CN102786664A - Low dielectric and high heat-resistant epoxy resin composition and its preparation method - Google Patents
Low dielectric and high heat-resistant epoxy resin composition and its preparation method Download PDFInfo
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- CN102786664A CN102786664A CN2012102460890A CN201210246089A CN102786664A CN 102786664 A CN102786664 A CN 102786664A CN 2012102460890 A CN2012102460890 A CN 2012102460890A CN 201210246089 A CN201210246089 A CN 201210246089A CN 102786664 A CN102786664 A CN 102786664A
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 45
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 45
- 239000000203 mixture Substances 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 claims abstract description 22
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims description 22
- 239000004593 Epoxy Substances 0.000 claims description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 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 11
- 238000000034 method Methods 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000009413 insulation Methods 0.000 claims description 8
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 8
- 238000010907 mechanical stirring Methods 0.000 claims description 8
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 7
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- DSCFFEYYQKSRSV-UHFFFAOYSA-N 1L-O1-methyl-muco-inositol Natural products COC1C(O)C(O)C(O)C(O)C1O DSCFFEYYQKSRSV-UHFFFAOYSA-N 0.000 claims description 3
- QNYBOILAKBSWFG-UHFFFAOYSA-N 2-(phenylmethoxymethyl)oxirane Chemical compound C1OC1COCC1=CC=CC=C1 QNYBOILAKBSWFG-UHFFFAOYSA-N 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 239000012456 homogeneous solution Substances 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 230000003252 repetitive effect Effects 0.000 claims description 2
- 238000005201 scrubbing Methods 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 229920001955 polyphenylene ether Polymers 0.000 abstract description 9
- 229920005989 resin Polymers 0.000 abstract description 8
- 239000011347 resin Substances 0.000 abstract description 8
- 239000003989 dielectric material Substances 0.000 abstract description 3
- 239000003085 diluting agent Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 20
- 239000000463 material Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 5
- 238000007306 functionalization reaction Methods 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000002118 epoxides Chemical group 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- OMIHGPLIXGGMJB-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]hepta-1,3,5-triene Chemical compound C1=CC=C2OC2=C1 OMIHGPLIXGGMJB-UHFFFAOYSA-N 0.000 description 1
- 239000004727 Noryl Substances 0.000 description 1
- 229920001207 Noryl Polymers 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002872 contrast media Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- -1 polycyclic heteroaryl oxygen compound Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005549 size reduction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229940126680 traditional chinese medicines Drugs 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
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- Epoxy Resins (AREA)
- Organic Insulating Materials (AREA)
Abstract
The invention relates to high performance resin systems used as dielectric materials, in particular to a low dielectric high heat-resistant epoxy resin composition and its preparation method. Based on the technical problem of poor compatibility in existing polyphenylene ether modified epoxy resin, the invention puts forward the scheme of using polyphenylene ether grafted maleic anhydride and an active diluent to reduce the system viscosity so as to solve the compatibility of polyphenylene ether and epoxy resin, thus improving the dielectric and mechanical properties of the system. By adding a proper amount of TGIC (triglycidyl isocyanurate) to improve the heat resistance of the resin system, a low dielectric and high heat-resistant high performance epoxy resin composition can be prepared.
Description
Technical field
The present invention relates to performance resins system, particularly a kind of low dielectric high heat epoxy composition and method of making the same as dielectric materials.
Background technology
Epoxy resin is owing to having excellent adhesiveproperties, being easy to modification, low cost and good processibility and being widely used in the copper-clad plate baseplate material; But along with the microelectronic growth requirement of semi-conductor in recent years; The copper-clad plate of general property can not satisfy high frequency, at a high speed, high heat-resisting, low dielectric, low-loss demand; Therefore to have a low-k significant with resin with the copper-clad plate of high heat resistance ability in development, is one of effective means the most and prepare high performance resin system.
Ppe (Polyphenyl ether, be called for short PPE), have high glass transition temperature (
T g=210 ℃), low-k (under the 1MHz,
D k=2.45) with low loss factors (
D fAdvantage such as=0.0007), dimensional stability is good and be used to the modification of epoxy resin; But the common engineering plastics with the ppe molecular weight big (
M nGenerally be higher than 21000g/mol), mobile poor, shortcomings such as processing difficulties are restricted it aspect modified epoxy; The method that addresses this is that at present has two kinds: the one, and the molecular weight of reduction ppe; Ppe molecular weight more little difficult more and epoxy resin (the Merfeld G D that is separated; Yeager G W; Chao H S, et al. Phase behavior and morphology of Poly (phenylene ether)/epoxy blend. Polymer, 2003 (44): 4981-4992); The 2nd, functional polyphenylene ether, the functionalization monomer that promptly grafting can react with epoxy on ppe; Usually properties-correcting agent has fumaric acid, epoxy chloropropane, dihydroxyphenyl propane, maleic anhydride etc.; Really having certain effect aspect the consistency of improving ppe and epoxy through these two kinds of more common methods; U.S. Pat 005843565A has disclosed the application of cured article in the copper-clad plate base material of the epoxy resin of a kind of low-molecular-weight ppe and different rings oxygen value; It is that ppe is degraded into small molecular weight very, to reach the purpose of improving the consistency between ppe and the epoxy resin; But test result shows, along with the reduction of the molecular weight of ppe, specific inductivity has also uprised in the time of itself and epoxy resin compatibility property improvement, does not meet the requirement of high performance copper clad laminate; Chinese patent CN1385454 has disclosed a kind of crosslinkable polyphenyl ether PPE resin with epoxy group(ing), and the ppe end after the modification has epoxy group(ing), so and the consistency between the epoxy resin obtain lifting greatly.
Reduce molecular weight and the improvement really of functional polyphenylene ether and the effective ways of epoxy consistency of ppe, except Noryl, the viscosity that can also reduce epoxy resin is to improve both blended homogeneities; Tradition reduces the epoxy method of viscosity and is to use a large amount of organic solvents that they are dissolved in together, for example toluene, acetone, chloroform etc.But big, the toxic not environmental protection of these solvent odor, and do not participate in reaction, still can separation of two phases after the volatilization; Reactive thinner is meant the low molecular weight epoxy compound that contains epoxide group; The curing reaction that they can participate in epoxy resin becomes the part of curable epoxide thing cross-linked network structure; Not only can improve complete processing but also can participate in curing reaction through adding the viscosity that reactive thinner reduces epoxy, the mechanics and the dielectric properties of epoxy-resin systems are all had some improvement; Though the dilution effect of reactive thinner is good, can make the thermotolerance of curable epoxide thing have the reduction of certain amplitude, help to improve the thermotolerance of compsn through adding an amount of trifunctional group cross-linking agent's isocyanuric acid three-glycidyl ester (TGIC).
Summary of the invention
The object of the present invention is to provide a kind of high performance composition epoxy resin; To be used as baseplate material in copper-clad plate; This epoxy resin composite comprises: (a) 100 weight parts bisphenol A type epoxy resin; (b) the ppe grafted maleic anhydride of 10～40 weight parts, number average be at 2000～8000g/mol, (c) 35 weight part high-temperature curing agent diaminodiphenylsulfone(DDS)s (DDS); (d) isocyanuric acid three-glycidyl ester of 1～7 weight part (TGIC), (e) the reactive thinner benzyl glycidyl ether E692 of 10 ~ 20 weight parts.
The structural formula of functional polyphenylene ether:
There is consistency difficult technologies problem in the present invention in view of present polyphenyl ether modified epoxy resin; The viscosity of proposition through using ppe grafted maleic anhydride and reactive thinner reduction system is to solve both compatibility problems; Thereby improve the dielectric and the mechanical property of system; Improve the resistance toheat of resin system through the adding of an amount of TGIC, prepare the high heat-stable high-performance epoxy resin composition of a kind of low dielectric.
The invention provides the preparation method of a kind of number average at the ppe grafted maleic anhydride of 2000～8000g/mol; It is characterized in that following steps: in the four-hole boiling flask of the 500mL that has condensation reflux unit; Add solvent toluene; After being heated to 95 ℃, be that the ratio of 2:1 joins ppe in the toluene according to mass ratio, mechanical stirring is until forming faint yellow homogeneous solution; Add dihydroxyphenyl propane (BPA), treat slowly to add Lucidol (BPO) again after its dissolving, add maleic anhydride after stirring 1h, continue to stir 3h down, be cooled to room temperature at 95 ℃, with the anhydrous methanol repetitive scrubbing more than 3 times, the dry product that gets.
Wherein BPO is 1% ~ 6% of a ppe quality, and BPA is 1% ~ 6% of a ppe quality, and maleic anhydride is 3% of a ppe quality.
The invention provides the preparation method of a kind of reactive thinner and TGIC modified epoxy-polyphenylene ether composition; It is characterized in that following steps: with reactive thinner; Epoxy resin and ppe grafted maleic anhydride mix stirring and are warming up to 130-150 ℃, behind the solution becomes homogeneous transparent to be mixed, behind the insulation 1-3h; Add TGIC, after the dissolving solution is cooled to 90-100 ℃; Add solidifying agent DDS; Stir 20-40min; Put into 90-100 ℃ vacuum drying oven vacuumizing and defoaming 30-50min, the solution that will take off bubble is poured into and is put into baking oven in the tetrafluoroethylene mould of preheating and be cured, at 120 ℃～140 ℃ Procuring 30～50min; Continue to solidify 120～240min at 160 ℃～190 ℃, at 210 ℃～240 ℃ after fixing 120min.
Wherein, by weight calculation, DDS is 35% of an epoxy resin content, and thinner E692 is 10% ~ 20% of an epoxy resin content, and TGIC is 1%～7% of an epoxy resin content, and the ppe grafted maleic anhydride is 10%～40% of a weight epoxy.
Effect of the present invention:
Select the suitable activity thinner; Reduce the viscosity of epoxy resin and improve ppe and the consistency of epoxy resin; Make ppe better in epoxy-resin systems, be uniformly dispersed; Simultaneously thinner has been introduced more phenyl, thereby makes molecule in electric field, polarize to become the difficult specific inductivity that can reduce material, and both interactions are exactly the dielectric materials that has obtained than low-k and dielectric loss; The affiliation that adds by original thinner makes heat-resisting decreasing, and adds the thermotolerance that an amount of TGIC improves compsn; And along with the adding of ppe, thinner and TGIC makes the mechanical property of compsn improve, the high heat-resisting high performance copper clad laminate baseplate material that is fit to very much be applied to of the low dielectric of preparing, concrete performance is seen table one.
Embodiment
To lift several embodiment below so that method of the present invention, characteristic, and advantage to be described, but and unrestricted scope of the present invention:
The functionalization small molecules ppe (PPE-g-MAH) that following examples adopted, number average
Mn=2000 ~ 8000g/mol, the laboratory self-control; Prompt chemical reagent ltd is moistened in Lucidol (BPO) Shanghai; Maleic anhydride, Chemical Reagent Co., Ltd., Sinopharm Group; Dihydroxyphenyl propane (BPA) Hubei Yihua Chemical Industry Co., Ltd.
Epoxy resin is the bisphenol A type epoxy resin of Lanxing Chemical New Material Co., Ltd., and oxirane value is 0.2 ~ 0.56; Isocyanuric acid three-glycidyl ester (TGIC), Yangzhou Sandeli Chemical Co., Ltd. produces; Reactive thinner E692, benzyl glycidyl ether is bought oxirane value >=0.43 from Hubei Greenhome Chemical Co., Ltd.; DDS is biochemical worker ltd purchase in the third of the twelve Earthly Branches from the Suzhou City, belongs to high-temperature curing agent; Toluene and anhydrous methanol solvent are traditional Chinese medicines group reagent.
Following examples 1-4 and Comparative Examples 1 can find out, along with increasing of ppe amount, the specific inductivity of epoxy composite has original 4.36 to be reduced to 3.86; Explain that the little functionalization small molecules ppe of polarity joins in the epoxy composite; Can significantly improve the dielectric properties of matrix material, but the adding of ppe makes vitrifying that reduction slightly arranged, because ppe can be to crosslinked inhibition of epoxy; Reduced cross-linking density; So second-order transition temperature has small size reduction, the ppe of functionalization can react with epoxy resin, has improved the bonding force between the interface; Make the tensile strength of epoxy composite improve, 48.4 MPa bring up to 56.9MPa
.
Following examples 3,5-7 and contrast medium 2 can be found out; Can significantly improve the second-order transition temperature of epoxy composite along with the adding of TGIC; Bring up to 202 ℃ by original 158 ℃; Because TGIC is the polycyclic heteroaryl oxygen compound, has good heat endurance and to the tensile strength effect that also improves.
Following examples 3,8-9 and Comparative Examples 3 can be found out; Along with increasing of reactive thinner amount; Specific inductivity has obvious variation, is reduced to 3.72 by original 4.23, because thinner can reduce the viscosity of epoxy; Thereby the dissolving and the reactive thinner itself that help ppe also have benzene ring structure makes molecule in electric field, polarize to become difficulty can reduce the specific inductivity of material, and the adding of reactive thinner makes tensile strength and second-order transition temperature that the reduction of certain amplitude all arranged.
Embodiment 1: the epoxy resin of 20g and the thinner of 2g and the ppe grafted maleic anhydride of 2g are put into there-necked flask successively, through mechanical stirring, in oil bath pan, slowly be heated to 130 ℃; After solution stirring to be mixed was even, insulation 1h added 1g TGIC; Stir the 10min dissolving, be cooled to 100 ℃, slowly join 7g solidifying agent DDS in the solution again; Stir 20min; Put into 100 ℃ vacuum drying oven vacuumizing and defoaming 30min, the solution that will take off bubble is poured into and is put into baking oven in the tetrafluoroethylene mould of preheating and be cured, and curing process is 140 ℃/0.5h+170 ℃/2h+210 ℃/2h.
Embodiment 2: according to the step of embodiment 1, the consumption that changes ppe is 20% (weight ratio, down together) of epoxy resin.
Embodiment 3: according to the step of embodiment 1, the consumption that changes ppe is 30% of an epoxy resin.
Embodiment 4: according to the step of embodiment 1, the consumption that changes ppe is 40% of an epoxy resin.
Embodiment 5: the epoxy resin of 20g and the thinner of 2g and the ppe grafted maleic anhydride of 6g are put into there-necked flask, through mechanical stirring, in oil bath pan, slowly be heated to 150 ℃; After solution stirring to be mixed was even, insulation 3h added 0.2g TGIC; Stir 10min, be cooled to 90 ℃, slowly join 7g solidifying agent DDS in the solution again; Stir 40min; Put into 90 ℃ vacuum drying oven vacuumizing and defoaming 50min, the solution that will take off bubble is poured into and is put into baking oven in the tetrafluoroethylene mould of preheating and be cured, and curing process is 120 ℃/0.5h+190 ℃/2h+240 ℃/2h
Embodiment 6: according to the step of embodiment 5, the consumption that changes TGIC is 3% (weight ratio, down together) of epoxy resin.
Embodiment 7: according to the step of embodiment 5, the consumption that changes TGIC is 7% of an epoxy resin.
Embodiment 8: the epoxy resin of 20g and the thinner of 3g and the ppe grafted maleic anhydride of 6g are put into there-necked flask, through mechanical stirring, in oil bath pan, slowly be heated to 140 ℃; After solution stirring to be mixed was even, insulation 2h added 1g TGIC; Stir 10min, be cooled to 95 ℃, slowly join 7g solidifying agent DDS in the solution again; Stir 30min, put into 100 ℃ vacuum drying oven vacuumizing and defoaming 40min, the solution that will take off bubble is poured into and is put into baking oven in the tetrafluoroethylene mould of preheating and be cured; The adding of thinner makes gel time elongated, need to prolong set time, and curing process is 140 ℃/50min+170 ℃/3h+210 ℃/2h.
Embodiment 9: according to the step of embodiment 8, the consumption that changes thinner is 20% of an epoxy resin.
Comparative Examples 1: in there-necked flask, add the epoxy resin of 20g and the thinner of 2g,, in oil bath excessively, be heated to 130 ℃, be stirred to homogeneous transparent through mechanical stirring; Insulation 1h adds 1g TGIC, and dissolving back temperature is cooled to 100 ℃; Join solidifying agent DDS in the solution; Stir 20min, the solution that will take off bubble is poured into and is put into baking oven in the tetrafluoroethylene mould of preheating and be cured, and curing process is: 140 ℃/0.5h+170 ℃/2h+210 ℃/2h.
Comparative Examples 2: the epoxy resin of 20g and the thinner of 2g and the ppe grafted maleic anhydride of 7g are put into there-necked flask,, in oil bath pan, slowly be heated to 130 ℃ through mechanical stirring; After solution stirring to be mixed is even; Insulation 1h is cooled to 100 ℃, slowly joins solidifying agent DDS in the solution again; Stir 20min; Put into 100 ℃ vacuum drying oven vacuumizing and defoaming 30min, the solution that will take off bubble is poured into and is put into baking oven in the tetrafluoroethylene mould of preheating and be cured, and curing process is 120 ℃/0.5h+190 ℃/2h+240 ℃/2h.
Comparative Examples 3: the epoxy resin of 20g and the ppe grafted maleic anhydride of 7g are put into there-necked flask,, in oil bath pan, slowly be heated to 130 ℃ through mechanical stirring; After solution stirring to be mixed was even, insulation 2h added 1g TGIC; Be cooled to 95 ℃; Again solidifying agent DDS is slowly joined in the solution after the dissolving, stir 20min, put into 100 ℃ vacuum drying oven vacuumizing and defoaming 30min; The solution that will take off bubble is poured into and is put into baking oven in the tetrafluoroethylene mould of preheating and be cured, and curing process is 140 ℃/50min+170 ℃/3h+210 ℃/2h.
Table one: the over-all properties of epoxy resin/thinner/polyphenylene oxide resin system
Claims (4)
1. one kind low dielectric high heat epoxy compsn; It is characterized in that: the component of said compsn is calculated as by weight: (a) 100 weight parts bisphenol A type epoxy resin; (b) the ppe grafted maleic anhydride of 10～40 weight parts; Number average is at 2000～8000g/mol; (c) 35 weight part high-temperature curing agent diaminodiphenylsulfone(DDS)s (DDS), (d) isocyanuric acid three-glycidyl ester of 1～7 weight part (TGIC), (e) the reactive thinner benzyl glycidyl ether E692 of 10 ~ 20 weight parts.
2. a kind of low dielectric high heat epoxy compsn as claimed in claim 1; It is characterized in that: the preparation method of said ppe grafted maleic anhydride is: in the four-hole boiling flask of the 500mL that has condensation reflux unit; Add solvent toluene; After being heated to 95 ℃, be that the ratio of 2:1 joins ppe in the toluene according to mass ratio, mechanical stirring is until forming faint yellow homogeneous solution; Add dihydroxyphenyl propane (BPA), treat slowly to add Lucidol (BPO) again after its dissolving, add maleic anhydride after stirring 1h, continue to stir 3h down, be cooled to room temperature at 95 ℃, with the anhydrous methanol repetitive scrubbing more than 3 times, the dry product that gets.
3. a kind of low dielectric high heat epoxy compsn as claimed in claim 2, it is characterized in that: BPO is 1% ~ 6% of a ppe quality, and BPA is 1% ~ 6% of a ppe quality, and maleic anhydride is 3% of a ppe quality.
4. one kind low dielectric high heat epoxy preparation of compositions method; It is characterized in that may further comprise the steps: with reactive thinner; Epoxy resin and ppe grafted maleic anhydride mix stirring and are warming up to 130-150 ℃, behind the solution becomes homogeneous transparent to be mixed, behind the insulation 1-3h; Add TGIC, after the dissolving solution is cooled to 90-100 ℃; Add solidifying agent DDS; Stir 20-40min; Put into 90-100 ℃ vacuum drying oven vacuumizing and defoaming 30-50min, the solution that will take off bubble is poured into and is put into baking oven in the tetrafluoroethylene mould of preheating and be cured, at 120 ℃～140 ℃ Procuring 30～50min; Continue to solidify 120～240min at 160 ℃～190 ℃, at 210 ℃～240 ℃ after fixing 120min.
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105086369A (en) * | 2015-08-26 | 2015-11-25 | 安徽吉思特智能装备有限公司 | High-transparency reinforced maleic anhydride grafted polyphenyl ether modified epoxide resin composite material for LED (light emitting diode) packaging and preparing method thereof |
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| CN106633668A (en) * | 2016-12-30 | 2017-05-10 | 铜陵华科电子材料有限公司 | Triglycidyl-isocyanurate-reinforced weather-resistant epoxy resin composite material for copper clad plates and preparation method thereof |
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| CN104045929A (en) * | 2014-07-10 | 2014-09-17 | 苏州新区华士达工程塑胶有限公司 | Antimicrobial polystyrene |
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| CN105273363A (en) * | 2015-08-21 | 2016-01-27 | 安徽吉思特智能装备有限公司 | Nano diamond-containing maleic anhydride grafted polyphenyl ether modified epoxy resin composite material for LED package and preparation method |
| CN105255106A (en) * | 2015-08-21 | 2016-01-20 | 安徽吉思特智能装备有限公司 | Maleic anhydride-grafted polyphenyl ether modified epoxy resin composite used for LED packaging and preparation method thereof |
| CN105255120A (en) * | 2015-08-21 | 2016-01-20 | 安徽吉思特智能装备有限公司 | Nanometer zinc borate-containing maleic anhydride-grafted polyphenyl ether modified epoxy resin composite used for LED packaging and preparation method thereof |
| CN105086369A (en) * | 2015-08-26 | 2015-11-25 | 安徽吉思特智能装备有限公司 | High-transparency reinforced maleic anhydride grafted polyphenyl ether modified epoxide resin composite material for LED (light emitting diode) packaging and preparing method thereof |
| CN105153641A (en) * | 2015-09-08 | 2015-12-16 | 安徽吉思特智能装备有限公司 | High-ultraviolet-aging-resistance maleic anhydride grafted polyphenylene ether modified epoxy resin composite material for LED (Light Emitting Diode) packaging and preparation method thereof |
| CN106633668A (en) * | 2016-12-30 | 2017-05-10 | 铜陵华科电子材料有限公司 | Triglycidyl-isocyanurate-reinforced weather-resistant epoxy resin composite material for copper clad plates and preparation method thereof |
| CN113278257A (en) * | 2021-06-02 | 2021-08-20 | 林州致远电子科技有限公司 | Halogen-free white thermosetting resin composition and preparation method and application thereof |
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