CN102924691A - Method for preparing low-dielectric epoxy resin composite material - Google Patents
Method for preparing low-dielectric epoxy resin composite material Download PDFInfo
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- CN102924691A CN102924691A CN2012104617783A CN201210461778A CN102924691A CN 102924691 A CN102924691 A CN 102924691A CN 2012104617783 A CN2012104617783 A CN 2012104617783A CN 201210461778 A CN201210461778 A CN 201210461778A CN 102924691 A CN102924691 A CN 102924691A
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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 the 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 transmission 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 the formula;
The K-constant;
The C-light velocity;
ε
rSpecific inductivity.
By following formula as can be known, the baseplate material that specific inductivity is lower satisfies the requirement of current electronic product high-speed high frequency.
Industry member has Resins, epoxy, polyimide resin, tetrafluoroethylene etc. as printed circuit board base board material resin commonly used at present.Tetrafluoroethylene has excellent dielectric properties, but exists following shortcoming: very poor in processability, and mechanics, the poor performance such as bonding, cost is high.Polyimide resin also is that the machine-shaping difficulty is large, and over-all properties is not good enough.Comparatively speaking, the Resins, epoxy raw material sources are abundant, and low price is easy to machine-shaping.Resins, epoxy after the curing has good physical and chemical performance, and solvent resistance is good, and linear expansivity is low, and physical strength is high, and Heat stability is good, good, the anti-surface leakage of dielectric properties, anti-electric arc etc. become present widespread use printed-wiring board (PWB) matrix material.But the in recent years develop rapidly of microelectronic is so that the dielectric properties of pure epoxy resin can't satisfy the requirement of current dielectric materials, and the specific inductivity that further reduces the epoxy resin-base material becomes the current problem that mainly solves.
At present research thinks that the main method that reduces material dielectric constant has two kinds: first method is chemical modification, namely in molecular structure, mix the strong electronegativity element, electronics is firmly held onto, reduce the polarity of material self, generally be used in now and mix fluorine in the material and reduce specific inductivity.The people such as Zhiqiang Tao have synthesized a kind of novel fluorine Resins, epoxy solidifies respectively at methyl hexahydrophthalic anhydride (MHHPA) and diaminodiphenylmethane (DDM), and with common bisphenol type epoxy contrast, specific inductivity has descended 0.2 ~ 0.3.The people such as J.R.Lee prepare a kind of fluorine-containing epoxy resin and DDM solidify after, than common bisphenol type epoxy contrast, under the different frequency condition reduced dielectric constant 0.2 ~ 0.4.Can reduce specific inductivity although mix fluorine, fall is little, and synthesis technique is complicated, cost is high.Another method is physical blending, physical blending can pass through two kinds of approach again: the first is made the molecular density that hole reduces material in dielectric materials, general use porous or hollow structure mineral filler such as how empty silicon-dioxide, molecular sieve, hollow glass microballoon, polyhedral oligomeric silsesquioxane (POSS) etc. more.Chinese patent CN 101638505A discloses a kind of low dielectric-epoxy resin/mesoporous molecular sieve hybrid material, and the specific inductivity maximum of pure epoxy resin has descended 0.9 relatively under 100kHz.Chinese patent CN 1783357A adds the mesoporous silicon oxide split respectively in Resins, epoxy and the polyimide resin, and under 1MHz, specific inductivity has descended respectively 0.82 and 0.57.Chinese patent CN101565545A discloses a kind of preparation method of ethylene rhodanate-epoxy-POSS hybrid resin, and POSS is scattered in the resin matrix with the molecular level level, and the mechanical property of the matrix material that obtains 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, adds hollow glass microballoon in epoxy resin-base, reduces the specific inductivity of Resins, epoxy.US Patent No. 20030143390A1 discloses a kind of polyarylene ether polymer that contains hollow structure, second-order transition temperature (T
g) being higher than 400 ℃, specific inductivity is lower than 2.5.In material, make the specific inductivity that hole can the decrease material, but the filler that adds a large amount of inorganic porous or hollow structures can cause the significant decline of material mechanical performance.It two is the specific inductivity that polymkeric substance (such as tetrafluoroethylene, the polyphenylene oxide etc.) blend of Resins, epoxy and low-k reduced material, disperses inequality but directly Resins, epoxy and low dielectric polymer blend are produced easily, and the problem such as be separated.The people such as Sixun Zheng are copolymer blended with Resins, epoxy and styrene-acrylonitrile, and studied consistency, pattern and the fracture toughness property of mixture, draw Resins, epoxy and two phase structure appears in styrene-acrylonitrile copolymer by scanning electron microscope and dynamic mechanical analysis.Chinese patent CN102372900A discloses a kind of composition epoxy resin and the prepreg of making and printed circuit board (PCB), said composition is Resins, epoxy and stiffening agent phenylethylene-maleic anhydride thereof, specific inductivity is 4.18 ~ 4.45 under 1GHz, and loss is 0.007 ~ 0.014.US Patent No. 005916683A discloses a kind of Resins, epoxy and the low dielectric polymer blend of aryl ester, and its specific inductivity is 2.70 ~ 2.90 under 1GHz.US Patent No. 006383660B2 discloses a kind of composition epoxy resin, and its component is: Resins, epoxy, resol, solidifying agent and promotor and hollow inorganic particle, prepare sample by different ingredients, its specific inductivity 2.7 ~ 3.2,105 ~ 167 ℃ of second-order transition temperatures.US Patent No. 6388009B1 discloses a kind of circuit card of low-k, and its component is Resins, epoxy, syndiotactic styrenic/aromatic polyamide-styrol copolymer, solidifying agent, specific inductivity is 2.9 ~ 3.6 after solidifying, specific inductivity is 3.1 ~ 4.5 behind the compound glass cloth.
In sum, chemical modification method, as mix fluorine and can reduce material dielectric constant, but the reduction amplitude is less, and synthesis technique is complicated, and cost is high.In matrix resin, add the specific inductivity that the hollow structure inorganics can significantly reduce material in the 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 simultaneously the performances such as the mechanics of material material, thermally-stabilised energy, but the POSS price is extremely expensive.Directly Resins, epoxy and low dielectric polymer blend are produced easily and disperse unevenly, the problem such as be separated.By simple, cost-effective method the Resins, epoxy dielectric properties being improved is current study hotspot, the present invention relevant report also do not occur at present by the monomer of the unsaturated polymer of low-k is disperseed to reduce the specific inductivity of Resins, epoxy in the polymerization of Resins, epoxy situ.
Summary of the invention
Technical problem to be solved by this invention is, a kind of preparation method of low dielectric-epoxy resin is provided, and can reduce specific inductivity and the dielectric loss of Resins, epoxy, and keep good physical strength.
The technical scheme that the present invention solve the technical problem employing is that the preparation method of low dielectric-epoxy resin composite materials is characterized in that, may further comprise the steps:
(1) epoxy monomer, solidifying agent and promotor are mixed under 70 ℃, vacuumize and remove bubble;
The unsaturated polymer monomer that (2) will contain initiator adds in the solution in the step (1), vacuumizes, and passes into N
2, be warming up to 80 ℃, stir pre-polymerization 2h;
(3) step (2) gained prepolymer is poured in the mould of 80 ℃ of lower preheatings, divide two stage solidification, ℃ (2h)+120, fs 80 ℃ of (2h)+100 ℃ (5h), ℃ (1h)+160,120 ℃ of (1h)+140 of subordinate phase ℃ (1h))+and 180 ℃ of (1h)+200 ℃ (2h), obtain the 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 the unsaturated polymer monomer is the rare or methyl methacrylate of benzene second.
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 of glyoxal ethyline, and initiator A IBN is 0.1 ~ 0.34 part, 20.22 ~ 67.4 parts of unsaturated polymer monomers.
Perhaps, 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, and initiator A IBN is 0.1 ~ 0.34 part, and the unsaturated polymer monomer is 20.22 ~ 67.4 parts of vinylbenzene.
Perhaps, 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, and initiator A IBN is 0.1 ~ 0.24 part, and the unsaturated polymer monomer is 20.22 ~ 47.2 parts of methyl methacrylates.
Perhaps, 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, and initiator is 0.17 part of AIBN, and the unsaturated polymer monomer is 11.2 ~ 16.8 parts of methyl methacrylates and 22.4 ~ 16.8 parts of cinnamic mixing.
Perhaps, 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, and initiator A IBN is 0.17 part, and the unsaturated polymer monomer is 33.7 parts of vinylbenzene.
Perhaps, 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, and initiator A IBN is 0.24 part, and the unsaturated polymer monomer is 47.21 parts of vinylbenzene.
The unsaturated polymer monomer of the present invention by will having low-k is in the polymerization of Resins, epoxy situ and dispersion, be scattered in the Resins, epoxy with nano-grade size, effectively reduce specific inductivity and the dielectric loss of Resins, epoxy, and keep good physical strength.Preparation technology is simple, and is solvent-free, low without toxic gas volatilization, environmental protection and cost.
Description of drawings
Fig. 1 is Resins, epoxy/poly styrene composite material cross-section morphology figure.From figure as can be known, ps particle is dispersed in the Resins, epoxy, and the median size of ps particle is about 50nm.
Embodiment
Embodiment 1
(1) with 40g bisphenol A type epoxy resin E-51,27.4g MHHPA and 0.4g DMP-30 at 70 ℃ of lower stirring and evenly mixings, vacuumize and remove bubble; (2) solution in the step (1) is poured in the mould of 80 ℃ of lower preheatings, curing molding, curing process is ℃ (1h)+200, ℃ (1h)+180, ℃ (1h)+160,120 ℃ of (1h)+140 ℃ (2h), obtains epoxy resin cured product, and its performance sees Table 2.
Embodiment 2
(1) with 40g bisphenol A type epoxy resin E-51,27.4g MHHPA and 0.4g DMP-30 at 70 ℃ of lower stirring and evenly mixings, vacuumize and remove bubble; (2) 0.10g AIBN fully is dissolved in the 20.22g vinylbenzene, vacuumizes in the solution in the adding step (1), pass into N
2, be warming up to 80 ℃, stir pre-polymerization 2h; (3) prepolymer in the step (2) is poured in the mould of 80 ℃ of lower preheatings, divide 2 stage solidification, ℃ (2h)+120, fs 80 ℃ of (2h)+100 ℃ (5h), ℃ (1h)+200, ℃ (1h)+180, ℃ (1h)+160,120 ℃ of (1h)+140 of subordinate phase ℃ (2h), obtain epoxy resin composite material, its performance sees Table 2.
Embodiment 3
(1) with 40g bisphenol A type epoxy resin E-51,27.4g MHHPA and 0.4g DMP-30 at 70 ℃ of lower stirring and evenly mixings, vacuumize and remove bubble; (2) 0.17g AIBN fully is dissolved in the 33.7g vinylbenzene, vacuumizes in the solution in the adding step (1), pass into N
2, be warming up to 80 ℃, stir pre-polymerization 2h; (3) prepolymer in the step (2) is poured in the mould of 80 ℃ of lower preheatings, divide 2 stage solidification, ℃ (2h)+120, fs 80 ℃ of (2h)+100 ℃ (5h), ℃ (1h)+200, ℃ (1h)+180, ℃ (1h)+160,120 ℃ of (1h)+140 of subordinate phase ℃ (2h), obtain epoxy resin composite material, its performance sees Table 2.
Embodiment 4
(1) with 40g bisphenol A type epoxy resin E-51,27.4g MHHPA and 0.4g DMP-30 at 70 ℃ of lower stirring and evenly mixings, vacuumize and remove bubble; (2) 0.24g AIBN fully is dissolved in the 47.21g vinylbenzene, vacuumizes in the solution in the adding step (1), pass into N
2, be warming up to 80 ℃, stir pre-polymerization 2h; (3) prepolymer in the step (2) is poured in the mould of 80 ℃ of lower preheatings, divide 2 stage solidification, ℃ (2h)+120, fs 80 ℃ of (2h)+100 ℃ (5h), ℃ (1h)+200, ℃ (1h)+180, ℃ (1h)+160,120 ℃ of (1h)+140 of subordinate phase ℃ (2h), obtain epoxy resin composite material, its performance sees Table 2.
Embodiment 5
(1) with 40g bisphenol A type epoxy resin E-51,27.4g MHHPA and 0.4g DMP-30 at 70 ℃ of lower stirring and evenly mixings, vacuumize and remove bubble; (2) 0.34g AIBN fully is dissolved in the 67.4g vinylbenzene, vacuumizes in the solution in the adding step (1), pass into N
2, be warming up to 80 ℃, stir pre-polymerization 2h; (3) prepolymer in the step (2) is poured in the mould of 80 ℃ of lower preheatings, divide 2 stage solidification, ℃ (2h)+120, fs 80 ℃ of (2h)+100 ℃ (5h), ℃ (1h)+200, ℃ (1h)+180, ℃ (1h)+160,120 ℃ of (1h)+140 of subordinate phase ℃ (2h), obtain epoxy resin composite material, its performance part sees Table 2.
Embodiment 6
(1) with 40g bisphenol A type epoxy resin E-51,27.4g MHHPA and 0.4g glyoxal ethyline at 70 ℃ of lower stirring and evenly mixings, vacuumize and remove bubble; (2) 0.10gAIBN fully is dissolved in the 20.22g methyl methacrylate, vacuumizes in the solution in the adding step (1), pass into N
2, be warming up to 80 ℃, stir pre-polymerization 2h; (3) the pre-thing liquid in the step (2) is poured in the mould of 80 ℃ of lower preheatings, divide 2 stage solidification, ℃ (2h)+120, fs 80 ℃ of (2h)+100 ℃ (5h), ℃ (1h)+200, ℃ (1h)+180, ℃ (1h)+160,120 ℃ of (1h)+140 of subordinate phase ℃ (2h), obtain epoxy resin composite material, its performance part sees Table 2.
Embodiment 7
(1) with 40g bisphenol A type epoxy resin E-51,27.4g MHHPA and 0.4g glyoxal ethyline at 70 ℃ of lower stirring and evenly mixings, vacuumize and remove bubble; (2) 0.17g AIBN fully is dissolved in the 33.7g methyl methacrylate, vacuumizes in the solution in the adding step (1), pass into N
2, be warming up to 80 ℃, stir pre-polymerization 2h; (3) prepolymer in the step (2) is poured in the mould of 80 ℃ of lower preheatings, divide 2 stage solidification, ℃ (2h)+120, fs 80 ℃ of (2h)+100 ℃ (5h), ℃ (1h)+200, ℃ (1h)+180, ℃ (1h)+160,120 ℃ of (1h)+140 of subordinate phase ℃ (2h), obtain epoxy resin composite material, its performance part sees Table 2.
(1) with 40g bisphenol A type epoxy resin E-51,27.4g MHHPA and 0.4g glyoxal ethyline at 70 ℃ of lower stirring and evenly mixings, vacuumize and remove bubble; (2) 0.24g AIBN fully is dissolved in the 47.2g methyl methacrylate, vacuumizes in the solution in the adding step (1), pass into N
2, be warming up to 80 ℃, stir pre-polymerization 2h; (3) prepolymer in the step (2) is poured in the mould of 80 ℃ of lower preheatings, divide 2 stage solidification, ℃ (2h)+120, fs 80 ℃ of (2h)+100 ℃ (5h), ℃ (1h)+200, ℃ (1h)+180, ℃ (1h)+160,120 ℃ of (1h)+140 of subordinate phase ℃ (2h), obtain epoxy resin composite material, its performance part sees Table 2.
Embodiment 9
(1) with 40g bisphenol A type epoxy resin E-51,27.4g MHHPA and 0.4g glyoxal ethyline at 70 ℃ of lower stirring and evenly mixings, vacuumize and remove bubble; (2) 0.17gAIBN fully is dissolved in 22.4g vinylbenzene and the 11.2g methyl methacrylate, vacuumizes in the solution in the adding step (1), pass into N
2, be warming up to 80 ℃, stir pre-polymerization 2h; (3) prepolymer in the step (2) is poured in the mould of 80 ℃ of lower preheatings, divide 2 stage solidification, ℃ (2h)+120, fs 80 ℃ of (2h)+100 ℃ (5h), ℃ (1h)+200, ℃ (1h)+180, ℃ (1h)+160,120 ℃ of (1h)+140 of subordinate phase ℃ (2h), obtain epoxy resin composite material, its performance part sees Table 2.
Embodiment 10
(1) with 40g bisphenol A type epoxy resin E-51,27.4g MHHPA and 0.4g glyoxal ethyline at 70 ℃ of lower stirring and evenly mixings, vacuumize and remove bubble; (2) 0.17gAIBN fully is dissolved in 16.8g vinylbenzene and the 16.8g methyl methacrylate, vacuumizes in the solution in the adding step (1), pass into N
2, be warming up to 80 ℃, stir pre-polymerization 2h; (3) prepolymer in the step (2) is poured in the mould of 80 ℃ of lower preheatings, divide 2 stage solidification, ℃ (2h)+120, fs 80 ℃ of (2h)+100 ℃ (5h), ℃ (1h)+200, ℃ (1h)+180, ℃ (1h)+160,120 ℃ of (1h)+140 of subordinate phase ℃ (2h), obtain epoxy resin composite material, its performance part sees Table 2.
Each embodiment material umber such as table 1:
Table 1
Comparative Examples 1
(1) prepares the fluorine-containing bisphenol A type epoxy resin of lower molecular weight take bisphenol AF and epoxy chloropropane as raw material by phase transfer catalysis process; (2) the fluorine-containing bisphenol A type epoxy resin of 40g, 21.7gMHHPA and 0.4gDMP-30 are mixed under 70 ℃, vacuumize and remove bubble; (3) solution in the step (2) is poured into curing molding in the mould of 80 ℃ of lower preheatings, curing process is ℃ (1h)+200, ℃ (1h)+180, ℃ (1h)+160,120 ℃ of (1h)+140 ℃ (2h), obtain epoxy resin cured product, its performance sees Table 2.
Comparative Examples 2
(1) 40g bisphenol A type epoxy resin E-51,27.44gMHHPA and 0.4gDMP-30 are mixed under 70 ℃, vacuumize and remove bubble; (2) the 6.74g polytetrafluorethylepowder powder is added in the step (1), stir, remove bubble; (3) mixture in the step (2) is poured into curing molding in the mould of 80 ℃ of lower preheatings, curing process is ℃ (1h)+200, ℃ (1h)+180, ℃ (1h)+160,120 ℃ of (1h)+140 ℃ (2h), obtain epoxy resin composite material, its performance sees Table 2.
Comparative Examples 3
(1) 40g bisphenol A type epoxy resin E-51,27.44gMHHPA and 0.4gDMP-30 are mixed under 70 ℃, vacuumize and remove bubble; (2) the 20.2g polytetrafluorethylepowder powder is added in the step (1), stir, remove bubble; (3) mixture in the step (2) is poured into curing molding in the mould of 80 ℃ of lower preheatings, curing process is ℃ (1h)+200, ℃ (1h)+180, ℃ (1h)+160,120 ℃ of (1h)+140 ℃ (2h), obtain epoxy resin composite material, its performance sees Table 2.
Comparative Examples 4
(1) with 40g bisphenol A type epoxy resin E-51,27.44gMHHPA, 2.02g nanometer SiO
2Mix under 70 ℃ with 0.4gDMP-30, vacuumize and remove bubble; (2) the 6.74g hollow glass microballoon is added in the step (1), stir, remove bubble; (3) mixture in the step (2) is poured into curing molding in the mould of 80 ℃ of lower preheatings, curing process is ℃ (1h)+200, ℃ (1h)+180, ℃ (1h)+160,120 ℃ of (1h)+140 ℃ (2h), obtain epoxy resin composite material, its performance sees Table 2.
Comparative Examples 5
(1) with 40g bisphenol A type epoxy resin E-51,27.44gMHHPA, 2.02g nanometer SiO
2Mix under 70 ℃ with 0.4gDMP-30, vacuumize and remove bubble; (2) the 20.2g hollow glass microballoon is added in the step (1), stir, remove bubble; (3) mixture in the step (2) is poured into curing molding in the mould of 80 ℃ of lower preheatings, curing process is ℃ (1h)+200, ℃ (1h)+180, ℃ (1h)+160,120 ℃ of (1h)+140 ℃ (2h), obtain epoxy resin composite material, its performance sees Table 2.
Comparative Examples 6
(1) with 40g bisphenol A type epoxy resin E-51,27.44gMHHPA, 2.02g nanometer SiO
2Mix under 70 ℃ with DMP-30, vacuumize and remove bubble; (2) the 33.7g hollow glass microballoon is added in the step (1), stir, remove bubble; (3) mixture in the step (2) is poured into curing molding in the mould of 80 ℃ of lower preheatings, curing process is ℃ (1h)+200, ℃ (1h)+180, ℃ (1h)+160,120 ℃ of (1h)+140 ℃ (2h), obtain epoxy resin composite material, its performance sees Table 2.
Table 2
Data by embodiment in the table 21 ~ 5 as can be known, when the unsaturated polymer monomer is vinylbenzene, and the increase of content, specific inductivity and the dielectric loss of Resins, epoxy/polystyrene nano composite material are on a declining curve, when vinylbenzene consumption and resin matrix mass ratio are 1:1, specific inductivity descends 0.57, and dielectric loss descends 0.0008.
When embodiment 6 ~ 8 was the methacrylic methyl esters when the unsaturated polymer monomer, the specific inductivity of material was also on a declining curve, but compared with the vinylbenzene system, and the specific inductivity fall is little; It is good that mechanical property is compared the vinylbenzene system.
Embodiment 9 ~ 10 when the unsaturated polymer monomer be two kinds of vinylbenzene and methyl methacrylates when composite, along with the increase of methyl methacrylate amount, the specific inductivity of material can increase, but the mechanical properties decrease amplitude reduces.
By comparative example 1 ~ 10, can draw embodiment 3,4 over-all propertieies the best.The mechanical system of comparing embodiment 4 with Comparative Examples 1 is lower.In the Comparative Examples the 2, the 3rd, Resins, epoxy/polytetrafluorethylepowder powder system, although have excellent dielectric properties, the mechanical property loss is too large.Be Resins, epoxy/hollow glass microballoon system in the Comparative Examples 4 ~ 6, embodiment 3,4 in contrast, specific inductivity is slightly high, but dielectric loss is starkly lower than Resins, epoxy/hollow glass microballoon system, and mechanical property is also than better.
In sum, by with the insatiable hunger polymer monomer in the polymerization of Resins, epoxy situ, be scattered in the Resins, epoxy with nano-grade size, when having improved the Resins, epoxy dielectric properties, also keeping preferably mechanical property.When monomer is vinylbenzene, and when being 5:10 ~ 7:10 with the Resins, epoxy mass ratio, the over-all properties of low dielectric-epoxy resin composite materials is best.
Claims (8)
1. the preparation method of low dielectric-epoxy resin composite materials is characterized in that, may further comprise the steps:
(1) epoxy monomer, solidifying agent and promotor are mixed under 70 ℃, vacuumize and remove bubble;
The unsaturated polymer monomer that (2) will contain initiator adds in the solution in the step (1), vacuumizes, and passes into N
2, be warming up to 80 ℃, stir pre-polymerization 2h;
(3) step (2) gained prepolymer is poured in the mould of 80 ℃ of lower preheatings, divide two stage solidification, ℃ (2h)+120, fs 80 ℃ of (2h)+100 ℃ (5h), ℃ (1h)+160,120 ℃ of (1h)+140 of subordinate phase ℃ (1h))+and 180 ℃ of (1h)+200 ℃ (2h), obtain the low dielectric-epoxy resin composite materials;
Described epoxy monomer is bisphenol A type epoxy resin E-51, and solidifying agent is MHHPA.
2. the preparation method of low dielectric-epoxy resin composite materials as claimed in claim 1 is characterized in that, described promotor is DMP-30 or glyoxal ethyline, and initiator is AIBN, and the unsaturated polymer monomer is the rare or methyl methacrylate of benzene second.
3. the preparation method of low dielectric-epoxy resin composite materials as claimed in claim 2, it is characterized in that, count by weight, bisphenol A type epoxy resin E-51 is 40 parts, MHHPA is 27.4 parts, promotor is 0.4 part of DMP-30 or 0.4 part of glyoxal ethyline, and initiator A IBN is 0.1 ~ 0.34 part, 20.22 ~ 67.4 parts of unsaturated polymer monomers.
4. the preparation method of low dielectric-epoxy resin composite materials as claimed in claim 2, it is characterized in that, count by weight, bisphenol A type epoxy resin E-51 is 40 parts, MHHPA is 27.4 parts, promotor is 0.4 part of DMP-30, and initiator A IBN is 0.1 ~ 0.34 part, and the unsaturated polymer monomer is 20.22 ~ 67.4 parts of vinylbenzene.
5. the preparation method of low dielectric-epoxy resin composite materials as claimed in claim 2, it is characterized in that, count by weight, bisphenol A type epoxy resin E-51 is 40 parts, MHHPA is 27.4 parts, promotor is 0.4 part of glyoxal ethyline, and initiator A IBN is 0.1 ~ 0.24 part, and the unsaturated polymer monomer is 20.22 ~ 47.2 parts of methyl methacrylates.
6. the preparation method of low dielectric-epoxy resin composite materials as claimed in claim 2, it is characterized in that, count by weight, bisphenol A type epoxy resin E-51 is 40 parts, MHHPA is 27.4 parts, promotor is 0.4 part of glyoxal ethyline, and initiator is 0.17 part of AIBN, and the unsaturated polymer monomer is 11.2 ~ 16.8 parts of methyl methacrylates and 22.4 ~ 16.8 parts of cinnamic mixing.
7. the preparation method of low dielectric-epoxy resin composite materials as claimed in claim 2, it is characterized in that, count by weight, bisphenol A type epoxy resin E-51 is 40 parts, MHHPA is 27.4 parts, promotor is 0.4 part of DMP-30, and initiator A IBN is 0.17 part, and the unsaturated polymer monomer is 33.7 parts of vinylbenzene.
8. the preparation method of low dielectric-epoxy resin composite materials as claimed in claim 2, it is characterized in that, count by weight, bisphenol A type epoxy resin E-51 is 40 parts, MHHPA is 27.4 parts, promotor is 0.4 part of DMP-30, and initiator A IBN is 0.24 part, and the unsaturated polymer monomer is 47.21 parts of vinylbenzene.
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Cited By (7)
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| CN104861123A (en) * | 2015-05-21 | 2015-08-26 | 浙江大学 | Method for modifying epoxy resin by reaction type multi-block copolymer |
| CN105542408A (en) * | 2015-12-29 | 2016-05-04 | 江苏沃特特种材料制造有限公司 | Modified wholly aromatic liquid crystal polyester resin composition and preparation method thereof |
| CN105802219A (en) * | 2016-06-02 | 2016-07-27 | 黑龙江省科学院石油化学研究院 | Ultralow-density low-loss cyanate-based composite foam material and preparation method thereof |
| CN106189087A (en) * | 2016-07-16 | 2016-12-07 | 北京化工大学 | Low dielectric poss type epoxy resin composite material 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 |
| CN112409759A (en) * | 2020-11-06 | 2021-02-26 | 裴佩 | Preparation method and application of resin-based low-dielectric composite material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104861123A (en) * | 2015-05-21 | 2015-08-26 | 浙江大学 | Method for modifying epoxy resin by reaction type multi-block copolymer |
| CN105542408A (en) * | 2015-12-29 | 2016-05-04 | 江苏沃特特种材料制造有限公司 | Modified wholly aromatic liquid crystal polyester resin composition and preparation method thereof |
| CN105802219A (en) * | 2016-06-02 | 2016-07-27 | 黑龙江省科学院石油化学研究院 | Ultralow-density low-loss cyanate-based composite foam material and preparation method thereof |
| CN105802219B (en) * | 2016-06-02 | 2018-10-12 | 黑龙江省科学院石油化学研究院 | A kind of extremely-low density, low-loss cyanic acid ester group composite foam material and preparation method thereof |
| CN106189087A (en) * | 2016-07-16 | 2016-12-07 | 北京化工大学 | Low dielectric poss type epoxy resin composite material and preparation method thereof |
| 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 |
| CN112409759A (en) * | 2020-11-06 | 2021-02-26 | 裴佩 | Preparation method and application of resin-based low-dielectric composite material |
| 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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