CN106589832A - Cage-like silsesquioxane modified epoxy adhesive solution for high-Tg low-dielectric copper-clad plate and preparation method of adhesive solution - Google Patents
Cage-like silsesquioxane modified epoxy adhesive solution for high-Tg low-dielectric copper-clad plate and preparation method of adhesive solution Download PDFInfo
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- CN106589832A CN106589832A CN201611260067.4A CN201611260067A CN106589832A CN 106589832 A CN106589832 A CN 106589832A CN 201611260067 A CN201611260067 A CN 201611260067A CN 106589832 A CN106589832 A CN 106589832A
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- polyphenylene oxide
- allyl
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/48—Polymers modified by chemical after-treatment
- C08G65/485—Polyphenylene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention discloses a cage-like silsesquioxane modified epoxy adhesive solution for a high-Tg low-dielectric copper-clad plate. The adhesive solution is prepared from, by weight, 100 parts of bisphenol A type epoxy resin, 29-40 parts of diamino diphenyl sulfone, 22-31 parts of polyphenyl ether, a proper amount of tetrahydrofuran, 1-3 parts of n-butyllithium, 8-19 parts of allyl bromide, 6-12 parts of trichlorovinyl silane, 85-120 parts of acetone, 18-32 parts of deionized water, 5-11 parts of 3-chloroperoxybenzoic acid, a proper amount of dichloromethane, a proper amount of methyl alcohol, 0.5-1.5 parts of N,N-dimethylaminopyridine and 2-6 parts of aluminum nitride. Cage-like silsesquioxane containing epoxy groups and unsaturated double bonds is synthesized, the group, namely allyl, capable of being used for a crosslinking reaction is introduced on polyphenyl ether molecule main chains, allyl and the polyphenyl ether main chains take participation in a curing reaction of epoxy resin, the cross-linking density of the resin is increased, and accordingly glass transition temperature of a substrate is increased and the dielectric constant is reduced.
Description
Technical field
The invention belongs to the preparing technical field of copper-clad plate, and in particular to a kind of low dielectric copper-clad plate cage model sesquialter of high Tg
Silicone-modified epoxy glue solution and preparation method thereof.
Background technology
Electron trade development at present is swift and violent, the requirement more and more higher to copper-clad plate performance, and can directly have influence on the above
The factor of properties of product, is rooted in the dielectric constant (Dk) of substrate and the height of dielectric loss angle tangent (Df) substantially.At present
The matrix resin of copper-clad plate is based on bisphenol A type epoxy resin, but the high speed with electronic product, high frequency and people's ring
Protect the raising of consciousness, bisphenol A type epoxy resin thermostability is poor, dielectric constant and dielectric damage Expendable it is higher the shortcomings of, cannot
The requirement of the high performance copper clad laminate that satisfaction is used under high frequency condition.
The features such as polyphenylene oxide (PPO) has good high frequency characteristics, such as low-k, low dielectric loss, and it has
Extremely low water absorption rate, excellent thermostability, good dimensional stability and the features such as there is excellent adhesive property with Copper Foil,
The wiring board material being suitable in high frequency electronic equipment.But PPO organic solvent resistances are poor, and epoxy resin is in chemical constitution
There is very big difference, be typically dispersed in epoxy matrix in the form of spheroidal particle, belong to thermodynamics Immiscible Polymer Blends, easily make
There is manufacturing deficiency such as hole etc. in the wiring board course of processing, cause wiring board quality unreliable.
Mo Jingchao, treasured minister in ancient times middle Tu et al. are at it《The high-frequency copper-clad plate preparation of polyphenyl ether modified epoxy resin composite material
And performance》In one text, using the polyphenyl ether modified epoxy resin of epoxy radicals end-blocking, epoxy-capped polyphenylene oxide can participate in curing reaction,
The diffusion hindered effect of polyphenylene oxide is effectively reduced, the solidification rate of system can not only be improved, moreover it is possible to improve the degree of cross linking of system.
The dielectric properties of epoxy resin can not only be improved by both advantages, while can also improve polyphenylene oxide organic solvent resistance difference etc.
Defect, can be used for the composite of high-frequency copper-clad plate.
The content of the invention
For the deficiencies in the prior art, it is modified that the present invention provides a kind of low dielectric copper-clad plate cage-type silsesquioxanes of high Tg
Epoxy glue solution and preparation method thereof.
The low dielectric copper-clad plate cage-type silsesquioxane modified epoxy glue of a kind of high Tg, by the raw material group of following weight portion
Into：100 parts of bisphenol A type epoxy resin, DADPS 29-40 parts, polyphenylene oxide 22-31 parts, appropriate tetrahydrofuran, normal-butyl
Lithium 1-3 parts, allyl bromide, bromoallylene 8-19 parts, vinyl trichlorosilane 6-12 parts, acetone 85-120 parts, deionized water 18-32 parts, m-chloro
Change benzoyl hydroperoxide 5-11 parts, methylene chloride q, appropriate methanol, N, N- dimethyl aminopyridine 0.5-1.5 parts, aluminium nitride 2-
6 parts.
Comprise the following steps that：
（1）The synthesis of epoxy cage type sesquialter siloxane：
1. vinyl trichlorosilane and acetone, are added in there-necked flask, be slowly added dropwise while stirring under nitrogen protection from
Sub- water, reacts 6-8 days under 25-35 DEG C of constant temperature, and solution becomes dark reddish brown, separates out white crystal, as eight vinyls
Cage-type silsesquioxane；
2., above-mentioned eight ethenyl cage model sesquialter siloxane and a chlorination benzoyl hydroperoxide are dissolved in into dichloromethane, electromagnetic agitation is simultaneously
40-60 DEG C is to slowly warm up to, back flow reaction 1-3 days is dissolved in methanol after concentration, magnetic agitation 22-26 hour is taken out
Filter, obtains white powder and is epoxy cage type sesquialter siloxane；
（2）The preparation of allyl capped polyphenylene oxide：
Polyphenylene oxide is dissolved in tetrahydrofuran, under the protection of nitrogen, n-BuLi, heating reflux reaction 1-2 is slowly added to
Hour, 20-30 DEG C is cooled to, allyl bromide, bromoallylene stirring reaction 20-40 minute is added, separated out using methanol precipitate afterwards, in 50-70
DEG C vacuum drying 9-13 hours, obtain allyl capped polyphenylene oxide；
（3）Cage-type silsesquioxane base is crosslinked polyphenylene oxide/epoxy mixed system：
Bisphenol A type epoxy resin is weighed, according to formula ratio step is added（1）Epoxy cage type sesquialter siloxane, at 110-130 DEG C
Lower stirring 10-18 minutes, it is sufficiently mixed uniformly, is warming up to 150-170 DEG C of addition step（2）Allyl capped polyphenylene oxide, at a high speed
Stirring 30-55 minutes, form uniform mixed liquor；
（4）To step（3）Addition DADPS, N in mixed liquor, N- dimethyl aminopyridines, high-speed stirred 8-15 minute,
Add aluminium nitride to continue to stir 20-35 minutes, after mix homogeneously at 110-130 DEG C vacuumizing and defoaming, obtain final product required glue.
Compared with prior art, the present invention has advantages below：
（1）The present invention has synthesized first eight ethenyl cage model sesquialter siloxanes, then by a chlorination benzoyl hydroperoxide oxidized portion
Vinyl is obtained epoxy cage type sesquialter siloxane, and the cage-type silsesquioxane of generation is simultaneously double containing epoxide group and unsaturation
Key, the cage modle of cage-type silsesquioxane itself, hollow structure form " nano bubble " equivalent in resin matrix, can be effective
The reduction dielectric constant of material, in addition because epoxy terminated presence reactivity is higher, can participate in epoxy resin cure reaction,
Larger cross-linked network is formed, so as to improve the glass transition temperature of substrate.
（2）The present invention can be with by introducing the group-pi-allyl of cross-linking reaction on polyphenylene oxide molecular backbone, on the one hand
Overcome the not curable shortcoming of polyphenylene oxide itself, the polyphenylene oxide of another aspect allyl capped can with contain unsaturated double-bond
Epoxy cage type sesquialter siloxane occur curing reaction, because curing reaction is double bond additive reaction, molecule after curing reaction
Between motion significantly suppressed, improve three-component compound system crosslink density so that the vitrification point liter of substrate
Height, the solvent resistance of polyphenylene oxide and bin stability strengthen, and the dielectric constant of system significantly declines.
Specific embodiment
The low dielectric copper-clad plate cage-type silsesquioxane modified epoxy glue of a kind of high Tg, by the raw material group of following weight portion
Into：100 parts of bisphenol A type epoxy resin, 35 parts of DADPS, 28 parts of polyphenylene oxide, appropriate tetrahydrofuran, 2 parts of n-BuLi,
13 parts of allyl bromide, bromoallylene, 9 parts of vinyl trichlorosilane, 110 parts of acetone, 27 parts of deionized water, 8 parts of a chlorination benzoyl hydroperoxide, two
Appropriate chloromethanes, appropriate methanol, 0.5 part of N, N- dimethyl aminopyridine, 4 parts of aluminium nitride.
Comprise the following steps that：
（1）The synthesis of epoxy cage type sesquialter siloxane：
1. vinyl trichlorosilane and acetone, are added in there-necked flask, be slowly added dropwise while stirring under nitrogen protection from
Sub- water, reacts 7 days under 30 DEG C of constant temperatures, and solution becomes dark reddish brown, separates out white crystal, as eight ethenyl cage models times
Half siloxanes；
2., above-mentioned eight ethenyl cage model sesquialter siloxane and a chlorination benzoyl hydroperoxide are dissolved in into dichloromethane, electromagnetic agitation is simultaneously
50 DEG C are to slowly warm up to, back flow reaction 2 days is dissolved in methanol after concentration, and magnetic agitation 24 hours, sucking filtration obtains white
Powder is epoxy cage type sesquialter siloxane；
（2）The preparation of allyl capped polyphenylene oxide：
Polyphenylene oxide is dissolved in tetrahydrofuran, under the protection of nitrogen, n-BuLi is slowly added to, heating reflux reaction 1 is little
When, 25 DEG C are cooled to, add allyl bromide, bromoallylene stirring reaction 30 minutes, separated out using methanol precipitate afterwards, in 60 DEG C of vacuum drying
11 hours, obtain allyl capped polyphenylene oxide；
（3）Cage-type silsesquioxane base is crosslinked polyphenylene oxide/epoxy mixed system：
Bisphenol A type epoxy resin is weighed, according to formula ratio step is added（1）Epoxy cage type sesquialter siloxane, stirs at 120 DEG C
Mix 16 minutes, be sufficiently mixed uniformly, be warming up to 160 DEG C of addition steps（2）Allyl capped polyphenylene oxide, high-speed stirred 45 minutes,
Form uniform mixed liquor；
（4）To step（3）Addition DADPS, N in mixed liquor, N- dimethyl aminopyridines, high-speed stirred 12 minutes, plus
Enter aluminium nitride to continue to stir 30 minutes, after mix homogeneously at 120 DEG C vacuumizing and defoaming, obtain final product required glue.
The glue prepared using the embodiment of the present invention is obtained copper-clad plate, to its performance test：
178 DEG C of Tg values, dielectric constant ＜ 3.6, dielectric loss ＜ 0.005, thermal conductivity reaches 0.52W/mK, water absorption rate<0.15%.
Claims (2)
1. a kind of high Tg low dielectric copper-clad plates cage-type silsesquioxane modified epoxy glue, it is characterised in that by following weight
The raw material composition of part：100 parts of bisphenol A type epoxy resin, DADPS 29-40 parts, polyphenylene oxide 22-31 parts, tetrahydrofuran
In right amount, n-BuLi 1-3 parts, allyl bromide, bromoallylene 8-19 parts, vinyl trichlorosilane 6-12 parts, acetone 85-120 parts, deionized water
18-32 parts, chlorination benzoyl hydroperoxide 5-11 parts, methylene chloride q, appropriate methanol, N, N- dimethyl aminopyridine 0.5-
1.5 parts, aluminium nitride 2-6 parts.
2. a kind of high Tg low dielectric copper-clad plate cage-type silsesquioxane modified epoxy glues according to claims 1
Preparation method, it is characterised in that comprise the following steps that：
（1）The synthesis of epoxy cage type sesquialter siloxane：
1. vinyl trichlorosilane and acetone, are added in there-necked flask, be slowly added dropwise while stirring under nitrogen protection from
Sub- water, reacts 6-8 days under 25-35 DEG C of constant temperature, and solution becomes dark reddish brown, separates out white crystal, as eight vinyls
Cage-type silsesquioxane；
2., above-mentioned eight ethenyl cage model sesquialter siloxane and a chlorination benzoyl hydroperoxide are dissolved in into dichloromethane, electromagnetic agitation is simultaneously
40-60 DEG C is to slowly warm up to, back flow reaction 1-3 days is dissolved in methanol after concentration, magnetic agitation 22-26 hour is taken out
Filter, obtains white powder and is epoxy cage type sesquialter siloxane；
（2）The preparation of allyl capped polyphenylene oxide：
Polyphenylene oxide is dissolved in tetrahydrofuran, under the protection of nitrogen, n-BuLi, heating reflux reaction 1-2 is slowly added to
Hour, 20-30 DEG C is cooled to, allyl bromide, bromoallylene stirring reaction 20-40 minute is added, separated out using methanol precipitate afterwards, in 50-70
DEG C vacuum drying 9-13 hours, obtain allyl capped polyphenylene oxide；
（3）Cage-type silsesquioxane base is crosslinked polyphenylene oxide/epoxy mixed system：
Bisphenol A type epoxy resin is weighed, according to formula ratio step is added（1）Epoxy cage type sesquialter siloxane, at 110-130 DEG C
Lower stirring 10-18 minutes, it is sufficiently mixed uniformly, is warming up to 150-170 DEG C of addition step（2）Allyl capped polyphenylene oxide, at a high speed
Stirring 30-55 minutes, form uniform mixed liquor；
（4）To step（3）Addition DADPS, N in mixed liquor, N- dimethyl aminopyridines, high-speed stirred 8-15 minute,
Add aluminium nitride to continue to stir 20-35 minutes, after mix homogeneously at 110-130 DEG C vacuumizing and defoaming, obtain final product required glue.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611260067.4A CN106589832A (en) | 2016-12-30 | 2016-12-30 | Cage-like silsesquioxane modified epoxy adhesive solution for high-Tg low-dielectric copper-clad plate and preparation method of adhesive solution |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611260067.4A CN106589832A (en) | 2016-12-30 | 2016-12-30 | Cage-like silsesquioxane modified epoxy adhesive solution for high-Tg low-dielectric copper-clad plate and preparation method of adhesive solution |
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| CN106589832A true CN106589832A (en) | 2017-04-26 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110358091A (en) * | 2018-03-26 | 2019-10-22 | 北京化工大学 | A kind of preparation method of epoxidation phenyl siloxane rubber |
| CN117533001A (en) * | 2023-10-25 | 2024-02-09 | 江门建滔积层板有限公司 | Impact-resistant flame-retardant copper-clad plate and preparation method thereof |
| CN117533001B (en) * | 2023-10-25 | 2024-05-10 | 江门建滔积层板有限公司 | Impact-resistant flame-retardant copper-clad plate and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104194273A (en) * | 2014-09-03 | 2014-12-10 | 合肥会通新材料有限公司 | Preparation method of environmentally-friendly flame-retardant epoxy resin composite material based modified epoxy-POSS (polysilsesquioxane) |
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2016
- 2016-12-30 CN CN201611260067.4A patent/CN106589832A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104194273A (en) * | 2014-09-03 | 2014-12-10 | 合肥会通新材料有限公司 | Preparation method of environmentally-friendly flame-retardant epoxy resin composite material based modified epoxy-POSS (polysilsesquioxane) |
Non-Patent Citations (2)
| Title |
|---|
| 司凌霞: "POSS/环氧树脂/氰酸酯纳米复合材料的研究", 《北京化工大学硕士研究生学位论文》 * |
| 田勇，等: "高性能覆铜板用热固性树脂", 《热固性树脂》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110358091A (en) * | 2018-03-26 | 2019-10-22 | 北京化工大学 | A kind of preparation method of epoxidation phenyl siloxane rubber |
| CN110358091B (en) * | 2018-03-26 | 2021-01-22 | 北京化工大学 | Preparation method of epoxidized phenyl silicone rubber |
| CN117533001A (en) * | 2023-10-25 | 2024-02-09 | 江门建滔积层板有限公司 | Impact-resistant flame-retardant copper-clad plate and preparation method thereof |
| CN117533001B (en) * | 2023-10-25 | 2024-05-10 | 江门建滔积层板有限公司 | Impact-resistant flame-retardant copper-clad plate and preparation method thereof |
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