dicyclopentadiene-phenol and 2,6-dimethylphenol of the present invention, other low-dielectric epoxy resins are used as comparative examples. 1 is the use of benzaldehyde-phenol epoxy resin (Nan Ya Plastics company model NPPN-433), Comparative Example 2 is the use of 2,6-dimethylphenol novolac epoxy resin (Nan Ya Plastics Company model NPPN-260), Comparative Example 3 To use a dicyclopentadiene-phenol epoxy resin (Nan Ya Plastics Co. model NPPN-272H).
表二比较例清漆组合物与玻纤层合板物性Table 2 Physical properties of varnish composition and glass fiber laminate of comparative example
由上测试结果可知，由本发明二环戊二烯-酚与2,6-二甲基苯酚的共聚物环氧树脂代入配方所制作玻纤层合板，其介电常数Dk与损号因素Df较比较例1的苯甲醛-酚环氧树脂与比较例2的2,6-二甲基苯酚，比较例3的二环戊二烯-酚环氧树脂更低，且本发明二环戊二烯-酚与2,6-二甲基苯酚的共聚物环氧树脂代入配方Tg高于比较例1～3。It can be seen from the above test results that the dielectric constant Dk and the loss factor Df of the glass fiber laminate made by substituting the epoxy resin of the copolymer of dicyclopentadiene-phenol and 2,6-dimethylphenol of the present invention into the formula are better than those of the loss factor Df. The benzaldehyde-phenol epoxy resin of Comparative Example 1 and the 2,6-dimethylphenol of Comparative Example 2, the dicyclopentadiene-phenol epoxy resin of Comparative Example 3 are lower, and the dicyclopentadiene of the present invention is lower - The epoxy resin substitution formula Tg of the copolymer of phenol and 2,6-dimethylphenol is higher than that of Comparative Examples 1-3.
1.吸水率测试(PCT压力锅2小时)1. Water absorption test (PCT pressure cooker for 2 hours)
吸水率测试方法为将以蚀刻后基板裁成5cm2正方形试片，于105℃烘箱内烘2hr后，将试片放于压力锅内，压力锅条件为2atm×120℃,经过压力锅120min后，记录试片于压力锅前后重量差÷试片初重即为吸水率。The test method for water absorption is to cut the etched substrate into a 5cm square test piece, bake it in a 105 ℃ oven for 2 hours, and place the test piece in a pressure cooker. The pressure cooker condition is 2 atm × 120 ℃. The weight difference between the pieces before and after the pressure cooker ÷ the initial weight of the test piece is the water absorption rate.
2.288℃耐焊锡耐热性(经PCT压力锅2小时)2.288℃ Solder resistance and heat resistance (2 hours after PCT pressure cooker)
测试方法则为将上述经过压力锅试片,浸入288℃焊锡炉,记录试片爆板分层所需时间。The test method is to immerse the above-mentioned pressure cooker test piece into a 288 ℃ soldering furnace, and record the time required for the test piece to explode and delaminate.
3.T-288耐热性(含铜)3. T-288 heat resistance (including copper)
以热机械分析仪分析，测试方法则为含铜的铜箔基板裁成6.35mm2正方形试片，于烘箱105℃×2小时烘烤，放入试片于热机械分析仪测试台，归零后，将热机械分析仪以10℃/分升温至288℃并维持288℃，记录试片铜箔基板分层所需时间。Analyzed by thermomechanical analyzer. The test method is to cut the copper-containing copper foil substrate into a 6.35mm2 square test piece, bake it in an oven at 105°C for 2 hours, put the test piece on the test bench of the thermomechanical analyzer, and return to zero. , the thermomechanical analyzer was heated to 288°C at 10°C/min and maintained at 288°C, and the time required for the delamination of the copper foil substrate of the test piece was recorded.
4.介电常数(Dielectric constant)测试：4. Dielectric constant test:
测试方法为将以去除酮箔的玻纤层合板5cm×5cm正方型试片，于105℃烘箱内烘2hr，以厚度测定仪量测厚度，再将试片夹入阻抗分析仪中(Agilent E4991A)，测得3点的介电常数Dk数据后取平均值。The test method is to bake the 5cm×5cm square test piece of the glass fiber laminate with the ketone foil removed, bake it in an oven at 105°C for 2hr, measure the thickness with a thickness measuring instrument, and then clamp the test piece into an impedance analyzer (Agilent E4991A). ), measure the dielectric constant Dk data at 3 points and take the average value.
5.消耗系数(Dissipation factor)测试：5. Dissipation factor test:
测试方法为将以去除酮箔的玻纤层合板5cm×5cm正方型试片，于105℃烘箱内烘2hr，以厚度测定仪量测厚度，再将试片夹入阻抗分析仪中(Agilent E4991A)，测得3点的消耗系数Df数据后取平均值。The test method is to bake the 5cm×5cm square test piece of the glass fiber laminate with the ketone foil removed, bake it in an oven at 105°C for 2hr, measure the thickness with a thickness measuring instrument, and then clamp the test piece into an impedance analyzer (Agilent E4991A). ), measure the consumption coefficient Df data of 3 points and take the average value.
6.玻璃转移温度(Temperature of glass transition)测试：6. Glass transition temperature (Temperature of glass transition) test:
使用微差扫描热分析仪(Differential scaning calorimeter简称DSC)，升温速率20℃/min。Differential scanning calorimeter (DSC for short) was used, and the heating rate was 20°C/min.
7.分子量Mw：7. Molecular weight Mw:
使用凝胶层析仪GPC分析，并用标准分子量polystyrene校正。GPC analysis was performed using a gel chromatograph and calibrated with standard molecular weight polystyrene.
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