CN102924691B - Method for preparing low-dielectric epoxy resin composite material - Google Patents
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Abstract
The invention relates to a method for preparing a low-dielectric epoxy resin composite material, belongs to the field of a high-molecular compound material. The method comprises the following steps that (1) an epoxy resin monomer, a curing agent and an accelerant are uniformly mixed at the temperature of 70 DEG C, and air bubbles are removed through vacuumization; (2) an unsaturated polymer monomer containing an initiator is added into the solution of the step (1) and is vacuumized, N2 is poured, and the mixture is heated to 80 DEG C and is stirred and prepolymerized for 2 hours; (3) the prepolymer obtained in the step (2) is poured into a mould which is preheated at the temperature of 80 DEG C and is cured in two stages, wherein the first stage is as follows: 80 DEG C (2 hours) +100 DEG C (2 hours) +120 DEG C (5 hours), and the second is as follows: 120 DEG C (1 hour) +140 DEC C (1 hour) +160 DEG C (1 hour) +180 DEG C (1 hour) +200 DEG C (2 hours), and the low-dielectric epoxy resin composite material is obtained; and the epoxy resin monomer is bisphenols A epoxy resin E-51, and the curing agent is MHHPA. The dielectric constant and the dielectric loss of the epoxy resin are effectively reduced, and the good mechanical strength is kept.
Description
Technical field
The present invention relates to macromolecular compound Material Field.
Technical background
Along with social informatization, information processing and Information Communication high speed, electronic product is just towards light, thin, short, little and multifunction future development, therefore its intraware density increases, cause Signal transmissions time delay, crosstalk noise enhancing and energy consumption increase etc., and wherein serious with the delay of signal, then in the urgent need to a kind of low-k, low-dielectric loss matrix material as baseplate material.In the line, the velocity of propagation of signal is relevant with the specific inductivity of body material, and its relation is as follows:
V＝K·C/ε
r 1/2
V-signal velocity in formula;
K-constant;
C-light velocity;
ε
r-specific inductivity.
From above formula, the baseplate material that specific inductivity is lower, more carrys out the requirement of satisfied current electronic product high-speed high frequency.
Current industry member has epoxy resin, polyimide resin, tetrafluoroethylene etc. as the resin that printed circuit board base board material is conventional.Tetrafluoroethylene has excellent dielectric properties, but there is following shortcoming: very poor in processability, and mechanics, the poor performance such as bonding, cost is high.Polyimide resin is also that machine-shaping difficulty is large, and over-all properties is not good enough.Comparatively speaking, epoxy source material abundance, low price, is easy to machine-shaping.Epoxy resin after solidification has good physical and chemical performance, and solvent resistance is good, and linear expansivity is low, and physical strength is high, and good, the resistance to surface leakage of Heat stability is good, dielectric properties, resistance to electric arc etc., become current widespread use printed-wiring board (PWB) matrix material.But the develop rapidly of microelectronic in recent years makes the dielectric properties of pure epoxy resin cannot meet the requirement of current dielectric materials, the specific inductivity reducing epoxy resin-base material further becomes the current problem mainly solved.
Current research thinks that the main method reducing material dielectric constant has two kinds: first method is chemical modification, namely strong electronegativity element is mixed in the molecular structure, electronics is firmly held onto, reducing the polarity of material self, generally reducing specific inductivity with mixing fluorine in the material now.The people such as Zhiqiang Tao have synthesized a kind of novel fluorine epoxy resin and have solidified respectively at methyl hexahydrophthalic anhydride (MHHPA) and diaminodiphenylmethane (DDM), and contrast with common bisphenol type epoxy, specific inductivity have dropped 0.2 ~ 0.3.The people such as J.R.Lee prepare after a kind of fluorine-containing epoxy resin and DDM solidify, and compared to the contrast of common bisphenol type epoxy, under different frequency condition, specific inductivity reduces 0.2 ~ 0.4.Although mix fluorine can reduce specific inductivity, fall is little, and synthesis technique is complicated, cost is high.Another method is physical blending, physical blending is again by two kinds of approach: the first manufactures the molecular density that hole reduces material in dielectric materials, general many use porous or hollow structure mineral filler, as how empty silicon-dioxide, molecular sieve, hollow glass microballoon, polyhedral oligomeric silsesquioxane (POSS) etc.Chinese patent CN 101638505A discloses a kind of low dielectric-epoxy resin/mesoporous molecular sieve hybrid material, and under 100kHz, the specific inductivity of relative pure epoxy resin is maximum have dropped 0.9.Mesoporous silicon oxide split is added in epoxy resin and polyimide resin by Chinese patent CN1783357A respectively, and under 1MHz, specific inductivity have dropped 0.82 and 0.57 respectively.Chinese patent CN101565545A discloses a kind of preparation method of ethylene rhodanate-epoxy-POSS hybrid resin, and POSS is scattered in resin matrix with molecular level level, and the mechanical property of the matrix material obtained significantly improves, and resistance toheat, dielectric properties are superior.US Patent No. 005785789A discloses a kind of low dielectric-epoxy resin/hollow glass microballoon matrix material, in epoxy resin-base, add hollow glass microballoon, reduces the specific inductivity of epoxy resin.US Patent No. 20030143390A1 discloses a kind of polyarylene ether polymer containing hollow structure, second-order transition temperature (T
g) higher than 400 DEG C, specific inductivity is lower than 2.5.Manufacture the specific inductivity that hole significantly can reduce material in the material, but the filler adding a large amount of inorganic porous or hollow structures can cause the significantly decline of material mechanical performance.It two is by the specific inductivity of polymkeric substance (as tetrafluoroethylene, polyphenylene oxide etc.) the blended reduction material of epoxy resin and low-k, but directly epoxy resin and blended easy generation of low dielectric polymer is disperseed inequality, and the problem such as be separated.The people such as Sixun Zheng are copolymer blended by epoxy resin and styrene-acrylonitrile, and have studied the consistency of mixture, pattern and fracture toughness property, show that two phase structure appears in epoxy resin and styrene-acrylonitrile copolymer by scanning electron microscope and dynamic mechanical analysis.Chinese patent CN102372900A discloses a kind of composition epoxy resin and the prepreg made thereof and printed circuit board (PCB), said composition is epoxy resin and stiffening agent phenylethylene-maleic anhydride thereof, specific inductivity is 4.18 ~ 4.45 at 1 GHz, and loss is 0.007 ~ 0.014.US Patent No. 005916683A discloses a kind of epoxy resin and the low dielectric polymer blend of aryl ester, and its specific inductivity is 2.70 ~ 2.90 at 1 GHz.US Patent No. 006383660B2 discloses a kind of composition epoxy resin, and its component is: epoxy resin, resol, solidifying agent and promotor and hollow inorganic particle, sample is prepared, its specific inductivity 2.7 ~ 3.2, second-order transition temperature 105 ~ 167 DEG C by different ingredients.US Patent No. 6388009B1 discloses a kind of circuit card of low-k, and its component is, epoxy resin, syndiotactic styrenic/aromatic poly amide-styrol copolymer, solidifying agent, after solidification, specific inductivity is 2.9 ~ 3.6, and after compound glass cloth, specific inductivity is 3.1 ~ 4.5.
In sum, chemical modification method, can reduce material dielectric constant as mixed fluorine, but the amplitude of reduction is less, and synthesis technique is complicated, and cost is high.In matrix resin, add the specific inductivity that hollow structure inorganics significantly can reduce material in physical blending method, but addition is large, affect processing characteristics with dispersed, and hollow structure can causes mechanical property to be lost in a large number.POSS has nano-pore structure not only can be reduced specific inductivity but also improve the performances such as the mechanics of material, thermally-stabilised energy simultaneously, but POSS price is extremely expensive.Directly epoxy resin and blended easy generation of low dielectric polymer are disperseed inequality, the problem such as be separated.Being improved epoxy resin dielectric properties by simple, cost-effective method is current study hotspot, the present invention by the monomer of the unsaturated polymer by low-k in the epoxy in-situ polymerization dispersion reduce the specific inductivity of epoxy resin, also there is not relevant report at present.
Summary of the invention
Technical problem to be solved by this invention is, provides a kind of preparation method of low dielectric-epoxy resin, can reduce specific inductivity and the dielectric loss of epoxy resin, and keep good physical strength.
The technical scheme that the present invention solve the technical problem employing is, the preparation method of low dielectric-epoxy resin composite materials, is characterized in that, comprises the following steps:
(1) epoxy monomer, solidifying agent and promotor are mixed at 70 DEG C, vacuumize and remove bubble;
(2) the unsaturated polymer monomer containing initiator is added in the solution in step (1), vacuumize, pass into N
2, be warming up to 80 DEG C, stir pre-polymerization 2h;
(3) step (2) gained prepolymer is poured in mould preheated at 80 DEG C, divide two stage solidification, first stage 80 DEG C (2h)+100 DEG C (2h)+120 DEG C (5h), subordinate phase 120 DEG C (1h)+140 DEG C (1h)+160 DEG C (1h))+180 DEG C (1h)+200 DEG C (2h), obtain low dielectric-epoxy resin composite materials;
Described epoxy monomer is bisphenol A type epoxy resin E-51, and solidifying agent is methyl hexahydrophthalic anhydride MHHPA.
Further, described promotor is DMP-30 or glyoxal ethyline, and initiator is AIBN, and unsaturated polymer monomer is vinylbenzene or methyl methacrylate.
Further, count by weight, bisphenol A type epoxy resin E-51 is 40 parts, and MHHPA is 27.4 parts, and promotor is 0.4 part of DMP-30 or 0.4 part glyoxal ethyline, and initiator A IBN is 0.1 ~ 0.34 part, unsaturated polymer monomer 20.22 ~ 67.4 parts.
Or bisphenol A type epoxy resin E-51 is 40 parts, MHHPA is 27.4 parts, and promotor is 0.4 part of DMP-30, initiator A IBN is 0.1 ~ 0.34 part, and unsaturated polymer monomer is 20.22 ~ 67.4 parts of vinylbenzene.
Or bisphenol A type epoxy resin E-51 is 40 parts, MHHPA is 27.4 parts, and promotor is 0.4 part of glyoxal ethyline, and initiator A IBN is 0.1 ~ 0.24 part, and unsaturated polymer monomer is 20.22 ~ 47.2 parts of methyl methacrylates.
Or, bisphenol A type epoxy resin E-51 is 40 parts, and MHHPA is 27.4 parts, and promotor is 0.4 part of glyoxal ethyline, initiator is 0.17 part of AIBN, and to be 11.2 ~ 16.8 parts of methyl methacrylates cinnamic with 22.4 ~ 16.8 parts mixes for unsaturated polymer monomer.
Or bisphenol A type epoxy resin E-51 is 40 parts, MHHPA is 27.4 parts, and promotor is 0.4 part of DMP-30, initiator A IBN is 0.17 part, and unsaturated polymer monomer is 33.7 parts of vinylbenzene.
Or bisphenol A type epoxy resin E-51 is 40 parts, MHHPA is 27.4 parts, and promotor is 0.4 part of DMP-30, initiator A IBN is 0.24 part, and unsaturated polymer monomer is 47.21 parts of vinylbenzene.
The present invention will be by having unsaturated polymer monomer in-situ polymerization and the dispersion in the epoxy of low-k, be scattered in epoxy resin with nano-grade size, effectively reduce specific inductivity and the dielectric loss of epoxy resin, and keep good physical strength.Preparation technology is simple, solvent-free, volatilizees, environmental protection and cost is low without toxic gas.
Accompanying drawing explanation
Fig. 1 is epoxy resin/poly styrene composite material cross-section morphology figure.From figure, ps particle is dispersed in epoxy resin, and the median size of ps particle is about 50nm.
Embodiment
Embodiment 1
(1) by 40g bisphenol A type epoxy resin E-51,27.4g MHHPA and 0.4g DMP-30 stirring and evenly mixing at 70 DEG C, removing bubble is vacuumized; (2) solution in step (1) is poured in the mould of preheating at 80 DEG C, curing molding, curing process is 120 DEG C (1h)+140 DEG C (1h)+160 DEG C (1h)+180 DEG C (1h)+200 DEG C (2h), obtain epoxy resin cured product, its performance is in table 2.
Embodiment 2
(1) by 40g bisphenol A type epoxy resin E-51,27.4g MHHPA and 0.4g DMP-30 stirring and evenly mixing at 70 DEG C, removing bubble is vacuumized; (2) 0.10g AIBN is fully dissolved in 20.22g vinylbenzene, adds in the solution in step (1) and vacuumize, pass into N
2, be warming up to 80 DEG C, stir pre-polymerization 2h; (3) prepolymer in step (2) is poured in mould preheated at 80 DEG C, divide 2 stage solidification, first stage 80 DEG C (2h)+100 DEG C (2h)+120 DEG C (5h), subordinate phase 120 DEG C (1h)+140 DEG C (1h)+160 DEG C (1h)+180 DEG C (1h)+200 DEG C (2h), obtain epoxy resin composite material, its performance is in table 2.
Embodiment 3
(1) by 40g bisphenol A type epoxy resin E-51,27.4g MHHPA and 0.4g DMP-30 stirring and evenly mixing at 70 DEG C, removing bubble is vacuumized; (2) 0.17g AIBN is fully dissolved in 33.7g vinylbenzene, adds in the solution in step (1) and vacuumize, pass into N
2, be warming up to 80 DEG C, stir pre-polymerization 2h; (3) prepolymer in step (2) is poured in mould preheated at 80 DEG C, divide 2 stage solidification, first stage 80 DEG C (2h)+100 DEG C (2h)+120 DEG C (5h), subordinate phase 120 DEG C (1h)+140 DEG C (1h)+160 DEG C (1h)+180 DEG C (1h)+200 DEG C (2h), obtain epoxy resin composite material, its performance is in table 2.
Embodiment 4
(1) by 40g bisphenol A type epoxy resin E-51,27.4g MHHPA and 0.4g DMP-30 stirring and evenly mixing at 70 DEG C, removing bubble is vacuumized; (2) 0.24g AIBN is fully dissolved in 47.21g vinylbenzene, adds in the solution in step (1) and vacuumize, pass into N
2, be warming up to 80 DEG C, stir pre-polymerization 2h; (3) prepolymer in step (2) is poured in mould preheated at 80 DEG C, divide 2 stage solidification, first stage 80 DEG C (2h)+100 DEG C (2h)+120 DEG C (5h), subordinate phase 120 DEG C (1h)+140 DEG C (1h)+160 DEG C (1h)+180 DEG C (1h)+200 DEG C (2h), obtain epoxy resin composite material, its performance is in table 2.
Embodiment 5
(1) by 40g bisphenol A type epoxy resin E-51,27.4g MHHPA and 0.4g DMP-30 stirring and evenly mixing at 70 DEG C, removing bubble is vacuumized; (2) 0.34g AIBN is fully dissolved in 67.4g vinylbenzene, adds in the solution in step (1) and vacuumize, pass into N
2, be warming up to 80 DEG C, stir pre-polymerization 2h; (3) prepolymer in step (2) is poured in mould preheated at 80 DEG C, divide 2 stage solidification, first stage 80 DEG C (2h)+100 DEG C (2h)+120 DEG C (5h), subordinate phase 120 DEG C (1h)+140 DEG C (1h)+160 DEG C (1h)+180 DEG C (1h)+200 DEG C (2h), obtain epoxy resin composite material, its performance part is in table 2.
Embodiment 6
(1) by 40g bisphenol A type epoxy resin E-51,27.4g MHHPA and 0.4g2-Methylimidazole stirring and evenly mixing at 70 DEG C, removing bubble is vacuumized; (2) 0.10g AIBN is fully dissolved in 20.22g methyl methacrylate, adds in the solution in step (1) and vacuumize, pass into N
2, be warming up to 80 DEG C, stir pre-polymerization 2h; (3) the pre-thing liquid in step (2) is poured in mould preheated at 80 DEG C, divide 2 stage solidification, first stage 80 DEG C (2h)+100 DEG C (2h)+120 DEG C (5h), subordinate phase 120 DEG C (1h)+140 DEG C (1h)+160 DEG C (1h)+180 DEG C (1h)+200 DEG C (2h), obtain epoxy resin composite material, its performance part is in table 2.
Embodiment 7
(1) by 40g bisphenol A type epoxy resin E-51,27.4g MHHPA and 0.4g2-Methylimidazole stirring and evenly mixing at 70 DEG C, removing bubble is vacuumized; (2) 0.17g AIBN is fully dissolved in 33.7g methyl methacrylate, adds in the solution in step (1) and vacuumize, pass into N
2, be warming up to 80 DEG C, stir pre-polymerization 2h; (3) prepolymer in step (2) is poured in mould preheated at 80 DEG C, divide 2 stage solidification, first stage 80 DEG C (2h)+100 DEG C (2h)+120 DEG C (5h), subordinate phase 120 DEG C (1h)+140 DEG C (1h)+160 DEG C (1h)+180 DEG C (1h)+200 DEG C (2h), obtain epoxy resin composite material, its performance part is in table 2.
Embodiment 8
(1) by 40g bisphenol A type epoxy resin E-51,27.4g MHHPA and 0.4g2-Methylimidazole stirring and evenly mixing at 70 DEG C, removing bubble is vacuumized; (2) 0.24g AIBN is fully dissolved in 47.2g methyl methacrylate, adds in the solution in step (1) and vacuumize, pass into N
2, be warming up to 80 DEG C, stir pre-polymerization 2h; (3) prepolymer in step (2) is poured in mould preheated at 80 DEG C, divide 2 stage solidification, first stage 80 DEG C (2h)+100 DEG C (2h)+120 DEG C (5h), subordinate phase 120 DEG C (1h)+140 DEG C (1h)+160 DEG C (1h)+180 DEG C (1h)+200 DEG C (2h), obtain epoxy resin composite material, its performance part is in table 2.
Embodiment 9
(1) by 40g bisphenol A type epoxy resin E-51,27.4g MHHPA and 0.4g2-Methylimidazole stirring and evenly mixing at 70 DEG C, removing bubble is vacuumized; (2) 0.17g AIBN is fully dissolved in 22.4g vinylbenzene and 11.2g methyl methacrylate, adds in the solution in step (1) and vacuumize, pass into N
2, be warming up to 80 DEG C, stir pre-polymerization 2h; (3) prepolymer in step (2) is poured in mould preheated at 80 DEG C, divide 2 stage solidification, first stage 80 DEG C (2h)+100 DEG C (2h)+120 DEG C (5h), subordinate phase 120 DEG C (1h)+140 DEG C (1h)+160 DEG C (1h)+180 DEG C (1h)+200 DEG C (2h), obtain epoxy resin composite material, its performance part is in table 2.
Embodiment 10
(1) by 40g bisphenol A type epoxy resin E-51,27.4g MHHPA and 0.4g2-Methylimidazole stirring and evenly mixing at 70 DEG C, removing bubble is vacuumized; (2) 0.17g AIBN is fully dissolved in 16.8g vinylbenzene and 16.8g methyl methacrylate, adds in the solution in step (1) and vacuumize, pass into N
2, be warming up to 80 DEG C, stir pre-polymerization 2h; (3) prepolymer in step (2) is poured in mould preheated at 80 DEG C, divide 2 stage solidification, first stage 80 DEG C (2h)+100 DEG C (2h)+120 DEG C (5h), subordinate phase 120 DEG C (1h)+140 DEG C (1h)+160 DEG C (1h)+180 DEG C (1h)+200 DEG C (2h), obtain epoxy resin composite material, its performance part is in table 2.
Each embodiment material number is as table 1:
Table 1
Comparative example 1
(1) with bisphenol AF and epoxy chloropropane for raw material prepares the fluorine-containing bisphenol A type epoxy resin of lower molecular weight by phase transfer catalysis process; (2) fluorine-containing for 40g bisphenol A type epoxy resin, 21.7gMHHPA and 0.4gDMP-30 are mixed at 70 DEG C, vacuumize removing bubble; (3) solution in step (2) is poured in mould preheated at 80 DEG C curing molding, curing process is 120 DEG C (1h)+140 DEG C (1h)+160 DEG C (1h)+180 DEG C (1h)+200 DEG C (2h), obtain epoxy resin cured product, its performance is in table 2.
Comparative example 2
(1) 40g bisphenol A type epoxy resin E-51,27.44gMHHPA and 0.4gDMP-30 are mixed at 70 DEG C, vacuumize removing bubble; (2) 6.74g polytetrafluorethylepowder powder is added in step (1), stir, removing bubble; (3) mixture in step (2) is poured in mould preheated at 80 DEG C curing molding, curing process is 120 DEG C (1h)+140 DEG C (1h)+160 DEG C (1h)+180 DEG C (1h)+200 DEG C (2h), obtain epoxy resin composite material, its performance is in table 2.
Comparative example 3
(1) 40g bisphenol A type epoxy resin E-51,27.44gMHHPA and 0.4gDMP-30 are mixed at 70 DEG C, vacuumize removing bubble; (2) 20.2g polytetrafluorethylepowder powder is added in step (1), stir, removing bubble; (3) mixture in step (2) is poured in mould preheated at 80 DEG C curing molding, curing process is 120 DEG C (1h)+140 DEG C (1h)+160 DEG C (1h)+180 DEG C (1h)+200 DEG C (2h), obtain epoxy resin composite material, its performance is in table 2.
Comparative example 4
(1) by 40g bisphenol A type epoxy resin E-51,27.44gMHHPA, 2.02g Nano-meter SiO_2
2mix at 70 DEG C with 0.4gDMP-30, vacuumize removing bubble; (2) 6.74g hollow glass microballoon is added in step (1), stir, removing bubble; (3) mixture in step (2) is poured in mould preheated at 80 DEG C curing molding, curing process is 120 DEG C (1h)+140 DEG C (1h)+160 DEG C (1h)+180 DEG C (1h)+200 DEG C (2h), obtain epoxy resin composite material, its performance is in table 2.
Comparative example 5
(1) by 40g bisphenol A type epoxy resin E-51,27.44gMHHPA, 2.02g Nano-meter SiO_2
2mix at 70 DEG C with 0.4gDMP-30, vacuumize removing bubble; (2) 20.2g hollow glass microballoon is added in step (1), stir, removing bubble; (3) mixture in step (2) is poured in mould preheated at 80 DEG C curing molding, curing process is 120 DEG C (1h)+140 DEG C (1h)+160 DEG C (1h)+180 DEG C (1h)+200 DEG C (2h), obtain epoxy resin composite material, its performance is in table 2.
Comparative example 6
(1) by 40g bisphenol A type epoxy resin E-51,27.44gMHHPA, 2.02g Nano-meter SiO_2
2mix at 70 DEG C with DMP-30, vacuumize removing bubble; (2) 33.7g hollow glass microballoon is added in step (1), stir, removing bubble; (3) mixture in step (2) is poured in mould preheated at 80 DEG C curing molding, curing process is 120 DEG C (1h)+140 DEG C (1h)+160 DEG C (1h)+180 DEG C (1h)+200 DEG C (2h), obtain epoxy resin composite material, its performance is in table 2.
Table 2
Known by the data of embodiment in table 21 ~ 5, when unsaturated polymer monomer is vinylbenzene, and the increase of content, specific inductivity and the dielectric loss of epoxy resin/polystyrene nano composite material are on a declining curve, when vinylbenzene consumption and resin matrix mass ratio are 1:1, specific inductivity declines 0.57, and dielectric loss declines 0.0008.
Embodiment 6 ~ 8 is when unsaturated polymer monomer is methyl methacrylate, and the specific inductivity of material is also on a declining curve, but compares with polystyrene systems, and specific inductivity fall is little; It is good that mechanical property compares polystyrene systems.
Embodiment 9 ~ 10 is when unsaturated polymer monomer is vinylbenzene and methyl methacrylate two kinds is composite, and along with the increase of methyl methacrylate amount, the specific inductivity of material can increase, but mechanical properties decrease amplitude reduces.
By comparative example 1 ~ 10, can show that embodiment 3,4 over-all properties is best.The mechanical system of embodiment 4 is lower compared with comparative example 1.In comparative example, 2,3 is epoxy resin/polytetrafluorethylepowder powder systems, although have excellent dielectric properties, mechanical property loss is too large.Be epoxy resin/hollow glass microspheres system in comparative example 4 ~ 6, in contrast, specific inductivity is slightly high for embodiment 3,4, but dielectric loss is starkly lower than epoxy resin/hollow glass microspheres system, and mechanical property is also than better.
In sum, by by insatiable hunger polymer monomer in-situ polymerization in the epoxy, be scattered in epoxy resin with nano-grade size, while improving epoxy resin dielectric properties, also remain good mechanical property.When monomer is vinylbenzene, and when being 5:10 ~ 7:10 with epoxy resin mass ratio, the over-all properties of low dielectric-epoxy resin composite materials is best.
Claims (1)
1. the preparation method of low dielectric-epoxy resin composite materials, is characterized in that, comprises the following steps:
(1) epoxy monomer, solidifying agent and promotor are mixed at 70 DEG C, vacuumize and remove bubble;
(2) the unsaturated polymer monomer containing initiator is added in the solution in step (1), vacuumize, pass into N
2, be warming up to 80 DEG C, stir pre-polymerization 2h;
(3) step (2) gained prepolymer is poured in mould preheated at 80 DEG C, divide two stage solidification, first stage 80 DEG C (2h)+100 DEG C (2h)+120 DEG C (5h), subordinate phase 120 DEG C (1h)+140 DEG C (1h)+160 DEG C (1h))+180 DEG C (1h)+200 DEG C (2h), obtain low dielectric-epoxy resin composite materials;
Described epoxy monomer is bisphenol A type epoxy resin E-51, and solidifying agent is MHHPA, and described promotor is DMP-30 or glyoxal ethyline, and initiator is AIBN, and unsaturated polymer monomer is vinylbenzene or methyl methacrylate;
Count by weight, each component is:
Bisphenol A type epoxy resin E-51 is 40 parts, and MHHPA is 27.4 parts, and promotor is 0.4 part of DMP-30 or 0.4 part glyoxal ethyline, and initiator A IBN is 0.1 ~ 0.34 part, unsaturated polymer monomer 20.22 ~ 67.4 parts;
Or bisphenol A type epoxy resin E-51 is 40 parts, MHHPA is 27.4 parts, and promotor is 0.4 part of DMP-30, initiator A IBN is 0.1 ~ 0.34 part, and unsaturated polymer monomer is 20.22 ~ 67.4 parts of vinylbenzene;
Or bisphenol A type epoxy resin E-51 is 40 parts, MHHPA is 27.4 parts, and promotor is 0.4 part of glyoxal ethyline, and initiator A IBN is 0.1 ~ 0.24 part, and unsaturated polymer monomer is 20.22 ~ 47.2 parts of methyl methacrylates;
Or bisphenol A type epoxy resin E-51 is 40 parts, MHHPA is 27.4 parts, and promotor is 0.4 part of DMP-30, initiator A IBN is 0.17 part, and unsaturated polymer monomer is 33.7 parts of vinylbenzene;
Or bisphenol A type epoxy resin E-51 is 40 parts, MHHPA is 27.4 parts, and promotor is 0.4 part of DMP-30, initiator A IBN is 0.24 part, and unsaturated polymer monomer is 47.21 parts of vinylbenzene.
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| CN106189087B (en) * | 2016-07-16 | 2018-06-26 | 北京化工大学 | Low dielectric POSS type ring epoxy resin composite materials and preparation method thereof |
| CN106633680A (en) * | 2016-12-29 | 2017-05-10 | 江苏沃特特种材料制造有限公司 | Modified liquid crystal polyester resin composition, preparation method thereof and application of composition |
| CN111349215A (en) * | 2020-04-30 | 2020-06-30 | 西安天元化工有限责任公司 | Thermally initiated free radical reaction curing and conventional curing combined epoxy resin compositions |
| CN112409759B (en) * | 2020-11-06 | 2023-10-17 | 江苏高驰新材料科技有限公司 | Preparation method and application of resin-based low-dielectric composite material |
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| CN102432729A (en) * | 2011-09-13 | 2012-05-02 | 武汉菲克斯复合材料有限公司 | Modified epoxy resin by in-situ polymerization of double-bond unsaturated monomer |
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| CN102432729A (en) * | 2011-09-13 | 2012-05-02 | 武汉菲克斯复合材料有限公司 | Modified epoxy resin by in-situ polymerization of double-bond unsaturated monomer |
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