CN118684861A - High heat-resistant, low dielectric and ultraviolet light resistant epoxy resin and composition for PCB substrate and preparation method thereof - Google Patents
High heat-resistant, low dielectric and ultraviolet light resistant epoxy resin and composition for PCB substrate and preparation method thereof Download PDFInfo
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 86
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 86
- 239000000758 substrate Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000000203 mixture Substances 0.000 title claims abstract description 28
- 229920005989 resin Polymers 0.000 claims abstract description 126
- 239000011347 resin Substances 0.000 claims abstract description 126
- 239000003054 catalyst Substances 0.000 claims abstract description 62
- 239000002904 solvent Substances 0.000 claims abstract description 47
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 45
- 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 abstract description 25
- 239000011342 resin composition Substances 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 20
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 claims abstract description 16
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011256 inorganic filler Substances 0.000 claims abstract description 12
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 12
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims abstract description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 48
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 40
- 238000004821 distillation Methods 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 24
- 239000000126 substance Substances 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 19
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 16
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 13
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 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
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 230000006750 UV protection Effects 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000008096 xylene Substances 0.000 claims description 8
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 7
- 238000001308 synthesis method Methods 0.000 claims description 7
- LLPKQRMDOFYSGZ-UHFFFAOYSA-N 2,5-dimethyl-1h-imidazole Chemical compound CC1=CN=C(C)N1 LLPKQRMDOFYSGZ-UHFFFAOYSA-N 0.000 claims description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 6
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 claims description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 5
- 229910015900 BF3 Inorganic materials 0.000 claims description 5
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 5
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 5
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 5
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 claims description 3
- ODJKHOBNYXJHRG-UHFFFAOYSA-N 1,3-dimethylimidazole Chemical compound CN1[CH]N(C)C=C1 ODJKHOBNYXJHRG-UHFFFAOYSA-N 0.000 claims description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 229910021485 fumed silica Inorganic materials 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- 239000004005 microsphere Substances 0.000 claims description 3
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 239000000454 talc Substances 0.000 claims description 3
- 235000012222 talc Nutrition 0.000 claims description 3
- 229910052623 talc Inorganic materials 0.000 claims description 3
- 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 claims description 3
- HDPBBNNDDQOWPJ-UHFFFAOYSA-N 4-[1,2,2-tris(4-hydroxyphenyl)ethyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)C(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 HDPBBNNDDQOWPJ-UHFFFAOYSA-N 0.000 abstract description 24
- 230000009471 action Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000009826 distribution Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000010025 steaming Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000013473 artificial intelligence Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000003049 inorganic solvent Substances 0.000 description 1
- 229910001867 inorganic solvent Inorganic materials 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
Abstract
The invention discloses a composition for high heat resistance, low dielectric and ultraviolet light resistant epoxy resin and PCB substrate shown in formula (I) and a preparation method thereof; the dicyclopentadiene and tetraphenolethane resin are adopted to form an intermediate under the action of a catalyst, and then react with epoxy chloropropane to synthesize epoxy resin; the resin composition for the PCB substrate is formed by mixing 100 parts by mass of high heat-resistant, low-dielectric and ultraviolet-resistant epoxy resin, 20-50 parts by mass of maleimide resin, 5-10 parts by mass of main chain type benzoxazine resin, 5-10 parts by mass of DCPD-tetraphenolethane resin, 0.5-3.5 parts by mass of imidazole catalyst, 90-300 parts by mass of inorganic filler and 70-300 parts by mass of solvent. The composition for the epoxy resin and the PCB substrate has the characteristics of low dielectric constant, low dielectric loss, ultraviolet light resistance and the like, and is suitable for manufacturing high-frequency and high-speed PCB substrates.
Description
Technical Field
The invention belongs to epoxy resin and composition for a PCB substrate and preparation thereof, and relates to epoxy resin and composition for a PCB substrate with high heat resistance, low dielectric property and ultraviolet light resistance and a preparation method thereof. The composition for the epoxy resin and the PCB substrate has the characteristics of low dielectric constant, low dielectric loss, ultraviolet light resistance and the like, and is particularly suitable for manufacturing high-frequency and high-speed PCB substrates.
Background
With the rapid development of artificial intelligence and 5G communication, the application end puts forward requirements on high precision, high density, high reliability, high frequency, high speed and the like on a printed circuit board (PCB for short), namely, the PCB substrate is required to have low dielectric property, high heat resistance, high dimensional stability and the like. In addition, the appearance requirements of the PCB substrate are becoming more and more stringent, and the substrate must have a function of shielding ultraviolet rays in order to prevent ghost images caused by the mutual influence of both sides of the PCB when the PCB is exposed. In the prior art, the substrate generally adopts tetrafunctional epoxy resin as an ultraviolet light shielding agent, for example: the invention patent application CN106189083A discloses a glass fiber cloth reinforced copper-clad plate, the CN101914265A discloses a halogen-free phosphorus-containing flame-retardant high-frequency epoxy resin composition and application thereof in bonding sheets and copper-clad plates, and the CN108676475A discloses a halogen-free resin composition, a covering film for flexible printed circuit boards, a flexible copper-clad plate and a preparation method thereof, wherein the adopted tetraphenolethane epoxy resin molecular structure contains 4 delocalized large pi bonds, the system energy is low and stable, most of the energy can be absorbed when irradiated by ultraviolet light, the ultraviolet light resistant characteristic is achieved, the tetraphenolethane epoxy resin is polyfunctional epoxy resin, a compact crosslinked structure can be formed after curing, the heat resistance of the board is improved, on the other hand, the tetraphenolethane epoxy resin has poorer self dielectric property, the low dielectric property of the board can be achieved only by being matched with other low dielectric resins, and the application of the tetraphenolethane epoxy resin in the field of PCB substrate is limited; the dicyclopentadiene (DCPD) epoxy resin has better dielectric property because the structure of the dicyclopentadiene epoxy resin contains nonpolar dicyclopentadiene framework, so that the free volume of molecules is increased; however, since the DCPD structure is an alicyclic chain, the DCPD epoxy resin has low heat resistance.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a composition for high heat resistance, low dielectric and ultraviolet light resistant epoxy resin and PCB substrate and a preparation method thereof. The invention firstly adopts dicyclopentadiene (DCPD) and tetraphenolethane resin to form an intermediate DCPD-tetraphenolethane resin under the action of a catalyst, and then the intermediate reacts with epoxy chloropropane under an alkaline environment to synthesize DCPD-tetraphenolethane epoxy resin (namely, high heat-resistant, low dielectric and ultraviolet light resistant epoxy resin); and then mixing the synthesized DCPD-tetraphenolethane epoxy resin with maleimide resin, main chain benzoxazine resin, DCPD-tetraphenolethane resin, imidazole catalyst, inorganic filler and solvent to obtain the composition for the PCB substrate, thereby providing the composition for the high heat resistance, low dielectric and ultraviolet light resistance epoxy resin and the PCB substrate and the preparation method thereof.
The invention comprises the following steps: an epoxy resin with high heat resistance, low dielectric and ultraviolet light resistance, which is characterized in that: the high heat-resistant, low-dielectric and ultraviolet light resistant epoxy resin (or DCPD-tetraphenolethane epoxy resin) has a chemical structural formula shown in a formula (I):
in formula (I): n 1、n2 is 0 to 6;
The number average molecular weight range of the DCPD-tetraphenolethane epoxy resin is 600-1000, the molecular weight distribution coefficient is 1.2-1.6, and the epoxy equivalent is 210-250 g/eq;
the definition of the molecular weight distribution coefficient is: the ratio of the weight average molecular weight to the number average molecular weight of the sample (i.e., the DCPD-tetraphenolethane epoxy resin produced);
The definition of the epoxy equivalent is: 1g of the mass of epoxy groups contained in the sample (i.e., the DCPD-tetraphenolethane epoxy resin produced) as a percentage of the total mass;
in the content of the invention: the preparation method of the high heat-resistant, low dielectric and ultraviolet light-resistant epoxy resin comprises the following steps: the DCPD-tetraphenolethane resin reacts with epoxy chloropropane and an alkaline catalyst to obtain the high heat-resistant, low-dielectric and ultraviolet-resistant epoxy resin.
The preparation method of the high heat-resistant, low dielectric and ultraviolet light-resistant epoxy resin specifically comprises the following steps: adding 1mol of DCPD-tetraphenolethane resin and 4mol to 8mol of epichlorohydrin into a four-port reactor provided with a stirring device, a thermometer and a condensing tube, heating to 50 to 90 ℃ and stirring for 1h, uniformly dripping 100 to 400g of alkaline catalyst by using a constant-pressure dripping funnel, controlling the dripping time to be 60 to 120min, maintaining the temperature to be 50 to 90 ℃ in the dripping process, and maintaining the temperature for 2 to 4h after the dripping is finished; removing excessive epichlorohydrin by reduced pressure distillation, dissolving with 1000-2000 mL of toluene, cooling to 40-60 ℃, adding 20-200 g of alkaline catalyst, maintaining 40-80 ℃ for reacting for 60-180 min, layering, and reserving a resin layer; washing the resin layer to neutrality, and rotary distilling to eliminate solvent to obtain epoxy resin with high heat resistance, low dielectric and ultraviolet resistance.
The chemical structural formula of the DCPD-tetraphenolethane resin is shown as the following formula (II):
In formula (II): n 1、n2 is 0 to 6.
The number average molecular weight of the DCPD-tetraphenolethane resin ranges from 450 to 800, the molecular weight distribution coefficient ranges from 1.2 to 1.5, and the hydroxyl equivalent weight ranges from 125 to 160g/eq;
The definition of the molecular weight distribution coefficient is: the ratio of the weight average molecular weight to the number average molecular weight of the sample (i.e., the DCPD-tetraphenolethane resin produced);
The definition of the hydroxyl equivalent is: 1g of the mass of hydroxyl groups contained in the sample (i.e., the DCPD-tetraphenolethane resin produced) as a percentage of the total mass;
The alkaline catalyst is one or a mixture of two of 30-70% sodium hydroxide aqueous solution and 30-70% potassium hydroxide aqueous solution.
The synthesis method of the DCPD-tetraphenolethane resin (or DCPD-tetraphenolethane) comprises the following steps:
a. Adding 1mol of dicyclopentadiene (DCPD for short), 1-4 mol of tetraphenolethane and 300g of solvent into a reactor A provided with a stirring thermometer and a (spherical) condensing tube, heating to 80-120 ℃ to maintain stirring and dissolving for 0.5h, mixing and stirring uniformly catalyst A accounting for 1%o-1% of the weight of the tetraphenolethane and 100g of methanol, and adding into a (constant pressure dropping) funnel for standby;
b. After the raw materials in the reactor A are stirred and dissolved (ended), switching the reactor A device into a distillation device (timely steaming out the methanol solvent in the system), starting to dropwise add (constant-pressure dropping) the catalyst A solution in a funnel, and maintaining the reaction temperature at 80-100 ℃ in the dropwise adding process after the dropwise adding is completed within 1-3 h;
c. After the dripping is finished, the device of the reactor A is switched to a reflux device, and the reaction is maintained at 100-140 ℃ for 2-4 h;
d. Switching the reactor A device into a distillation device, decompressing and distilling out the solvent in the reactor A, pouring out the resin in the reactor A when the resin is hot, and cooling to obtain (tan) DCPD-tetraphenolethane resin (solid);
The catalyst A is one or a mixture of more than two of boron trifluoride diethyl ether, trifluoromethanesulfonic acid, anhydrous aluminum trichloride, p-toluenesulfonic acid, boron trifluoride, stannic chloride, ferric trichloride, concentrated sulfuric acid and phosphoric acid;
The solvent is one or more than two of toluene, xylene, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol methyl ether and ethylene glycol methyl ether;
the chemical structural formula of the tetraphenolethane is shown as the following formula (III), which is purchased from Shandong Ai Mengte new materials Co., ltd,
Another aspect of the invention is: a resin composition for a PCB substrate is characterized in that: the resin composition for the PCB substrate is formed by mixing 100 parts by mass of high heat-resistant, low-dielectric and ultraviolet-resistant epoxy resin, 20-50 parts by mass of maleimide resin, 5-10 parts by mass of main chain type benzoxazine resin, 5-10 parts by mass of DCPD-tetraphenolethane resin, 0.5-3.5 parts by mass of imidazole catalyst, 90-300 parts by mass of inorganic filler and 70-300 parts by mass of solvent;
The high heat-resistant, low-dielectric and ultraviolet light-resistant epoxy resin has a chemical structural formula shown in a formula (I):
In formula (I): n 1、n2 is 0 to 6.
The number average molecular weight range of the DCPD-tetraphenolethane epoxy resin is 600-1000, the molecular weight distribution coefficient is 1.2-1.6, and the epoxy equivalent is 210-250 g/eq;
the definition of the molecular weight distribution coefficient is: the ratio of the weight average molecular weight to the number average molecular weight of the sample (i.e., the DCPD-tetraphenolethane epoxy resin produced);
The definition of the epoxy equivalent is: 1g of the mass of epoxy groups contained in the sample (i.e., the DCPD-tetraphenolethane epoxy resin produced) as a percentage of the total mass;
the chemical structural formula of the DCPD-tetraphenolethane resin is shown as the following formula (II):
In formula (II): n 1、n2 is 0 to 6;
The number average molecular weight of the DCPD-tetraphenolethane resin ranges from 450 to 800, the molecular weight distribution coefficient ranges from 1.2 to 1.5, and the hydroxyl equivalent weight ranges from 125 to 160g/eq;
The definition of the molecular weight distribution coefficient is: the ratio of the weight average molecular weight to the number average molecular weight of the sample (i.e., the DCPD-tetraphenolethane resin produced);
The definition of the hydroxyl equivalent is: 1g of the mass of hydroxyl groups contained in the sample (i.e., the DCPD-tetraphenolethane resin produced) as a percentage of the total mass;
the chemical structural formula of the maleimide resin is shown as the following formula (IV):
R 1 is-H, -CH 3;R2 is-H, -CH 3、-CH2CH3;
The maleimide resin is selected from one or more of DFE928, DFE930 and DFE936 of Sichuan Dong materials technology group Co., ltd.
The chemical structural formula of the main chain type benzoxazine resin is shown as the following formula (V);
In formula (V): n is 1-10;
R 3 is -CH2-、-SO2、-O-、-CO-、-S2-、-(CH2)2-、-(CH2)4-、-(CH2)6-、
-(CH2)8-、-(CH2)10-,-(CH2)12-，
R 4 is -CH2-、-SO2、-C(CH3)2-、-C(CH3)(C2H5)-、-C(CF3)2-、
The main chain benzoxazine resin is selected from one or more than two of DFE149, DFE152 and DFE153 of Sichuan Material technology group Co.
The imidazole catalyst is one or a mixture of more than two of imidazole, 2-methylimidazole, 1, 2-dimethylimidazole, 1, 3-dimethylimidazole and 2, 4-dimethylimidazole;
The solvent is one or more than two of acetone, butanone, toluene, xylene, cyclohexanone, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, N-dimethylformamide, N-dimethylacetamide and methyl isobutyl ketone;
The inorganic filler is one or more than two of montmorillonite, calcium carbonate, magnesium hydroxide, zinc borate, talcum, aluminum hydroxide, kaolin, barium sulfate, silicon dioxide, silicon micropowder, mica powder, hollow glass microsphere and fumed silica.
In another aspect of the invention: the preparation method of the high heat-resistant, low dielectric and ultraviolet light-resistant epoxy resin comprises the following steps: the DCPD-tetraphenolethane resin reacts with epoxy chloropropane and an alkaline catalyst to obtain the high heat-resistant, low-dielectric and ultraviolet-resistant epoxy resin.
The preparation method of the high heat-resistant, low dielectric and ultraviolet light-resistant epoxy resin specifically comprises the following steps: adding 1mol of DCPD-tetraphenolethane resin and 4mol to 8mol of epichlorohydrin into a four-port reactor provided with a stirring device, a thermometer and a condensing tube, heating to 50 to 90 ℃ and stirring for 1h, uniformly dripping 100 to 400g of alkaline catalyst by using a constant-pressure dripping funnel, controlling the dripping time to be 60 to 120min, maintaining the temperature to be 50 to 90 ℃ in the dripping process, and maintaining the temperature for 2 to 4h after the dripping is finished; removing excessive epichlorohydrin by reduced pressure distillation, dissolving with 1000-2000 mL of toluene, cooling to 40-60 ℃, adding 20-200 g of alkaline catalyst, maintaining 40-80 ℃ for reacting for 60-180 min, layering, and reserving a resin layer; washing the resin layer to neutrality, and rotary distilling to remove solvent to obtain epoxy resin with high heat resistance, low dielectric and ultraviolet resistance;
The alkaline catalyst is one or a mixture of two of 30-70% sodium hydroxide aqueous solution and 30-70% potassium hydroxide aqueous solution.
The synthesis method of the DCPD-tetraphenolethane resin (or DCPD-tetraphenolethane) comprises the following steps:
a. Adding 1mol of dicyclopentadiene (DCPD for short), 1-4 mol of tetraphenolethane and 300g of solvent into a reactor A provided with a stirring thermometer and a (spherical) condensing tube, heating to 80-120 ℃ to maintain stirring and dissolving for 0.5h, mixing and stirring uniformly catalyst A accounting for 1%o-1% of the weight of the tetraphenolethane and 100g of methanol, and adding into a (constant pressure dropping) funnel for standby;
b. After the raw materials in the reactor A are stirred and dissolved (ended), switching the reactor A device into a distillation device (timely steaming out the methanol solvent in the system), starting to dropwise add (constant-pressure dropping) the catalyst A solution in a funnel, and maintaining the reaction temperature to be 80-100 ℃ in the dropwise adding process after the dropwise adding is completed within 1-3 hours;
c. After the dripping is finished, the device of the reactor A is switched to a reflux device, and the reaction is maintained at 100-140 ℃ for 2-4 h;
d. Switching the reactor A device into a distillation device, decompressing and distilling out the solvent in the reactor A, pouring out the resin in the reactor A when the resin is hot, and cooling to obtain (tan) DCPD-tetraphenolethane resin (solid);
The catalyst A is one or a mixture of more than two of boron trifluoride diethyl ether, trifluoromethanesulfonic acid, anhydrous aluminum trichloride, p-toluenesulfonic acid, boron trifluoride, stannic chloride, ferric trichloride, concentrated sulfuric acid and phosphoric acid;
The solvent is one or more than two of toluene, xylene, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol methyl ether and ethylene glycol methyl ether;
the chemical structural formula of the tetraphenolethane is shown as the following formula (III), which is purchased from Shandong Ai Mengte new materials Co., ltd,
Another aspect of the invention is: the preparation method of the resin composition for the PCB substrate comprises the steps of mixing and stirring 100 parts by mass of high heat-resistant, low-dielectric and ultraviolet-resistant epoxy resin, 20-50 parts by mass of maleimide resin, 5-10 parts by mass of main chain benzoxazine resin, 5-10 parts by mass of DCPD-tetraphenolethane resin, 0.5-3.5 parts by mass of imidazole catalyst, 90-300 parts by mass of inorganic filler and 70-300 parts by mass of solvent uniformly at room temperature to obtain the resin composition for the PCB substrate;
the solid content of the prepared composition for the PCB substrate is 60% -76%;
The definition of the solid content is as follows: 1gPCB the total mass of the substances other than the solvent contained in the composition for a substrate is a percentage of the total mass.
Compared with the prior art, the invention has the following characteristics and beneficial effects:
(1) By adopting the invention, the DCPD structure is introduced into the tetraphenolethane epoxy resin to prepare the epoxy resin with high heat resistance, low dielectric and ultraviolet resistance, and the nonpolar double alicyclic chain segment has larger free volume, so that the dielectric constant and dielectric loss of the condensate can be effectively reduced; the four-functional epoxy structure is introduced into the structure, so that the crosslinking density of the system is greatly improved after curing, the benzene ring content in the molecular structure is increased, the heat resistance of the resin is improved, and the Tg is more than or equal to 210 ℃; the structure contains 4 delocalized large pi bonds, the system energy is low and stable, and most of energy can be absorbed when the ultraviolet light is used for irradiation, thus playing a role in ultraviolet light resistance
(2) In the resin composition for the PCB substrate, the maleimide resin is introduced into the formula, so that the dielectric constant and dielectric loss of the product are further reduced, and the heat resistance is further improved; by introducing main chain type benzoxazine resin, carbon and nitrogen in the structure are utilized to cooperate to play a role of a flame retardant; the DCPD-tetraphenolethane resin is introduced, and the product has smaller molecular polarity and excellent dielectric property due to the better reactivity and lower dielectric constant brought by DCPD ring;
(3) The invention provides a resin composition for a PCB substrate, which is prepared by pressing: the dielectric constant is less than or equal to 3.40; the dielectric loss is less than or equal to 0.007; the heat resistance Td is 5 percent or more than 390 ℃, and the Tg is more than 220 ℃; flame retardant: UL-V0 grade; the resin has the characteristics of low dielectric constant, low dielectric loss, high glass transition temperature and good flame retardance, has excellent comprehensive performance, and can be used as resin for high-performance PCB substrates;
(4) The product of the invention has simple preparation process, good product performance and strong practicability.
Detailed Description
The following examples are intended to further illustrate the present invention but are not to be construed as limiting its scope, as many insubstantial modifications and adaptations of the invention that are within the scope of the invention as described above would be within the skill of the art.
First part preparation of DCPD-tetraphenolethane resin
Examples 1-1 to 1-4:
The synthesis of DCPD-tetraphenolethane resin includes the following steps:
a. Adding 1mol of dicyclopentadiene (DCPD for short), 1-4 mol of tetraphenolethane and 300g of solvent into a reactor A provided with a stirring thermometer and a spherical condensing tube, heating to 80-120 ℃ to maintain stirring and dissolving for 0.5h, mixing and stirring uniformly catalyst A accounting for 1%o-1% of the weight of the tetraphenolethane and 100g of methanol, and adding into a constant-pressure dropping funnel for standby;
b. After the raw materials in the reactor A are stirred and dissolved (ended), switching the reactor A device into a distillation device (timely steaming out the methanol solvent in the system), starting to dropwise add the catalyst A solution in a constant-pressure dropping funnel, and maintaining the reaction temperature at 80-100 ℃ in the dropwise adding process after the dropwise adding is completed within 1-3 hours;
c. After the dripping is finished, the device of the reactor A is switched to a reflux device, and the reaction is maintained at 100-140 ℃ for 2-4 h;
d. Switching the reactor A device into a distillation device, decompressing and distilling out the solvent in the reactor A, pouring out the resin in the reactor A when the resin is hot, and cooling to obtain the tan DCPD-tetraphenolyl ethane resin (solid);
examples 1-4 specific raw material amounts of each component, process parameters and performance parameters for preparing DCPD-tetraphenolethane resins are shown in Table 1 below:
table 1:
the second part is used for preparing the epoxy resin with high heat resistance, low dielectric and ultraviolet light resistance
Examples 2-1 to 2-4:
The preparation method of the epoxy resin with high heat resistance, low dielectric and ultraviolet light resistance comprises the following specific steps: adding 1mol of DCPD-tetraphenolethane resin (prepared in examples 1-4) and 4 mol-8 mol of epichlorohydrin into a four-port reactor provided with a stirring device, a thermometer and a condensing tube, heating to 50-90 ℃ and stirring for 1h, uniformly dripping 100-400 g of alkaline catalyst by using a constant-pressure dropping funnel, controlling the dripping time to 60-120 min, maintaining the temperature at 50-90 ℃ in the dripping process, and maintaining the temperature for 2-4 h after the dripping is finished; removing excessive epichlorohydrin by reduced pressure distillation, dissolving with 1000-2000 mL of toluene, cooling to 40-60 ℃, adding 20-200 g of alkaline catalyst, maintaining 40-80 ℃ for reacting for 60-180 min, layering, and reserving a resin layer; washing the resin layer to neutrality, and rotary distilling to remove solvent to obtain epoxy resin with high heat resistance, low dielectric and ultraviolet resistance;
The alkaline catalyst is one or a mixture of two of 30-70% sodium hydroxide aqueous solution and 30-70% potassium hydroxide aqueous solution.
Examples 2-1 to 2-4 specific raw material amounts, process parameters (arranged according to the time sequence of the reaction) and performance technical indexes of each component in the preparation of the high heat-resistant, low dielectric and ultraviolet light resistant epoxy resin are shown in the following table 2:
Table 2:
Note that: the high heat, low dielectric, ultraviolet light resistant epoxy resin and phenol novolac resin (EMTP 141 of new materials Co., ltd. In Shandong Ai Mengte) prepared in examples 2-1 to 2-4 were prepared in a weight ratio of 10:2, pouring into an aluminum box, curing at 140 ℃ for 1h,160 ℃ for 1h,180 ℃ for 1h, and 200 ℃ for 2h, and testing the heat resistance Tg of the cured product.
Third part of preparation of resin composition for PCB substrate, and Board and performance results
Examples 3-1 to 3-4:
Preparation of a resin composition for a PCB substrate: the resin composition for the PCB substrate consists of 100 parts by mass of high heat-resistant, low dielectric and ultraviolet light-resistant epoxy resin, 20-50 parts by mass of maleimide resin, 5-10 parts by mass of main chain type benzoxazine resin, 5-10 parts by mass of DCPD-tetraphenolethane resin, 0.5-3.5 parts by mass of imidazole catalyst, 90-300 parts by mass of inorganic filler and 70-300 parts by mass of solvent; and mixing and stirring the raw materials at room temperature uniformly to obtain the resin composition for the PCB substrate.
Comparative examples 1-2: in the PCB composition, the high heat resistance, low dielectric and ultraviolet light resistant epoxy resin is replaced by tetraphenolethane epoxy resin, which is purchased from Shandong Ai Mengte new materials Co., ltd, and has the model number of EMTE/EMTE H.
Examples 2-1 to 2-4 resin compositions for PCB substrates, the specific amounts of raw materials (unit: g) of the respective components in comparative examples 1-2 are shown in Table 3 below:
Table 3:
Note that: tetraphenolethyleneoxide (I) is EMTE H of Shandong Ai Mengte New Material Co., ltd, and tetraphenolethyleneoxide (II) is EMTE H of Shandong Ai Mengte New Material Co., ltd; the maleimide resin was DFE936 of Sichuan Material technologies Co., ltd, and the main chain benzoxazine resin was DFE149 of Sichuan Material technologies Co., ltd.
Examples 4-1 to 4-4:
Preparing a PCB substrate: 8 pieces of E-glass fiber cloth with the thickness of 0.2mm are immersed in the resin composition (glue solution) for the PCB substrate for 1h, taken out and dried, and then baked for 4 to 7 minutes in an oven at the temperature of 130 to 170 ℃ to obtain a prepreg; and (3) laminating the prepregs, and carrying out copper foil on two sides or one side of the prepregs, and pressing for 1-4 hours at the pressure of 0.2-3 MPa and the temperature of 130-250 ℃ to obtain the PCB substrate.
Comparative examples 3 to 4: comparative example 1 and comparative example 2 in table 3 were pressed into PCB substrates according to the preparation process of the PCB substrates.
The performance results of the PCB substrates prepared in examples 4-1 to 4-4 and comparative examples 3-4 are shown in Table 4 below:
Table 4:
The technical performance test method in table 4 is as follows:
(1) Dielectric constant
The dielectric constant at 1GHz was determined according to the flat plate method in IPC-TM-650 2.5.5.9.
(2) Dielectric loss tangent
The dielectric loss tangent at 1GHz was measured according to the flat panel method in IPC-TM-650 at 2.5.5.9.
(3) Glass transition temperature (Tg)
The measurement was performed according to the DSC method specified in IPC-TM-650 by 2.4.25.
(4) Thermal decomposition temperature (Td)
The measurement was performed according to the method specified in IPC-TM-650 at 2.4.26.
(5) Flame retardancy
Reference UL94 measurement standard.
As can be seen from table 4, the sheet obtained by applying the examples of the present invention has excellent heat resistance, lower dielectric constant and dielectric loss tangent, and better flame retardancy. The composition can be used for packaging laminated boards and integrated circuits, particularly for the fields of deep high-frequency high-speed PCB substrates, high-density Internet and the like, and has wide application prospect.
Example 5:
a high heat-resistant, low dielectric and ultraviolet light resistant epoxy resin has a chemical structural formula shown in a formula (I):
In formula (I): n 1、n2 is 0 to 6.
Example 6:
the preparation method of the epoxy resin with high heat resistance, low dielectric and ultraviolet light resistance comprises the following steps: the DCPD-tetraphenolethane resin reacts with epoxy chloropropane and an alkaline catalyst to obtain the high heat-resistant, low-dielectric and ultraviolet-resistant epoxy resin.
Example 7:
The preparation method of the epoxy resin with high heat resistance, low dielectric and ultraviolet light resistance comprises the following specific steps: adding 1mol of DCPD-tetraphenolethane resin and 4mol of epoxy chloropropane into a four-port reactor provided with a stirrer, a thermometer and a condenser, heating to 50 ℃ and stirring for 1h, uniformly dripping 100g of alkaline catalyst by using a constant-pressure dripping funnel, controlling the dripping time to be 60min, maintaining the temperature at 50 ℃ in the dripping process, and maintaining the temperature for 4h after the dripping is finished; removing excessive epichlorohydrin by reduced pressure distillation, dissolving with 1000mL of toluene, cooling to 40 ℃, adding 20g of alkaline catalyst, maintaining the temperature at 40 ℃ for reacting for 180min, layering, and reserving a resin layer; washing the resin layer to neutrality, and rotary distilling to eliminate solvent to obtain epoxy resin with high heat resistance, low dielectric and ultraviolet resistance.
Example 8:
The preparation method of the epoxy resin with high heat resistance, low dielectric and ultraviolet light resistance comprises the following specific steps: adding 1mol of DCPD-tetraphenolethane resin and 8mol of epoxy chloropropane into a four-port reactor provided with a stirrer, a thermometer and a condenser, heating to 90 ℃ and stirring for 1h, uniformly dripping 400g of alkaline catalyst by using a constant-pressure dripping funnel, controlling the dripping time to 120min, maintaining the temperature at 90 ℃ in the dripping process, and maintaining the temperature for 2h after the dripping is finished; removing excessive epichlorohydrin by reduced pressure distillation, dissolving with 2000mL of toluene, cooling to 60 ℃, adding 200g of alkaline catalyst, maintaining at 80 ℃ for reaction for 60min, layering, and reserving a resin layer; washing the resin layer to neutrality, and rotary distilling to eliminate solvent to obtain epoxy resin with high heat resistance, low dielectric and ultraviolet resistance.
Example 9:
the preparation method of the epoxy resin with high heat resistance, low dielectric and ultraviolet light resistance comprises the following specific steps: adding 1mol of DCPD-tetraphenolethane resin and 6mol of epoxy chloropropane into a four-port reactor provided with a stirrer, a thermometer and a condenser, heating to 70 ℃ and stirring for 1h, uniformly dripping 250g of alkaline catalyst by using a constant-pressure dripping funnel, controlling the dripping time to 90min, maintaining the temperature at 70 ℃ in the dripping process, and maintaining the temperature for 3h after the dripping is finished; removing excessive epichlorohydrin by reduced pressure distillation, dissolving with 1500mL of toluene, cooling to 50 ℃, adding 110g of alkaline catalyst, maintaining at 60 ℃ for reaction for 120min, layering, and reserving a resin layer; washing the resin layer to neutrality, and rotary distilling to eliminate solvent to obtain epoxy resin with high heat resistance, low dielectric and ultraviolet resistance.
In examples 7 to 9 above:
the chemical structural formula of the DCPD-tetraphenolethane resin is shown as the following formula (II):
In formula (II): n 1、n2 is 0 to 6;
The alkaline catalyst is one or two of sodium hydroxide aqueous solution with the mass percent concentration of 30-70% and potassium hydroxide aqueous solution with the mass percent concentration of 30-70%.
Example 10:
In the preparation of the epoxy resin with high heat resistance, low dielectric and ultraviolet light resistance, the synthesis method of the DCPD-tetraphenolethane resin comprises the following steps:
a. Adding 1mol of dicyclopentadiene (DCPD for short), 1mol of tetraphenolethane and 300g of solvent into a reactor A provided with a stirring thermometer and a (spherical) condensing tube, heating to 80 ℃ to maintain stirring and dissolving for 0.5h, mixing and stirring uniformly 1%o of the weight of the tetraphenolethane of the catalyst A with 100g of methanol, and adding into a (constant pressure dropping) funnel for later use;
b. After the raw materials in the reactor A are stirred and dissolved (ended), switching the reactor A device into a distillation device (timely evaporating a methanol solvent in a system), starting to dropwise add (constant-pressure dropping) the catalyst A solution in a funnel, and maintaining the reaction temperature at 80 ℃ in the dropwise adding process after the dropwise adding is completed in 1 h;
c. after the dripping is finished, the device of the reactor A is switched to a reflux device, and the reaction is maintained at 100 ℃ for 4 hours;
d. and switching the reactor A device into a distillation device, decompressing and distilling the solvent in the reactor A, pouring out the resin in the reactor A when the resin is hot, and cooling to obtain (tan) DCPD-tetraphenolethane resin (solid).
Example 11:
In the preparation of the epoxy resin with high heat resistance, low dielectric and ultraviolet light resistance, the synthesis method of the DCPD-tetraphenolethane resin comprises the following steps:
a. Adding 1mol of dicyclopentadiene (DCPD for short), 4mol of tetraphenolethane and 300g of solvent into a reactor A provided with a stirring thermometer and a (spherical) condensing tube, heating to 120 ℃ to maintain stirring and dissolving for 0.5h, mixing and stirring a catalyst A accounting for 1% of the weight of the tetraphenolethane with 100g of methanol uniformly, and adding into a (constant pressure dropping) funnel for later use;
b. After the raw materials in the reactor A are stirred and dissolved (ended), switching the reactor A device into a distillation device (timely evaporating a methanol solvent in a system), starting to dropwise add (constant-pressure dropping) the catalyst A solution in a funnel, and maintaining the reaction temperature at 100 ℃ in the dropwise adding process after 3 hours;
c. after the dripping is finished, the device of the reactor A is switched to a reflux device, and the reaction is maintained at 140 ℃ for 2 hours;
d. and switching the reactor A device into a distillation device, decompressing and distilling the solvent in the reactor A, pouring out the resin in the reactor A when the resin is hot, and cooling to obtain (tan) DCPD-tetraphenolethane resin (solid).
Example 12:
In the preparation of the epoxy resin with high heat resistance, low dielectric and ultraviolet light resistance, the synthesis method of the DCPD-tetraphenolethane resin comprises the following steps:
a. Adding 1mol of dicyclopentadiene (DCPD for short), 2.5mol of tetraphenolethane and 300g of solvent into a reactor A provided with a stirring thermometer and a (spherical) condensing tube, heating to 100 ℃ to maintain stirring and dissolving for 0.5h, mixing and stirring a catalyst A accounting for 0.5% of the weight of the tetraphenolethane and 100g of methanol uniformly, and adding into a (constant pressure dropping) funnel for standby;
b. After the raw materials in the reactor A are stirred and dissolved (ended), switching the reactor A device into a distillation device (timely evaporating a methanol solvent in a system), starting to dropwise add (constant-pressure dropping) the catalyst A solution in a funnel, and maintaining the reaction temperature at 90 ℃ in the dropwise adding process after the dropwise adding is completed in 2 hours;
c. after the dripping is finished, the device of the reactor A is switched to a reflux device, and the reaction is carried out for 3 hours at 120 ℃;
d. and switching the reactor A device into a distillation device, decompressing and distilling the solvent in the reactor A, pouring out the resin in the reactor A when the resin is hot, and cooling to obtain (tan) DCPD-tetraphenolethane resin (solid).
In the above examples 10 to 12:
The catalyst A is one or a mixture of more than two of boron trifluoride diethyl ether, trifluoromethanesulfonic acid, anhydrous aluminum trichloride, p-toluenesulfonic acid, boron trifluoride, stannic chloride, ferric trichloride, concentrated sulfuric acid and phosphoric acid;
The solvent is one or more than two of toluene, xylene, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol methyl ether and ethylene glycol methyl ether;
the chemical structural formula of the tetraphenolethane is shown as the following formula (III), and the tetraphenolethane is purchased from Shandong Ai Mengte new materials Co., ltd;
example 13:
the resin composition for the PCB substrate is prepared by mixing 100 parts by mass of high heat-resistant, low-dielectric and ultraviolet-resistant epoxy resin, 20 parts by mass of maleimide resin, 5 parts by mass of main chain benzoxazine resin, 5 parts by mass of DCPD-tetraphenolethane resin, 0.5 part by mass of imidazole catalyst, 90 parts by mass of inorganic filler and 70 parts by mass of solvent; and mixing and stirring the raw materials at room temperature uniformly to obtain the resin composition for the PCB substrate.
Example 14:
The resin composition for the PCB substrate is prepared by mixing 100 parts by mass of high heat-resistant, low-dielectric and ultraviolet-resistant epoxy resin, 50 parts by mass of maleimide resin, 10 parts by mass of main chain benzoxazine resin, 10 parts by mass of DCPD-tetraphenolethane resin, 3.5 parts by mass of imidazole catalyst, 300 parts by mass of inorganic filler and 300 parts by mass of solvent; and mixing and stirring the raw materials at room temperature uniformly to obtain the resin composition for the PCB substrate.
Example 15:
The resin composition for the PCB substrate is prepared by mixing 100 parts by mass of high heat-resistant, low-dielectric and ultraviolet-resistant epoxy resin, 35 parts by mass of maleimide resin, 7 parts by mass of main chain benzoxazine resin, 8 parts by mass of DCPD-tetraphenolethane resin, 2 parts by mass of imidazole catalyst, 190 parts by mass of inorganic filler and 190 parts by mass of solvent; and mixing and stirring the raw materials at room temperature uniformly to obtain the resin composition for the PCB substrate.
In examples 13 to 15 described above:
The high heat-resistant, low-dielectric and ultraviolet light-resistant epoxy resin has a chemical structural formula shown in a formula (I):
in formula (I): n 1、n2 is 0 to 6;
The preparation method of the high heat-resistant, low dielectric and ultraviolet light resistant epoxy resin is the same as any one of the above embodiments 7 to 9;
the chemical structural formula of the DCPD-tetraphenolethane resin is shown as the following formula (II):
In formula (II): n 1、n2 is 0 to 6;
The preparation method of the DCPD-tetraphenolethane resin is the same as any one of the above examples 10 to 12;
the chemical structural formula of the maleimide resin is shown as the following formula (IV):
R 1 is-H, -CH 3;R2 is-H, -CH 3、-CH2CH3;
The maleimide resin is selected from one or more than two of DFE928, DFE930 and DFE936 of Sichuan Dong materials technology group Co., ltd;
The chemical structural formula of the main chain type benzoxazine resin is shown as the following formula (V);
In formula (V): n is 1-10;
R 3 is -CH2-、-SO2、-O-、-CO-、-S2-、-(CH2)2-、-(CH2)4-、-(CH2)6-、-(CH2)8-、-(CH2)10-,-(CH2)12-,
R 4 is -CH2-、-SO2、-C(CH3)2-、-C(CH3)(C2H5)-、-C(CF3)2-、
The main chain benzoxazine resin is selected from one or more than two of DFE149, DFE152 and DFE153 of Sichuan Material technology group Co., ltd;
The chemical structural formula of the DCPD-tetraphenolethane resin is shown as formula (2);
The imidazole catalyst is one or a mixture of more than two of imidazole, 2-methylimidazole, 1, 2-dimethylimidazole, 1, 3-dimethylimidazole and 2, 4-dimethylimidazole;
The solvent is one or more than two of acetone, butanone, toluene, xylene, cyclohexanone, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, N-dimethylformamide, N-dimethylacetamide and methyl isobutyl ketone;
The inorganic filler is one or more than two of montmorillonite, calcium carbonate, magnesium hydroxide, zinc borate, talcum, aluminum hydroxide, kaolin, barium sulfate, silicon dioxide, silicon micropowder, mica powder, hollow glass microsphere and fumed silica.
In the above embodiment: the percentages used are not particularly indicated, and are all percentages by mass (weight) or percentages known to those skilled in the art; the proportions used are not particularly specified, but are mass (weight) proportions; the parts by weight may all be g or kg.
In the above embodiment: the process parameters (temperature, time, concentration, etc.) and the amount of each component in each step are within the range, and any point is applicable.
The technical contents of the invention and the technical contents not specifically described in the above embodiments are the same as the prior art, and the raw materials are all commercial products.
The present invention is not limited to the above-described embodiments, and the present invention can be implemented with the above-described advantageous effects.
Claims (8)
1. An epoxy resin with high heat resistance, low dielectric and ultraviolet light resistance, which is characterized in that: the high heat-resistant, low-dielectric and ultraviolet-resistant epoxy resin has a chemical structural formula shown in a formula (I):
In formula (I): n 1、n2 is 0 to 6.
2. The high heat, low dielectric, ultraviolet light resistant epoxy resin of claim 1, wherein: the preparation method of the high heat-resistant, low dielectric and ultraviolet light-resistant epoxy resin comprises the following steps: the DCPD-tetraphenolethane resin reacts with epoxy chloropropane and an alkaline catalyst to obtain the high heat-resistant, low-dielectric and ultraviolet-resistant epoxy resin.
3. The high heat, low dielectric, ultraviolet light resistant epoxy resin of claim 2, wherein: the preparation method of the high heat-resistant, low dielectric and ultraviolet light-resistant epoxy resin specifically comprises the following steps: adding 1mol of DCPD-tetraphenolethane resin and 4mol to 8mol of epichlorohydrin into a four-port reactor provided with a stirring device, a thermometer and a condensing tube, heating to 50 to 90 ℃ and stirring for 1h, uniformly dripping 100 to 400g of alkaline catalyst by using a constant-pressure dripping funnel, controlling the dripping time to be 60 to 120min, maintaining the temperature to be 50 to 90 ℃ in the dripping process, and maintaining the temperature for 2 to 4h after the dripping is finished; removing excessive epichlorohydrin by reduced pressure distillation, dissolving with 1000-2000 mL of toluene, cooling to 40-60 ℃, adding 20-200 g of alkaline catalyst, maintaining 40-80 ℃ for reacting for 60-180 min, layering, and reserving a resin layer; washing the resin layer to neutrality, and rotary distilling to remove solvent to obtain epoxy resin with high heat resistance, low dielectric and ultraviolet resistance;
the chemical structural formula of the DCPD-tetraphenolethane resin is shown as the following formula (II):
In formula (II): n 1、n2 is 0 to 6;
The alkaline catalyst is one or a mixture of two of 30-70% sodium hydroxide aqueous solution and 30-70% potassium hydroxide aqueous solution.
4. A high heat, low dielectric, uv resistant epoxy resin as claimed in claim 2 or 3, characterized in that: the synthesis method of the DCPD-tetraphenolethane resin comprises the following steps:
a. Adding 1mol of dicyclopentadiene, 1-4 mol of tetraphenolyl ethane and 300g of solvent into a reactor A provided with a stirrer, a thermometer and a condenser, heating to 80-120 ℃ to maintain stirring and dissolving for 0.5h, mixing and stirring uniformly catalyst A accounting for 1-1% of the weight of the tetraphenolyl ethane and 100g of methanol, and adding into a funnel for standby;
b. After the raw materials in the reactor A are stirred and dissolved, switching the reactor A device into a distillation device, starting to dropwise add the catalyst A solution in a funnel, and maintaining the reaction temperature at 80-100 ℃ in the dropwise adding process after the dropwise adding is completed within 1-3 hours;
c. After the dripping is finished, the device of the reactor A is switched to a reflux device, and the reaction is maintained at 100-140 ℃ for 2-4 h;
d. switching the reactor A device into a distillation device, decompressing and distilling out the solvent in the reactor A, pouring out the resin in the reactor A while the resin is hot, and cooling to obtain DCPD-tetraphenolyl ethane resin;
The catalyst A is one or a mixture of more than two of boron trifluoride diethyl ether, trifluoromethanesulfonic acid, anhydrous aluminum trichloride, p-toluenesulfonic acid, boron trifluoride, stannic chloride, ferric trichloride, concentrated sulfuric acid and phosphoric acid;
The solvent is one or more of toluene, xylene, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol methyl ether and ethylene glycol methyl ether.
A resin composition for a pcb substrate, characterized by: the resin composition for the PCB substrate is formed by mixing 100 parts by mass of high heat-resistant, low-dielectric and ultraviolet-resistant epoxy resin, 20-50 parts by mass of maleimide resin, 5-10 parts by mass of main chain type benzoxazine resin, 5-10 parts by mass of DCPD-tetraphenolethane resin, 0.5-3.5 parts by mass of imidazole catalyst, 90-300 parts by mass of inorganic filler and 70-300 parts by mass of solvent;
The high heat-resistant, low-dielectric and ultraviolet light-resistant epoxy resin has a chemical structural formula shown in a formula (I):
in formula (I): n 1、n2 is 0 to 6;
the chemical structural formula of the DCPD-tetraphenolethane resin is shown as the following formula (II):
In formula (II): n 1、n2 is 0 to 6;
The chemical structural formula of the maleimide resin is shown as the following formula (IV):
R 1 is-H, -CH 3;R2 is-H, -CH 3、-CH2CH3;
(Ⅳ)
The chemical structural formula of the main chain type benzoxazine resin is shown as the following formula (V);
In formula (V): n is 1-10;
R 3 is -CH2-、-SO2、-O-、-CO-、-S2-、-(CH2)2-、-(CH2)4-、-(CH2)6-、
-(CH2)8-、-(CH2)10-,-(CH2)12-，
R 4 is -CH2-、-SO2、-C(CH3)2-、-C(CH3)(C2H5)-、-C(CF3)2-、
The imidazole catalyst is one or a mixture of more than two of imidazole, 2-methylimidazole, 1, 2-dimethylimidazole, 1, 3-dimethylimidazole and 2, 4-dimethylimidazole;
The solvent is one or more than two of acetone, butanone, toluene, xylene, cyclohexanone, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, N-dimethylformamide, N-dimethylacetamide and methyl isobutyl ketone;
The inorganic filler is one or more than two of montmorillonite, calcium carbonate, magnesium hydroxide, zinc borate, talcum, aluminum hydroxide, kaolin, barium sulfate, silicon dioxide, silicon micropowder, mica powder, hollow glass microsphere and fumed silica.
6. The resin composition for a PCB substrate according to claim 5, wherein: the preparation method of the high heat-resistant, low dielectric and ultraviolet light-resistant epoxy resin comprises the following steps: the DCPD-tetraphenolethane resin reacts with epoxy chloropropane and an alkaline catalyst to obtain the high heat-resistant, low-dielectric and ultraviolet-resistant epoxy resin.
7. The resin composition for a PCB substrate according to claim 6, wherein: the preparation method of the high heat-resistant, low dielectric and ultraviolet light-resistant epoxy resin specifically comprises the following steps: adding 1mol of DCPD-tetraphenolethane resin and 4mol to 8mol of epichlorohydrin into a four-port reactor provided with a stirring device, a thermometer and a condensing tube, heating to 50 to 90 ℃ and stirring for 1h, uniformly dripping 100 to 400g of alkaline catalyst by using a constant-pressure dripping funnel, controlling the dripping time to be 60 to 120min, maintaining the temperature to be 50 to 90 ℃ in the dripping process, and maintaining the temperature for 2 to 4h after the dripping is finished; removing excessive epichlorohydrin by reduced pressure distillation, dissolving with 1000-2000 mL of toluene, cooling to 40-60 ℃, adding 20-200 g of alkaline catalyst, maintaining 40-80 ℃ for reacting for 60-180 min, layering, and reserving a resin layer; washing the resin layer to neutrality, and rotary distilling to remove solvent to obtain epoxy resin with high heat resistance, low dielectric and ultraviolet resistance;
The alkaline catalyst is one or a mixture of two of 30-70% sodium hydroxide aqueous solution and 30-70% potassium hydroxide aqueous solution.
8. The resin composition for a PCB substrate according to claim 5, 6 or 7, wherein: the synthesis method of the DCPD-tetraphenolethane resin comprises the following steps:
a. Adding 1mol of dicyclopentadiene, 1-4 mol of tetraphenolyl ethane and 300g of solvent into a reactor A provided with a stirrer, a thermometer and a condenser, heating to 80-120 ℃ to maintain stirring and dissolving for 0.5h, mixing and stirring uniformly catalyst A accounting for 1-1% of the weight of the tetraphenolyl ethane and 100g of methanol, and adding into a funnel for standby;
b. After the raw materials in the reactor A are stirred and dissolved, switching the reactor A device into a distillation device, starting to dropwise add the catalyst A solution in a funnel, and maintaining the reaction temperature at 80-100 ℃ in the dropwise adding process after the dropwise adding is completed within 1-3 hours;
c. After the dripping is finished, the device of the reactor A is switched to a reflux device, and the reaction is maintained at 100-140 ℃ for 2-4 h;
d. switching the reactor A device into a distillation device, decompressing and distilling out the solvent in the reactor A, pouring out the resin in the reactor A while the resin is hot, and cooling to obtain DCPD-tetraphenolyl ethane resin;
The catalyst A is one or a mixture of more than two of boron trifluoride diethyl ether, trifluoromethanesulfonic acid, anhydrous aluminum trichloride, p-toluenesulfonic acid, boron trifluoride, stannic chloride, ferric trichloride, concentrated sulfuric acid and phosphoric acid;
The solvent is one or more of toluene, xylene, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol methyl ether and ethylene glycol methyl ether.
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|---|---|---|---|
| CN202410910557.2A CN118684861A (en) | 2024-07-09 | 2024-07-09 | High heat-resistant, low dielectric and ultraviolet light resistant epoxy resin and composition for PCB substrate and preparation method thereof |
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| CN202410910557.2A CN118684861A (en) | 2024-07-09 | 2024-07-09 | High heat-resistant, low dielectric and ultraviolet light resistant epoxy resin and composition for PCB substrate and preparation method thereof |
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