CN104448713A - Open-cell type heat-conducting epoxy matrix composite porous material and preparation method and application thereof - Google Patents
Open-cell type heat-conducting epoxy matrix composite porous material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an open-cell type heat-conducting epoxy matrix composite porous material and a preparation method and an application of the porous material. The porous material is prepared from 20 to 40wt% of epoxy resin-heat conducting ceramic powder-modified amine pre-mixed solution and 80 to 60wt% of inorganic filler-aqueous suspension; the epoxy resin-heat conducting ceramic powder-modified amine pre-mixed solution is prepared from 100 parts by weight of epoxy resin, 3 to 30 parts by weight of heat conducting ceramic powder and 50 to 100 parts by weight of poly-oxypropylene polyether modified amine curing agent by pre-mixing for 3 to 10 minutes under a temperature of 20 to 35 DEG C. The porous material is of an open-cell structure, remarkable in air and water permeability, and outstanding in toughness and heat conductivity, and has a good application prospect in the ceramics field, the electronic field, the battery diaphragm field, the environmental protection field, the air purifying field, the chemicals field, the building field and other fields.
Description
Technical field
The invention belongs to field of porous materials, particularly a kind of open cell type thermal conductivity epoxy group(ing) composite porous material and method for making thereof and application.
Background technology
Porous material is the solid material that a large amount of bubble space is contained in a kind of inside, owing to having the characteristics such as special periodic structure, high-specific surface area, high absorbability, drillability rate, high porosity, has shown in a lot of fields and has applied widely.Porous material is divided into open cell type and obturator-type.Porous material can be divided into micropore (be less than 2nm), mesopore (2 ~ 50nm), macropore (be greater than 50nm) by international theory chemistry with the division of application association (IUPAC) according to pore size, and they each corresponding corresponding purposes.
Open cell porous material is the solid material be interconnected between finger-hole and hole, also known as via material, be characterized in that the foam structure in material is open, complicated passage can be formed, allow micro-molecular gas or fluid be flowed by material, separation and concentration material, permeable filtering material, battery diaphragm, support of the catalyst, controlled drug release etc. can be done.
At present, porous material is become to study for thermoplastic resin both at home and abroad many, research and the organic polymer porous material applied are prepared by macromolecular solution or melt (thermoplastic polymer) usually, and main method has the continuous extrusion molding of phase separation method, physical blowing, chemical blowing process, hot-forming method, stripping method, stretching method, radiation exposure method, sintering process.
The thermosetting polymer that polyaddition reaction is cross-linked to form the tridimensional network of certain degree of crosslinking can be there is under epoxy resin-amine system room temperature, small molecules product is not had to produce in reaction process, there is very strong force of cohesion and molecular structure density and good heat resistance, cure shrinkage be little, adhesiveproperties is excellent, acid and alkali-resistance and solvent resistance good characteristics, be widely used in tackiness agent, coating, water-proof material, electronic circuit plate substrate and plastic cement etc.
The research preparing the base composite porous material of high-strength epoxy with thermosetting epoxy resin rarely has to be mentioned.Chinese patent ZL98117513.9 " a kind of resin die material " adopts the method for adding softening agent to improve the toughness of mould, repeatedly using clearly along with mould, softening agent can to external migration under ambient pressure, and the strength of materials is greatly affected, and reusable number of times is limited.ZL201110272600.X " a kind of preparation method of epoxy resin porous material " discloses the organic by-products in an organic solvent producing with water extraction Epoxy Industry, the dissolved organic matter drawn and salt are to prepare epoxy resin porous material, its intensity is low, and range of application is little.ZL200810198509.6 " a kind of multi-microporous epoxy thermosetting resin and preparation method thereof " discloses and carrys out gate ring epoxy resins pore-forming with organic solvent and supercritical co, but does not relate to the intensity of prepared porous material.
Summary of the invention
In order to overcome the shortcoming and defect of prior art, primary and foremost purpose of the present invention is to provide a kind of without the need to open cell type thermal conductivity epoxy group(ing) composite porous material with an organic solvent.
Another object of the present invention is to the preparation method that above-mentioned open cell type thermal conductivity epoxy group(ing) composite porous material is provided.
Another object of the present invention is the application providing above-mentioned open cell type thermal conductivity epoxy group(ing) composite porous material.
Object of the present invention is achieved through the following technical solutions:
A kind of open cell type thermal conductivity epoxy group(ing) composite porous material, is prepared from by following component by mass percentage:
Epoxy resin-thermal conductive ceramic powder-modified amine premix 20 ~ 40wt%
Mineral filler-aqeous suspension 80 ~ 60wt%
Above each component amounts to 100wt%.
Described epoxy resin-thermal conductive ceramic powder-modified amine premix is prepared by following preparation method: by the pre-mixing 3 ~ 10 minutes at 20 ~ 35 DEG C of 100 parts by weight epoxy resin, 3 ~ 30 weight part thermal conductive ceramic powders and 50 ~ 100 part by weight modified amine curing agents;
Described epoxy resin is more than one in the bisphenol A type epoxy resin of bisphenol A type epoxy resin or polyoxypropylene polyether Type Polyurethane Prepolymer chemical modification; Described bisphenol A type epoxy resin is epoxy resin E-51, epoxy resin E-44 or epoxy resin E-20.
Described polyoxypropylene polyether Type Polyurethane Prepolymer reacts by tolylene diisocyanate (TDI) and polyether glycol the adduct containing active isocyano prepared, and its headformulae is
wherein n is the integer of 17 ~ 35;
Described polyether glycol is more than one in polyethers N210 or polyethers N220.
Described thermal conductive ceramic powder is more than one in aluminum oxide, aluminium hydroxide, boron nitride, aluminium nitride, silicon carbide, silicon nitride or silicon-dioxide; The median size of described thermal conductive ceramic powder is 3 ~ 100 μm, and the thermal conductive ceramic powder of preferred different-grain diameter is arranged in pairs or groups mutually.
Described modified amine curing agent is the whole PAMAM PAMAM of dendroid of polyoxypropylene polyether modification Amino End Group, polyoxypropylene polyether modified low molecular weight polyamide 6 50, polyoxypropylene polyether modified low molecular weight polyamide 6 51, polyoxypropylene polyether modified phenolic amine or containing more than one in the polyetheramine of polyoxypropylene segment.
The described polyetheramine containing polyoxypropylene segment be in polyetheramine D230, polyetheramine D400 or polyetheramine T403 more than one.
The whole PAMAM of dendroid (PAMAM) of described polyoxypropylene polyether modification Amino End Group is the whole PAMAM of dendroid (PAMAM) and the reaction product of polyoxypropylene diglycidylether (or claiming polypropylene glycol diglycidyl ether); Polyoxypropylene polyether modified polyamide 6 50 is the reaction product of epoxy hardener polyamide 6 50 and polyoxypropylene diglycidylether, polyoxypropylene polyether modified polyamide 6 51 is the reaction product of epoxy hardener polyamide 6 51 and polyoxypropylene diglycidylether, and polyoxypropylene polyether modified phenolic amine is the reaction product of epoxy hardener phenolic aldehyde amine and polyoxypropylene diglycidylether.
In described epoxy resin-thermal conductive ceramic powder-amine pre-mixing system, polyoxypropylene polyether accounts for 5 ~ 25% of epoxy resin and modified amine curing agent gross weight.
Described mineral filler-aqeous suspension prepares by the following method: by the pre-mixing 3 ~ 20 minutes at 20 ~ 50 DEG C of the water of 100 parts by weight of inorganic fillers and 55 ~ 75 weight parts.
Described mineral filler be thermal conductive ceramic filler or silicate minerals more than one; Described mineral filler median size is at 3 ~ 100 μm, and the powder that described mineral filler is preferably different-grain diameter is arranged in pairs or groups mutually.Described thermal conductive ceramic filler be in aluminum oxide, aluminium hydroxide, boron nitride, aluminium nitride, silicon carbide, silicon nitride, silicon-dioxide or conductive graphite powder more than one; Described silicate minerals be in polynite, kaolin, wilkinite, mica powder or talcum powder more than one.
The preparation method of described open cell type thermal conductivity epoxy group(ing) composite porous material, comprises the following steps:
(1) under the condition of rapid stirring and 20 ~ 35 DEG C, in epoxy resin-thermal conductive ceramic powder-modified amine premix, add mineral filler-aqeous suspension, continue rapid stirring 3 ~ 10 minutes, be uniformly mixed liquid;
(2) poured in mould by mixed solution in 3 minutes, solidification, obtains open cell type thermal conductivity epoxy group(ing) composite porous material.
The stirring velocity of described rapid stirring is 2000 ~ 300 revs/min.
Described condition of cure is in 20 ~ 35 DEG C of solidifications 3 ~ 7 days, or within 1 day, solidifies 1 ~ 2 day at 36 ~ 50 DEG C prior to 20 ~ 35 DEG C of solidifications again.
Described porous material has the ventilative water permeability of open-celled structure and excellence and good toughness, and ultimate compression strength is up to more than 15MPa, folding strength up to more than 5MPa, and thermal conductivity is up to more than 0.5W/ (mK).
Described open cell type thermal conductivity epoxy group(ing) composite porous material hole is little, containing excessive active amino or can introduce other function base, there is the functions such as selective filter, separation and absorption, have broad application prospects in the fields such as pottery, electronics, battery porous diaphragm, environmental protection, purifying air, chemical industry, building.
Dendrimer is a kind of is vegetative point with small molecules, the a series of relative molecular masses obtained by step reaction are constantly increased and the dendritic compound of similar, and branch outwards stretches, externally to spherical, inside is cavity, can form vesicular structure well.Dendritic interphase PAMAM molecule of whole generation outside is primary amino, can with epoxide group generation chemical reaction, inner containing tertiary amine groups, can the ring-opening reaction of effective catalysis epoxide group.Meanwhile, dendritic interphase PAMAM, low molecular polyamides and polyether-modified polymeric amide etc. all effectively can improve the toughness of epoxy resin.
Polyoxypropylene polyether segment has surface-active action, pendant hydrophobic methyl wherein makes water droplet at the stable tiny emulsion droplet of the dispersed one-tenth of whole mixed system, these emulsion droplets are dispersed between epoxy resin and inorganic filler particle, effect because of hydrophobic meth group makes epoxy resin and inorganic filler particle form certain hole and passage, and the through-hole structure that final formation is stable after the epoxy resin is cured.It is the main source of hole that tiny water and milk drips, and by through hole effect, innerly mutually to run through with surface, has excellent air-and water-permeable performance.
The present invention adopts polyoxypropylene polyether segment and epoxy resin prepolymer binding, polyoxypropylene polyether segment and polyamide prepolymer binding, after making epoxy resin and solidifying agent short period of time hybrid reaction, (before uncrosslinked) has self-emulsifying action, make whole resin-filler-aqueous suspension mixed system keep stable always, separate out without small molecules or extrude, there is the feature of environmental protection.Owing to using thermal conductive ceramic powder filler boron nitride, aluminium nitride, silicon carbide, silicon nitride, aluminum oxide, aluminium hydroxide, silicon-dioxide or/and conductive graphite powder, the porous material of curing molding is made to have excellent thermal conductivity.
Compared with prior art, the present invention has the following advantages and beneficial effect:
(1) the present invention is with polymerisable polyoxypropylene polyether segment epoxy resin or modified amine for active emulsifier, is pore-creating agent with water, has the feature of the easy and environmental protection of preparation technology.
(2) epoxy matrix composite of the present invention has open-celled structure, and ventilative water permeability is excellent, and intensity is high, good toughness, can repeatedly use.
(3) prepared by the present invention epoxy group(ing) composite porous there is good heat conductivility.
Accompanying drawing explanation
The SEM figure of the thermal conductivity epoxy group(ing) composite porous material of Fig. 1 prepared by embodiment 3.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
The preparation of polyoxypropylene polyether modified epoxy:
In the there-necked flask of 5000mL, add the polyethers N210 of 800g, then under agitation add the TDI of 167g, be warming up to 90 DEG C of reactions 3 hours.Then add E-44 epoxy resin 2500g, continue maintenance 90 DEG C reaction 3 hours, cooling, namely obtained polyoxypropylene polyether percentage composition is the modified epoxy E1 of 23.1wt%.
Embodiment 2
The preparation of modified amine curing agent:
(1) the whole PAMAM of the dendroid of Amino End Group (PAMAM)
1 of 0.3mol (34.86g) is added in the there-necked flask of 500mL, the anhydrous methanol of 6-hexanediamine and 150g, the methyl acrylate of 1.2mol (103.2g) is slowly dripped under room temperature, drip off in 1 hour, continue at room temperature to stir 4 hours, then be warming up to 70 DEG C of back flow reaction 5 hours.Then underpressure distillation, removing methyl alcohol.Cooling, then adds 1, the 6-hexanediamine of 1.2mol (139.44g) and the methyl alcohol of 5g, is warming up to 70 DEG C of back flow reaction after 2 hours, underpressure distillation, and removing methyl alcohol, cooling, obtains the dendroid 1 PAMAM PAMAM of Amino End Group, count PAMAM1.
Take out the PAMAM1 of 1/4 weight, again add the anhydrous methanol of 150g, under room temperature, slowly drip the methyl acrylate of 1.2mol (103.2g), drip off in 1 hour, continue at room temperature to stir 4 hours, then be warming up to 70 DEG C of back flow reaction 5 hours.Then underpressure distillation, removing methyl alcohol.Cooling, then adds 1, the 6-hexanediamine of 1.2mol (139.44g) and the methyl alcohol of 5g, is warming up to 70 DEG C of back flow reaction after 2 hours, underpressure distillation, and removing methyl alcohol, cooling, obtains the dendroid 2 PAMAM PAMAM of Amino End Group, count PAMAM2.
(2) whole generation dendritic interphase (polyoxypropylene polyether modification PAMAM) of polyoxypropylene polyether modification Amino End Group
The PAMAM1 of 190g is added in the there-necked flask of 500mL, add under stirring at room temperature 10g polyoxypropylene diglycidylether (or claim polypropylene glycol diglycidyl ether, XY207, An Weixin Chemicals far away), be warming up to 50 DEG C of reactions 3 hours, cooling, obtains modified polyamide-amine PAMAM that polyoxypropylene polyether percentage composition is 5wt%, counts MPAMAM1.
The PAMAM2 of 180g is added in the there-necked flask of 500mL, polyoxypropylene diglycidylether (the XY207 of 20g is added under stirring at room temperature, An Weixin Chemicals far away), be warming up to 50 DEG C of reactions 3 hours, cooling, obtain modified polyamide-amine PAMAM that polyoxypropylene polyether percentage composition is 10wt%, count MPAMAM2.
(3) polyoxypropylene polyether modified low molecular weight polyamide 6 50 (epoxy hardener)
The low molecular polyamides 650 (changzhou De Ye Chemical Co., Ltd. product) of 300g is added in the there-necked flask of 500mL, polyoxypropylene diglycidylether (the XY207 of 30g is added under stirring at room temperature, An Weixin Chemicals far away), be warming up to 50 DEG C of reactions 3 hours, cooling, obtain the modified low molecular weight polyamide 6 50 that polyoxypropylene polyether percentage composition is 9.1wt%, count PAM1.
The low molecular polyamides 650 of 300g is added in the there-necked flask of 500mL, polyoxypropylene diglycidylether (the XY207 of 75g is added under stirring at room temperature, An Weixin Chemicals far away), be warming up to 50 DEG C of reactions 3 hours, cooling, obtain the modified low molecular weight polyamide 6 50 that polyoxypropylene polyether percentage composition is 20wt%, count PAM2.
(4) polyoxypropylene polyether modified low molecular weight polyamide 6 51 (epoxy hardener)
The low molecular polyamides 651 (changzhou De Ye Chemical Co., Ltd. product) of 300g is added in the there-necked flask of 500mL, polyoxypropylene diglycidylether (the XY207 of 45g is added under stirring at room temperature, An Weixin Chemicals far away), be warming up to 50 DEG C of reactions 3 hours, cooling, obtain the modified low molecular weight polyamide 6 51 that polyoxypropylene polyether percentage composition is 13wt%, count PAM3.
The low molecular polyamides 651 of 300g is added in the there-necked flask of 500mL, polyoxypropylene diglycidylether (the XY207 of 90g is added under stirring at room temperature, An Weixin Chemicals far away), be warming up to 50 DEG C of reactions 3 hours, cooling, obtain the modified low molecular weight polyamide 6 51 that polyoxypropylene polyether percentage composition is 23.1wt%, count PAM4.
(5) polyoxypropylene polyether modified phenolic amine (epoxy hardener)
In the there-necked flask of 500mL, add 94g phenol and 146g triethylene tetramine, add paraformaldehyde 30g, be warming up to 90 DEG C of reactions 3 hours, cooling, obtained epoxy hardener phenolic aldehyde amine.Then add the polyoxypropylene diglycidylether (XY207, An Weixin Chemicals far away) of 54g, be warming up to 50 DEG C of reactions 3 hours, cooling, obtains the modified phenolic amine that polyoxypropylene polyether percentage composition is 16.7%, counts MT31.
Embodiment 3
A kind of open cell type thermal conductivity epoxy group(ing) composite porous material, is prepared by following steps:
(1) at room temperature 35 DEG C, in the plastic measuring glass of 1000mL, add median size be successively respectively the silicon oxide 50g of 100 μm, the silicon carbide 200g of 30 μm, the polynite 65g of 10 μm and water 175g, stirring, (time of stirring is 10min, mixing speed is 500r/min), obtain filler-aqeous suspension 490g;
(2) at room temperature 35 DEG C, in the plastic measuring glass of another 1000mL, add the obtained polyoxypropylene polyether modified epoxy E1 of 93g example 1 successively, median size to be aluminium hydroxide 15g, the median size of 3 μm the be silicon carbide 12g of 30 μm and the obtained modified polyamide PAM2 of 90g embodiment 2, at 35 DEG C, with the stirring velocity rapid stirring 3 minutes of 1000r/min, obtain epoxy resin-thermal conductive ceramic powder-modified amine premix 210g;
(3) 490g filler-aqeous suspension is poured in 210g epoxy resin-thermal conductive ceramic powder-amine premix, in the stirring velocity rapid stirring 3 minutes of 1000r/min, then be all poured in mould in 1 minute, solidify 3 days at room temperature 35 DEG C, obtain open cell type thermal conductivity epoxy group(ing) composite porous material, its structural characterization as shown in Figure 1.As can be seen from Figure 1, this composite porous material has obvious vesicular structure.
At 25 DEG C, test the ventilative water permeability of curing module (i.e. composite porous material), pressure-proof and snap-resistent intensity and thermal conductivity, result is as shown in table 1.
Embodiment 4
A kind of open cell type thermal conductivity epoxy group(ing) composite porous material, is prepared by following steps:
(1) at room temperature 20 DEG C, in the plastic measuring glass of 1000mL, add median size be successively respectively the aluminum oxide 150g of 3 μm, the silicon nitride 30g of 10 μm, the kaolin 100g of 20 μm and water 210g, stirring, (time of stirring is 15min, mixing speed is 500r/min), obtain filler-aqeous suspension 490g;
(2) in the plastic measuring glass of another 1000mL, add the obtained polyoxypropylene polyether modified epoxy E1 of 100g example 1 successively, median size to be silica 1 0g, the median size of 10 μm the be silicon carbide 10g of 30 μm and the obtained MPAMAM1 of 90g embodiment 2, at 20 DEG C, with the stirring velocity rapid stirring 5 minutes of 500r/min, obtain epoxy resin-thermal conductive ceramic powder-modified amine premix 210g;
(3) 490g filler-aqeous suspension is poured in 210g epoxy resin-thermal conductive ceramic powder-amine premix, in the stirring velocity rapid stirring 5 minutes of 500r/min, then be all poured in mould in 3 minutes, solidify 7 days at room temperature 20 DEG C, obtain open cell type thermal conductivity epoxy group(ing) composite porous material.
At 25 DEG C, test the ventilative water permeability of curing module (i.e. composite porous material), pressure-proof and snap-resistent intensity and thermal conductivity, result is as shown in table 1.
Embodiment 5
A kind of open cell type thermal conductivity epoxy group(ing) composite porous material, is prepared by following steps:
(1) at room temperature 20 DEG C, Graphite Powder 99 111g and water 199g that the aluminum oxide 100g that to add median size in the plastic measuring glass of 1000mL be successively aluminum oxide 150g, the median size of 3 μm is 30 μm, median size are 10 μm, stirring, (time of stirring is 10min, mixing speed is 1500r/min), obtain filler-aqeous suspension 560g.
(2) in the plastic measuring glass of another 1000mL, add obtained polyoxypropylene polyether modified epoxy E1,49g E-51 epoxy resin of 31g example 1 successively, 2.5g median size is the aluminium nitride of 10 μm and 57.5g embodiment 2 is obtained MPAMAM2, at 20 DEG C, with the stirring velocity rapid stirring 10 minutes of 300r/min, obtain epoxy resin-thermal conductive ceramic powder-modified amine premix 140g;
(3) 560g filler-aqeous suspension is poured in 140g epoxy resin-thermal conductive ceramic powder-modified amine premix, in the stirring velocity rapid stirring 10 minutes of 300r/min, then be all poured in mould in 3 minutes, solidify 7 days at room temperature 20 DEG C, obtain open cell type thermal conductivity epoxy group(ing) composite porous material.
At 25 DEG C, test the ventilative water permeability of curing module (i.e. composite porous material), pressure-proof and snap-resistent intensity and thermal conductivity, result is as shown in table 1.
Embodiment 6
A kind of open cell type thermal conductivity epoxy group(ing) composite porous material, is prepared by following steps:
(1) at room temperature 25 DEG C, in the plastic measuring glass of 1000mL, add median size be successively aluminum oxide 160g, the median size of 5 μm is silicon carbide 80g and the water 180g of 50 μm, stirring, (time of stirring is 5min, mixing speed is 2000r/min), obtain filler-aqeous suspension 420g.
(2) in the plastic measuring glass of another 1000mL, add 140g blending epoxy (100g E-51 epoxy resin and 40g E-20 epoxy resin) successively, median size to be silicon carbide 20g, the median size of 10 μm the be boron nitride 20g of 5 μm and 100g embodiment 2 obtain modified polyamide PAM3, at 25 DEG C, with the stirring velocity rapid stirring 5 minutes of 2000r/min, obtain epoxy resin-thermal conductive ceramic powder-modified amine premix 280g;
(3) 420g filler-aqeous suspension is poured in 280g epoxy resin-thermal conductive ceramic powder-modified amine premix, with the stirring velocity rapid stirring 6 minutes of 2000r/min, then be all poured in mould in 3 minutes, solidify 1 day at room temperature 25 DEG C, then solidify 1 day under being placed in 50 DEG C of environment, obtain open cell type thermal conductivity epoxy group(ing) composite porous material.
At 25 DEG C, test the ventilative water permeability of curing module (i.e. composite porous material), pressure-proof and snap-resistent intensity and thermal conductivity, result is as shown in table 1.
Embodiment 7
A kind of open cell type thermal conductivity epoxy group(ing) composite porous material, is prepared by following steps:
(1) at room temperature 30 DEG C, wilkinite 90g and water 150g that the silicon carbide 90g that to add median size in the plastic measuring glass of 1000mL be successively mica powder 90g, the median size of 10 μm is 50 μm, median size are 20 μm, stir after (time of stirring is 20min, and mixing speed is 300r/min) and obtain filler-aqeous suspension 420g.
(2) in the plastic measuring glass of another 1000mL, add 140g epoxy resin E-51 successively, median size is respectively the silicon nitride 10g of 10 μm, the silicon carbide 10g of 50 μm and 20g embodiment 2 obtain modified polyamide PAM1 and 100g PAM4, at 30 DEG C, the stirring velocity rapid stirring of 800r/min 5 minutes, obtains epoxy resin-thermal conductive ceramic powder-modified amine premix 280g.
(3) filler-aqeous suspension of 420g is poured in 280g epoxy resin-thermal conductive ceramic powder-modified amine premix, in the stirring velocity rapid stirring 3 minutes of 800r/min, then be all poured in mould in 3 minutes, solidify 1 day at room temperature 30 DEG C, then solidify 2 days under being placed in 40 DEG C of environment, obtain open cell type thermal conductivity epoxy group(ing) composite porous material.
At 25 DEG C, test the ventilative water permeability of curing module (i.e. composite porous material), pressure-proof and snap-resistent intensity and thermal conductivity, result is as shown in table 1.
Embodiment 8
A kind of open cell type thermal conductivity epoxy group(ing) composite porous material, is prepared by following steps:
(1) at room temperature 35 DEG C, talcum powder 112g and water 188g that the silicon carbide 150g that to add median size in the plastic measuring glass of 1000mL be successively aluminum oxide 50g, the median size of 100 μm is 30 μm, median size are 10 μm, stirring, (time of stirring is 15min, mixing speed is 100r/min), obtain filler-aqeous suspension 500g;
(2) in the plastic measuring glass of another 1000mL, add 50g blending epoxy (E-51:E-20=100:20 (weight ratio)) successively, polyoxypropylene polyether modified epoxy E1, median size prepared by 70g embodiment 1 to be silicon carbide 10g, the median size of 10 μm the be aluminum oxide 10g of 3 μm and 60g embodiment 2 obtain modified phenolic amine MT31, at 35 DEG C, the stirring velocity rapid stirring of 1000r/min 3 minutes, obtains epoxy resin-thermal conductive ceramic powder-modified amine premix 200g;
(3) 500g filler-aqeous suspension is poured in 200g epoxy resin-thermal conductive ceramic powder-modified amine premix, in the stirring velocity rapid stirring 3 minutes of 1000r/min, then be all poured in mould in 2 minutes, solidify 3 days at room temperature 35 DEG C, obtain open cell type thermal conductivity epoxy group(ing) composite porous material.
At 25 DEG C, test the ventilative water permeability of curing module (i.e. composite porous material), pressure-proof and snap-resistent intensity and thermal conductivity, result is as shown in table 1.
Embodiment 9
A kind of open cell type thermal conductivity epoxy group(ing) composite porous material, is prepared by following steps:
(1) at room temperature 30 DEG C, Graphite Powder 99 110g and water 190g that the silicon carbide 150g that to add median size in the plastic measuring glass of 1000mL be successively silicon oxide 50g, the median size of 100 μm is 30 μm, median size are 10 μm, stirring, (time of stirring is 15min, mixing speed is 500r/min), obtain filler-aqeous suspension 500g;
(2) in the plastic measuring glass of another 1000mL, 61g epoxy resin E-51 is added successively, polyoxypropylene polyether modified epoxy E1 prepared by 60g embodiment 1, median size is the silica 1 0g of 10 μm, median size is that the silicon carbide 10g of 3 μm and 30g embodiment 2 obtain modified phenolic amine MT31 and 30g polyetheramine T403 (the graceful product of U.S.'s Hensel) (percentage composition of polyoxypropylene polyether is 88wt%), at 30 DEG C, with the stirring velocity rapid stirring 3 minutes of 1000r/min, obtain epoxy resin-thermal conductive ceramic powder-modified amine premix 200g,
(3) 500g filler-aqeous suspension is poured in 200g epoxy resin-thermal conductive ceramic powder-modified amine premix, in the stirring velocity rapid stirring 3 minutes of 1000r/min, then be all poured in mould in 2 minutes, solidify 3 days at room temperature 30 DEG C, obtain open cell type thermal conductivity epoxy group(ing) composite porous material.
At 25 DEG C, test the ventilative water permeability of curing module (i.e. composite porous material), pressure-proof and snap-resistent intensity and thermal conductivity, result is as shown in table 1.
Performance test:
Folding strength be first make the rectangular parallelepiped test block of 40mm*40mm*160mm by the casting forming method in example, ultimate compression strength is after the square making 40mm*40mm*40mm, then tests with reference to standard GB/T/T17671-1999 after the corresponding residue number of days of natural drying at room temperature;
The inspection of air-and water-permeable implementations inserts a plastic syringe in advance being just poured in the slurry in mould, depth of penetration is 1/3 of forming module height, plastic conduit is extracted after solidification, form one and preset duck eye, carry out with the pressure of 0.3MPa respectively with air compressor doing air-and water-permeable inspection in the pipeline insertion hole of pressurized air or pressurized water after the corresponding time, Observation Blocks surface is immersed in module circumferential surface when testing in water and constantly emits water bubbling, and emits water bubbling evenly and the large expression ventilative water permeability of area is good.
Thermal conductivity is cured to the specified time at casting, tests at natural drying at room temperature 7 days in 25 DEG C after the demoulding again.
Table 1: embodiment 3 ~ 9 test result
From test result, the epoxy matrix composite prepared in example of the present invention has excellent ventilative water permeability and higher mechanical strength, there is open-celled structure, and thermal conductivity, far above matrix pure epoxy resin-amine cured article (0.12W/ (mK)), has good heat conductivility.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. an open cell type thermal conductivity epoxy group(ing) composite porous material, is characterized in that: be prepared from by following component by mass percentage:
Epoxy resin-thermal conductive ceramic powder-modified amine premix 20 ~ 40%
Mineral filler-aqeous suspension 80 ~ 60%
Above each component amounts to 100%;
Described epoxy resin-thermal conductive ceramic powder-modified amine premix prepares by the following method: by the pre-mixing 3 ~ 10 minutes at 20 ~ 35 DEG C of 100 parts by weight epoxy resin, 3 ~ 30 weight part thermal conductive ceramic powders and 50 ~ 100 part by weight modified amine curing agents; Described epoxy resin is more than one in the bisphenol A type epoxy resin of bisphenol A epoxide resin or polyoxypropylene polyether type polyurethane prepolymer chemical modification; Described modified amine curing agent adopts polyoxypropylene polyether type polymer modification amine curing agent to prepare.
2. open cell type thermal conductivity epoxy group(ing) composite porous material according to claim 1, is characterized in that:
The bisphenol A type epoxy resin of described polyoxypropylene polyether type polyurethane prepolymer chemical modification is reacted by polyoxypropylene polyether type polyurethane prepolymer and bisphenol A epoxide resin to prepare; Described polyoxypropylene polyether type polyurethane prepolymer is reacted by tolylene diisocyanate and polyether glycol and prepares.
3. open cell type thermal conductivity epoxy group(ing) composite porous material according to claim 1, is characterized in that:
Described bisphenol A type epoxy resin is more than one in epoxy resin E-51, epoxy resin E-44 or epoxy resin E-20.
4. open cell type thermal conductivity epoxy group(ing) composite porous material according to claim 1, is characterized in that:
Described modified amine curing agent be the whole PAMAM PAMAM of polyoxypropylene polyether modification Amino End Group dendroid, polyoxypropylene polyether modified low molecular weight polyamide 6 50, polyoxypropylene polyether modified low molecular weight polyamide 6 51, polyoxypropylene polyether modified phenolic amine or containing polyoxypropylene segment polyetheramine in more than one.
5. open cell type thermal conductivity epoxy group(ing) composite porous material according to claim 4, is characterized in that:
Described polyoxypropylene polyether is polyoxypropylene diglycidylether; The described polyetheramine containing polyoxypropylene segment be in polyetheramine D230, polyetheramine D400 or polyetheramine T403 more than one.
6. open cell type thermal conductivity epoxy group(ing) composite porous material according to claim 1, is characterized in that:
Described thermal conductive ceramic powder is more than one in aluminum oxide, aluminium hydroxide, boron nitride, aluminium nitride, silicon carbide, silicon nitride or silicon-dioxide.
7. open cell type thermal conductivity epoxy group(ing) composite porous material according to claim 1, is characterized in that:
Described mineral filler-aqeous suspension prepares by the following method: by the pre-mixing 3 ~ 20 minutes at 20 ~ 50 DEG C of the water of 100 parts by weight of inorganic fillers and 55 ~ 75 weight parts.
8. open cell type thermal conductivity epoxy group(ing) composite porous material according to claim 7, is characterized in that:
Described mineral filler be thermal conductive ceramic filler or silicate minerals more than one; Described thermal conductive ceramic filler be in aluminum oxide, aluminium hydroxide, boron nitride, aluminium nitride, silicon carbide, silicon nitride, silicon-dioxide or conductive graphite powder more than one; Described silicate minerals be in polynite, kaolin, wilkinite, mica powder or talcum powder more than one.
9. the preparation method of open cell type thermal conductivity epoxy group(ing) composite porous material according to any one of claim 1 ~ 8, is characterized in that: comprise the following steps:
(1) under the condition of rapid stirring and 20 ~ 35 DEG C, in epoxy resin-thermal conductive ceramic powder-modified amine premix, add mineral filler-aqeous suspension, continue rapid stirring 3 ~ 10 minutes, obtain mixed solution;
(2) poured in mould by mixed solution in 3 minutes, solidification, obtains open cell type thermal conductivity epoxy group(ing) composite porous material;
The stirring velocity of described rapid stirring is 2000 ~ 300r/min;
Described condition of cure is in 20 ~ 35 DEG C of solidifications 3 ~ 7 days, or within 1 day, solidifies 1 ~ 2 day at 36 ~ 50 DEG C prior to 20 ~ 35 DEG C of solidifications again.
10. the application of open cell type thermal conductivity epoxy group(ing) composite porous material according to any one of claim 1 ~ 8, is characterized in that: described open cell type thermal conductivity epoxy group(ing) composite porous material is applied to pottery, electronics, battery diaphragm, environmental protection, purifying air, chemical industry and building field.
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