CN103725003A - Modified bismaleimide resin composition with high dampness and heat resistance and preparation method thereof - Google Patents
Modified bismaleimide resin composition with high dampness and heat resistance and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a modified bismaleimide resin composition with high dampness and heat resistance and a preparation method thereof. The modified bismaleimide resin composition with high dampness and heat resistance is prepared from the following components in parts by weight: 100 parts of bismaleimide resin, 50-100 parts of allyl compound, 15-50 parts of phenolic modified xylene formaldehyde resin and 0.5-5 parts of curing agent. The preparation method comprises the steps of placing the bismaleimide resin and the allyl compound with formula ratio in a reactor, heating to be at 120-145 DEG C, keeping the temperature until the resin is melted, keeping the temperature continuously, and stirring for reaction for 10-30min; adding the phenolic modified xylene formaldehyde resin and mixing uniformly, reducing the temperature to be at 90-100 DEG C, adding the curing agent, mixing uniformly, and carrying out vacuum defoaming treatment to obtain the modified bismaleimide resin composition. The modified bismaleimide resin composition can keep the excellent performances of the bismaleimide resin and can improve the moisture resistance, the chemical resistance and the reliability of electrical electronic devices after being subjected to curing.
Description
Technical field
The present invention relates to a kind of resin combination, be specifically related to a kind of modified bismaleimide resin composition and method of making the same with high wet-hot aging performance.
Background technology
Bismaleimides (BMI) resin is as the main matrix resin of advanced composite material, there is good resistance toheat and mechanical property, but the fragility that its main deficiency of unmodified BMI resin is its cured article is large, must just there is practical value through toughening modifying, the molecular configuration of BMI resin is firm, although thermotolerance is high, but processing characteristics is not good enough, in order to overcome above-mentioned these deficiencies, researchist has carried out a lot of study on the modification to BMI resin, the most frequently used method of modifying is to carry out modification by copolymerization with epoxy resin etc., and good progress and effect have been obtained.Along with the raising of the application requiring of the high-end technical fields such as electric appliance and electronic, bimaleimide resin has been proposed to more requirement, but add diallyl compound, diamine, epoxy resin can cause the reduction of thermotolerance or humidity resistance, therefore the over-all properties of existing bimaleimide resin composition needs further to be improved.Those skilled in the art will know that, bimaleimide resin is obtained through polycondensation cyclodehydration by two maleinamic acids, thereby the group of bimaleimide resin still has very strong wetting ability in molecular configuration, moisture resistivity is poor, after making moist or soaking, insulating property can sharply decline, and water molecules can permeate to material internal along intermolecular hole, and under damp and hot or moist environment, its reliability can obviously reduce.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of modified bismaleimide resin composition and method of making the same with high wet-hot aging performance.Modified bismaleimide resin composition obtained by this method has higher impelling strength, better humidity resistance and higher second-order transition temperature after solidifying.
The modified bismaleimide resin composition with high wet-hot aging performance of the present invention, by weight, comprises following component:
100 parts of bimaleimide resins, 50～100 parts of allylic cpds, 15～50 parts of phenol modification xylene formaldehyde resins, 0.5～5 part, solidifying agent.
The present invention has improved the anti-moisture performance of bimaleimide resin effectively by adding phenol modification xylene formaldehyde resin.In the resin structure of phenol modification xylene formaldehyde resin, containing a large amount of diformazan phenyl ring is introduced in system and finally can be present in gained modified bismaleimide resin composition to increase its hydrophobic property, also contain in addition hydroxyl, methoxyl group and the ehter bond that can react, being introduced in system to make the cross-linking density of gained modified bismaleimide resin composition decrease, toughness can increase to some extent, thereby makes gained modified bismaleimide resin composition have higher physical strength and shelf stability; In addition, phenol modification xylene formaldehyde resin has a certain proportion of phenol ring structure, thereby can make the last crosslinking curing of modified resin become reticulated structure; Therefore, by adding phenol modification xylene formaldehyde resin, bimaleimide resin is carried out to modification, when keeping the thermotolerance and toughness reguirements of bimaleimide resin, effectively improved humidity resistance and the wet-hot aging performance of gained modified bismaleimide resin composition.
In above-mentioned modified bismaleimide resin composition, the weight part of each component is preferably:
100 parts of bimaleimide resins, 60～80 parts of allylic cpds, 15～35 parts of phenol modification xylene formaldehyde resins, 0.5～3 part, solidifying agent.
In technique scheme,
Described bimaleimide resin can be to be specifically selected from 4,4'-diphenyl methane dimaleimide, 4, the combination of one or more in 4'-Diphenyl Ether Bismaleimide and 4,4'-sulfobenzide bismaleimides.When the above-mentioned two or more combination of being chosen as of bimaleimide resin, the proportioning between them can be any proportioning.
Described allylic cpd can be specifically one or more the combination being selected from diallyl bisphenol (DABPA), diallyl bisphenol S, allyl group cresols (AC) and chavicol, chavicol wherein can be o-allyl phenol or p-allylphenol, can be also the mixing of their both arbitrary proportions.When the above-mentioned two or more combination of being chosen as of diallyl compound, the proportioning between them can be any proportioning.
Described phenol modification xylene formaldehyde resin is (also referred to as phenol modification xylene resin, or be called xylene resin or xylene resin oligopolymer), for phenol reacts and obtains under the existence of acid catalyst with xylene resin, its molecular weight is generally 300～500Da, 70～100 ℃ of fusing points.The phenol modification xylene formaldehyde resin that specifically can adopt the companies such as Suzhou Speical Chemical Co., Ltd., Shanghai Jin Yue Chemical Co., Ltd. to produce.
Described solidifying agent is same as the prior art, can be specifically hexamethylenetetramine.
The preparation method of the above-mentioned modified bismaleimide resin composition with high wet-hot aging performance, be specially: get the bimaleimide resin of 100 weight parts and the allylic cpd of 50～100 parts and be placed in reactor, be warming up to 120～145 ℃, insulated and stirred, until resin melting is transparent, continues insulated and stirred reaction 10～30min; Then the phenol modification xylene formaldehyde resin that adds 10～50 weight parts, mixes; Be cooled to afterwards 90～100 ℃ of solidifying agent that add 0.5～5 weight part, mix; Through vacuum defoaming treatment, obtain having the modified bismaleimide resin composition of high wet-hot aging performance again.
In above-mentioned preparation method, the diallyl compound of the bimaleimide resin of 100 weight parts and 50～100 parts is placed in to reactor, be warming up to after 120～145 ℃, insulated and stirred until the transparent time of resin melting approximately need 10～30min.
In above-mentioned preparation method, adding after phenol modification xylene formaldehyde resin normally insulated and stirred 20～30min to reach the object mixing.
In above-mentioned preparation method, adding after solidifying agent normally insulated and stirred 8～15min to reach the object mixing.
In above-mentioned preparation method, the bimaleimide resin cured article that the modified bismaleimide resin composition of gained can be obtained routinely to modification after solidification treatment, concrete curing process is generally: 120 ℃/1h+150 ℃/2h+180 ℃/2h+210 ℃/5h.
In above-mentioned preparation method, described bimaleimide resin can be to be specifically selected from 4,4'-diphenyl methane dimaleimide, 4, the combination of one or more in 4'-Diphenyl Ether Bismaleimide and 4,4'-sulfobenzide bismaleimides; When the above-mentioned two or more combination of being chosen as of bimaleimide resin, the proportioning between them can be any proportioning.Described diallyl compound can be specifically one or more the combination being selected from diallyl bisphenol, diallyl bisphenol S, allyl group cresols and chavicol, chavicol wherein can be o-allyl phenol or p-allylphenol, can be also the mixing of their both arbitrary proportions; When the above-mentioned two or more combination of being chosen as of diallyl compound, the proportioning between them can be any proportioning.Described phenol modification xylene formaldehyde resin is (also referred to as phenol modification xylene resin, or be called xylene resin phenol modification xylene formaldehyde resin), for phenol reacts and obtains under the existence of acid catalyst with xylene resin, its molecular weight is generally 300～500Da, 70～100 ℃ of fusing points.The phenol modification xylene formaldehyde resin that specifically can adopt the companies such as Suzhou Speical Chemical Co., Ltd., Shanghai Jin Yue Chemical Co., Ltd. to produce.Described solidifying agent is same as the prior art, can be specifically hexamethylenetetramine.
Applicant finds through lot of experiments, the modified bismaleimide resin composition being made by the method for the invention is after solidifying, there are excellent electromechanical properties, not only keep the excellent properties (as stable on heating feature) of bimaleimide resin itself, also can improve moistureproofness, chemical proofing and the unfailing performance of appliance electronic component.
Compared with prior art, feature of the present invention is:
1, the bismaleimides of the present invention by adopting high heat resistance with the blend in specific proportions of two kinds of thermosetting resins of phenol modification xylene formaldehyde resin with benzene ring structure to reach the object of performances such as improving resin structure, water-intake rate and humidity resistance, make the blending resin casting matrix of gained have than the bismaleimides cured article of homopolymerization and have higher impelling strength, better humidity resistance and higher second-order transition temperature after solidifying, raising equipment is reliability of operation under moist environment;
2, the resin system of gained has good manufacturability, can prepare high temperature resistant, high performance matrix material by techniques such as mold pressing, cast.
Embodiment
Below by specific embodiment, the invention will be further described, but the present invention is not limited to these embodiment.
Umber described in following embodiment is weight part.
Chavicol related in following embodiment is all purchased from Honghu City span novel material Science and Technology Ltd., and described phenol modification xylene formaldehyde resin is all purchased from Suzhou Speical Chemical Co., Ltd..
Embodiment 1
By 100 parts 4,4'-diphenyl methane dimaleimide, the diallyl bisphenol of 60 parts is placed in reactor, be warming up to 140 ℃, insulated and stirred is until resin melting transparent (now 4,4'-diphenyl methane dimaleimide and diallyl bisphenol are melting vitreous state), continue insulated and stirred reaction 20min; Then under insulated and stirred condition, add the phenol modification xylene formaldehyde resin of 10 parts, insulated and stirred 20min; Be cooled to afterwards 95 ℃ and add the hexamethylenetetramine of 0.5 part, at this temperature, stir 10min; Finally through vacuum defoaming treatment, obtain modified bismaleimide resin composition again.
After the modified bismaleimide resin composition of the present embodiment gained is solidified by the technique of 120 ℃/1h+150 ℃/2h+180 ℃/2h+210 ℃/5h, obtain the bimaleimide resin cured article of modification.The electromechanical properties of the bimaleimide resin cured article of the modification to gained are tested, and result is as shown in table 1.
Comparative example 1
By 100 parts 4,4'-diphenyl methane dimaleimide, 60 parts of diallyl bisphenols, be placed in reactor, be warming up to 140 ℃, insulated and stirred is until resin melting transparent (now 4,4'-diphenyl methane dimaleimide and diallyl bisphenol are melting vitreous state) continues insulated and stirred reaction 20min; Then under insulated and stirred condition, add the epoxy resin CYD-128 insulated and stirred 20min of 30 parts; While being cooled to afterwards 95 ℃, add the epoxy hardener methyl hexahydrophthalic anhydride of 20 parts, 10min under this temperature stirs; The last bimaleimide resin composition that obtains again modification after vacuum froth breaking.
After the modified bismaleimide resin of this comparative example gained is solidified by the technique of 120 ℃/1h+150 ℃/2h+180 ℃/2h+210 ℃/5h, obtain the bimaleimide resin cured article of modification.The electromechanical properties of the bimaleimide resin cured article of the modification to gained are tested, and result is as shown in table 1.
Embodiment 2
By 100 parts 4,4'-diphenyl methane dimaleimide, the diallyl bisphenol of 80 parts is placed in reactor, be warming up to 130 ℃, insulated and stirred is until resin melting transparent (now 4,4'-diphenyl methane dimaleimide and diallyl bisphenol are melting vitreous state), continue insulated and stirred reaction 30min; Then under insulated and stirred condition, add the phenol modification xylene formaldehyde resin of 20 parts, insulated and stirred 30min; Be cooled to afterwards 100 ℃ and add the hexamethylenetetramine of 1 part, at this temperature, stir 8min; Finally through vacuum defoaming treatment, obtain modified bismaleimide resin composition again.
After the modified bismaleimide resin composition of the present embodiment gained is solidified by the technique of 120 ℃/1h+150 ℃/2h+180 ℃/2h+210 ℃/5h, obtain the bimaleimide resin cured article of modification.The electromechanical properties of the bimaleimide resin cured article of the modification to gained are tested, and result is as shown in table 1.
Embodiment 3
By 100 parts 4,4'-diphenyl methane dimaleimide, the diallyl bisphenol of 55 parts and the allyl group cresols of 25 parts are placed in reactor, be warming up to 130 ℃, insulated and stirred is until resin melting transparent (now 4,4'-diphenyl methane dimaleimide, diallyl bisphenol and allyl group cresols are melting vitreous state), continue insulated and stirred reaction 30min; Then under insulated and stirred condition, add the phenol modification xylene formaldehyde resin of 10 parts, insulated and stirred 20min; Be cooled to afterwards 90 ℃ and add the hexamethylenetetramine of 0.5 part, at this temperature, stir 10min; Finally through vacuum defoaming treatment, obtain modified bismaleimide resin composition again.
After the modified bismaleimide resin composition of the present embodiment gained is solidified by the technique of 120 ℃/1h+150 ℃/2h+180 ℃/2h+210 ℃/5h, obtain the bimaleimide resin cured article of modification.The electromechanical properties of the bimaleimide resin cured article of the modification to gained are tested, and result is as shown in table 1.
Embodiment 4
By 100 parts 4,4'-sulfobenzide bismaleimides, diallyl bisphenol and 25 parts of allyl group cresols of 55 parts are placed in reactor, be warming up to 130 ℃, insulated and stirred is until resin melting transparent (now 4,4'-sulfobenzide bismaleimides, diallyl bisphenol and allyl group cresols are melting vitreous state), continue insulated and stirred reaction 30min; Then under insulated and stirred condition, add the phenol modification xylene formaldehyde resin of 30 parts, insulated and stirred 20min; Be cooled to afterwards 90 ℃ and add the hexamethylenetetramine of 1.5 parts, 8min under this temperature stirs; Finally through vacuum defoaming treatment, obtain modified bismaleimide resin composition again.
After the modified bismaleimide resin composition of the present embodiment gained is solidified by the technique of 120 ℃/1h+150 ℃/2h+180 ℃/2h+210 ℃/5h, obtain the bimaleimide resin cured article of modification.The electromechanical properties of the bimaleimide resin cured article of the modification to gained are tested, and result is as shown in table 1.
Embodiment 5
By 50 parts 4,4'-diphenyl methane dimaleimide, 50 parts 4,4'-sulfobenzide bismaleimides, diallyl bisphenol and 40 parts of allyl group cresols of 30 parts are placed in reactor, be warming up to 130 ℃, insulated and stirred is until resin melting transparent (now 4,4'-diphenyl methane dimaleimide, 4,4'-sulfobenzide bismaleimides, diallyl bisphenol and allyl group cresols are melting vitreous state), continue insulated and stirred reaction 25min; Then under insulated and stirred condition, add the phenol modification xylene formaldehyde resin of 30 parts, insulated and stirred 20min; Be cooled to afterwards 90 ℃ and add the hexamethylenetetramine of 1.5 parts, 10min under this temperature stirs; Finally through vacuum defoaming treatment, obtain modified bismaleimide resin composition again.
After the modified bismaleimide resin composition of the present embodiment gained is solidified by the technique of 120 ℃/1h+150 ℃/2h+180 ℃/2h+210 ℃/5h, obtain the bimaleimide resin cured article of modification.The electromechanical properties of the bimaleimide resin cured article of the modification to gained are tested, and result is as shown in table 1.
Embodiment 6
By 60 parts 4,4'-diphenyl methane dimaleimide, 40 parts 4,4'-Diphenyl Ether Bismaleimide, diallyl bisphenol and 25 parts of allyl group cresols of 55 parts are placed in reactor, be warming up to 145 ℃, insulated and stirred is until resin melting transparent (now 4,4'-diphenyl methane dimaleimide, 4,4'-Diphenyl Ether Bismaleimide, diallyl bisphenol and allyl group cresols are melting vitreous state), continue insulated and stirred reaction 20min; Then under insulated and stirred condition, add the phenol modification xylene formaldehyde resin of 35 parts, insulated and stirred 25min; Be cooled to afterwards 90 ℃ and add the hexamethylenetetramine of 1.5 parts, 12min under this temperature stirs; Finally through vacuum defoaming treatment, obtain modified bismaleimide resin composition again.
After the modified bismaleimide resin composition of the present embodiment gained is solidified by the technique of 120 ℃/1h+150 ℃/2h+180 ℃/2h+210 ℃/5h, obtain the bimaleimide resin cured article of modification.The electromechanical properties of the bimaleimide resin cured article of the modification to gained are tested, and result is as shown in table 1.
Embodiment 7
By 100 parts 4,4'-Diphenyl Ether Bismaleimide, diallyl bisphenol and 20 parts of chavicols of 60 parts are placed in reactor, be warming up to 130 ℃, insulated and stirred is until resin melting transparent (now 4,4'-Diphenyl Ether Bismaleimide, diallyl bisphenol and chavicol are melting vitreous state), continue insulated and stirred reaction 30min; Then under insulated and stirred condition, add the phenol modification xylene formaldehyde resin of 40 parts, insulated and stirred 25min; Be cooled to afterwards 90 ℃ and add the hexamethylenetetramine of 1.5 parts, 10min under this temperature stirs; Finally through vacuum defoaming treatment, obtain modified bismaleimide resin composition again.
After the modified bismaleimide resin composition of the present embodiment gained is solidified by the technique of 120 ℃/1h+150 ℃/2h+180 ℃/2h+210 ℃/5h, obtain the bimaleimide resin cured article of modification.The electromechanical properties of the bimaleimide resin cured article of the modification to gained are tested, and result is as shown in table 1.
Comparative example 2 (the corresponding embodiment 7 of this comparative example)
By 100 parts 4, the chavicol of 4'-Diphenyl Ether Bismaleimide, 60 parts of diallyl bisphenols and 20 parts is placed in reactor, be warming up to 130 ℃, insulated and stirred is until resin melting transparent (now 4,4'-Diphenyl Ether Bismaleimide, diallyl bisphenol and chavicol are melting vitreous state), continue insulated and stirred reaction 30min; Then under insulated and stirred condition, add the epoxy resin CYD-128 insulated and stirred 20min of 40 parts; While being cooled to afterwards 90 ℃, add the epoxy hardener methyl hexahydrophthalic anhydride of 35 parts, under this temperature stirs 10 minutes; 10min under this temperature stirs; The last bimaleimide resin composition that obtains again modification after vacuum froth breaking.
After the modified bismaleimide resin of this comparative example gained is solidified by the technique of 120 ℃/1h+150 ℃/2h+180 ℃/2h+210 ℃/5h, obtain the bimaleimide resin cured article of modification.The electromechanical properties of the bimaleimide resin cured article of the modification to gained are tested, and result is as shown in table 1.
Embodiment 8
By 100 parts 4,4'-Diphenyl Ether Bismaleimide, the diallyl bisphenol of 90 parts are placed in reactor, be warming up to 120 ℃, insulated and stirred is until resin melting transparent (now 4,4'-Diphenyl Ether Bismaleimide and diallyl bisphenol are melting vitreous state), continue insulated and stirred reaction 30min; Then under insulated and stirred condition, add the phenol modification xylene formaldehyde resin of 50 parts to mix, be cooled to 95 ℃ and add the hexamethylenetetramine of 1.5 parts, 15min under this temperature stirs; Finally through vacuum defoaming treatment, obtain modified bismaleimide resin composition again.
After the modified bismaleimide resin composition of the present embodiment gained is solidified by the technique of 120 ℃/1h+150 ℃/2h+180 ℃/2h+210 ℃/5h, obtain the bimaleimide resin cured article of modification.The electromechanical properties of the bimaleimide resin cured article of the modification to gained are tested, and result is as shown in table 1.
Embodiment 9
By 100 parts 4,4'-Diphenyl Ether Bismaleimide, the diallyl bisphenol S of 100 parts are placed in reactor, be warming up to 130 ℃, insulated and stirred is until resin melting transparent (now 4,4'-Diphenyl Ether Bismaleimide and diallyl bisphenol S are melting vitreous state), continue insulated and stirred reaction 25min; Then under insulated and stirred condition, add the phenol modification xylene formaldehyde resin of 15 parts, insulated and stirred 20min; Be cooled to afterwards 90 ℃ and add the hexamethylenetetramine of 5 parts, 10min under this temperature stirs; Finally through vacuum defoaming treatment, obtain modified bismaleimide resin composition again.
After the modified bismaleimide resin composition of the present embodiment gained is solidified by the technique of 120 ℃/1h+150 ℃/2h+180 ℃/2h+210 ℃/5h, obtain the bimaleimide resin cured article of modification.The electromechanical properties of the bimaleimide resin cured article of the modification to gained are tested, and result is as shown in table 1.
Table 1:
Note: water tolerance test condition: 100 ℃ of water, 96 hours.
From data in table 1, with the bimaleimide resin composition of phenol modification xylene formaldehyde resin modification, the original thermotolerance of bimaleimide resin and higher heat-drawn wire have been kept on the one hand, make on the other hand bimaleimide resin have better humidity resistance, electromechanical properties are improved.Test-results shows, along with the increase of phenol modification xylene formaldehyde resin add-on, the heat-drawn wire of the modified bismaleimide resin composition wet-hot aging performance that slightly declines has raising by a relatively large margin.When the add-on of phenol modification xylene formaldehyde resin is controlled at the scope of 15～35 parts, the over-all properties of prepared modified bismaleimide resin composition is more good, can meet the requirement of appliance electronic component reliability under the severe environment such as damp and hot.
Claims (10)
1. a modified bismaleimide resin composition with high wet-hot aging performance, is characterized in that: by weight, comprise following component:
100 parts of bimaleimide resins, 50～100 parts of allylic cpds, 15～50 parts of phenol modification xylene formaldehyde resins, 0.5～5 part, solidifying agent.
2. the modified bismaleimide resin composition with high wet-hot aging performance according to claim 1, is characterized in that: the weight part of each component is:
100 parts of bimaleimide resins, 60～80 parts of allylic cpds, 15～35 parts of phenol modification xylene formaldehyde resins, 0.5～1.5 part, solidifying agent.
3. the modified bismaleimide resin composition with high wet-hot aging performance according to claim 1 and 2, it is characterized in that: described bimaleimide resin is for being selected from 4,4'-diphenyl methane dimaleimide, 4, the combination of one or more in 4'-Diphenyl Ether Bismaleimide and 4,4'-sulfobenzide bismaleimides.
4. the modified bismaleimide resin composition with high wet-hot aging performance according to claim 1 and 2, is characterized in that: described allylic cpd is one or more the combination being selected from diallyl bisphenol, diallyl bisphenol S, allyl group cresols and chavicol.
5. the modified bismaleimide resin composition with high wet-hot aging performance according to claim 1 and 2, is characterized in that: described solidifying agent is hexamethylenetetramine.
6. the preparation method of the modified bismaleimide resin composition with high wet-hot aging performance claimed in claim 1, it is characterized in that: get the bimaleimide resin of 100 weight parts and the allylic cpd of 50～100 parts and be placed in reactor, be warming up to 120～145 ℃, insulated and stirred, until resin melting is transparent, continues insulated and stirred reaction 10～30min; Then the phenol modification xylene formaldehyde resin that adds 10～50 weight parts, mixes; Be cooled to afterwards 90～100 ℃ of solidifying agent that add 0.5～5 weight part, mix; Through vacuum defoaming treatment, obtain having the modified bismaleimide resin composition of high wet-hot aging performance again.
7. the preparation method of the modified bismaleimide resin composition with high wet-hot aging performance according to claim 6, is characterized in that: adding insulated and stirred 20～30min after phenol modification xylene formaldehyde resin.
8. according to the preparation method of the modified bismaleimide resin composition with high wet-hot aging performance described in claim 6 or 7, it is characterized in that: the modified bismaleimide resin composition of gained obtains the bimaleimide resin cured article of modification after conventional solidification treatment.
9. according to the preparation method of the modified bismaleimide resin composition with high wet-hot aging performance described in claim 6 or 7, it is characterized in that: described bimaleimide resin is for being selected from 4,4'-diphenyl methane dimaleimide, 4, the combination of one or more in 4'-Diphenyl Ether Bismaleimide and 4,4'-sulfobenzide bismaleimides.
10. according to the preparation method of the modified bismaleimide resin composition with high wet-hot aging performance described in claim 6 or 7, it is characterized in that: described allylic cpd is one or more the combination being selected from diallyl bisphenol, diallyl bisphenol S, allyl group cresols and chavicol.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107011657A (en) * | 2017-03-28 | 2017-08-04 | 中国科学院化学研究所 | A kind of high-ductility bimaleimide resin and its preparation method and application |
| CN109336416A (en) * | 2018-09-17 | 2019-02-15 | 佛山朝鸿新材料科技有限公司 | A kind of mineral wool and preparation method thereof |
| CN109563344A (en) * | 2016-08-05 | 2019-04-02 | 日本化药株式会社 | Maleimide resin composition, prepreg, its hardening thing and semiconductor device |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003327663A (en) * | 2002-05-10 | 2003-11-19 | Kyocera Chemical Corp | Resin composition for sealing and semiconductor sealed device |
| CN101735611A (en) * | 2009-11-24 | 2010-06-16 | 广东生益科技股份有限公司 | Thermosetting resin composition with high heat conductivity, prepreg manufactured by adopting same and copper-clad laminate |
| CN101735456A (en) * | 2009-11-24 | 2010-06-16 | 广东生益科技股份有限公司 | High weather-proof thermosetting resin composite and prepreg and copper-clad laminate prepared thereby |
| CN101974226A (en) * | 2010-11-11 | 2011-02-16 | 苏州大学 | Flame-retardant bismaleimide resin and preparation method thereof |
| CN102304343A (en) * | 2011-08-19 | 2012-01-04 | 腾辉电子（苏州）有限公司 | Glue solution for copper-clad substrate, and preparation method thereof |
-
2013
- 2013-12-30 CN CN201310744080.7A patent/CN103725003B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003327663A (en) * | 2002-05-10 | 2003-11-19 | Kyocera Chemical Corp | Resin composition for sealing and semiconductor sealed device |
| CN101735611A (en) * | 2009-11-24 | 2010-06-16 | 广东生益科技股份有限公司 | Thermosetting resin composition with high heat conductivity, prepreg manufactured by adopting same and copper-clad laminate |
| CN101735456A (en) * | 2009-11-24 | 2010-06-16 | 广东生益科技股份有限公司 | High weather-proof thermosetting resin composite and prepreg and copper-clad laminate prepared thereby |
| CN101974226A (en) * | 2010-11-11 | 2011-02-16 | 苏州大学 | Flame-retardant bismaleimide resin and preparation method thereof |
| CN102304343A (en) * | 2011-08-19 | 2012-01-04 | 腾辉电子（苏州）有限公司 | Glue solution for copper-clad substrate, and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 王欢: "二甲苯改性酚醛树脂", 《沈阳化工》, no. 4, 29 August 1993 (1993-08-29), pages 50 - 51 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109563344A (en) * | 2016-08-05 | 2019-04-02 | 日本化药株式会社 | Maleimide resin composition, prepreg, its hardening thing and semiconductor device |
| CN107011657A (en) * | 2017-03-28 | 2017-08-04 | 中国科学院化学研究所 | A kind of high-ductility bimaleimide resin and its preparation method and application |
| CN109336416A (en) * | 2018-09-17 | 2019-02-15 | 佛山朝鸿新材料科技有限公司 | A kind of mineral wool and preparation method thereof |
| CN109336416B (en) * | 2018-09-17 | 2021-07-30 | 常州市北洋建材有限公司 | Glass wool and preparation method thereof |
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| CN103725003B (en) | 2016-02-03 |
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