CN1282349A - Conductive thermoset molding composition and method for producing same - Google Patents
Conductive thermoset molding composition and method for producing same Download PDFInfo
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- CN1282349A CN1282349A CN98812178A CN98812178A CN1282349A CN 1282349 A CN1282349 A CN 1282349A CN 98812178 A CN98812178 A CN 98812178A CN 98812178 A CN98812178 A CN 98812178A CN 1282349 A CN1282349 A CN 1282349A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0213—Gas-impermeable carbon-containing materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0223—Composites
- H01M8/0226—Composites in the form of mixtures
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
A high filler conductive thermoset composite that may be used in bipolar plates is provided in which the composite may be used to form thin wall, electrically and thermally conductive structures that have sufficient toughness and are resistant to the harsh fuel cell environment.
Description
The application is the part continuation application of the United States Patent (USP) provisional application series number 60/021,920 of submission on October 14th, 1997, and its full content is incorporated this paper into as a reference.
Background of invention
The present invention relates to same with thermosetting compound material, and particularly is the method that relates to by the same with thermosetting compound material manufacturing structure body with high thermal conductivity and high conductivity.In addition, the present invention relates to the method making the starting raw material of this class formation body and make this class starting raw material.
Have good heat conductive and conductivity and have thin-wall construction and the structure of enough anti-cracking processing characteristics is very useful for the application that has conductive performance such as the requirement the fuel cell double polar plate.
The long-term subject matter of being concerned about in this area is to leak into the ion that goes in the fuel cell environment by bipolar plates.Why the effect of this ionic seepage becomes problem, is because it can make the film inefficacy that is used to isolate the stacked bipolar plate in the fuel cell.The ionic seepage can be quickened owing to charging effect, corrosive nature and the sour environment of fuel cell.Because the ionic seepage comprises high conductivity and conductive metal at those interior known structures, use is fully proved invalid as bipolar plates in fuel cells applications.Even contain the known structure body of the ionogenous impurities (being ionizable conductive metal) of a great deal of, when being used as the bipolar plates of fuel cell, it also can produce the ion seepage.
To make another relevant problem be high cost to the class formation system therewith.Have thermal conductivity and electroconductibility for being devoted to solve the structure that the ion leakage problems keeps making again, some common structure has all adopted rare, expensive material, for example carbon-carbon composite or other exotic material.But, manufacturing time that these exotic materials need be grown and higher material cost and manpower tooling cost, these costs can be married again on client's head of buying fuel cell usually.
Another relevant problem of class formation body is that its processing characteristics descends therewith.For example, carbon-to-carbon base bipolar plates normally adopts machine-tooled method to make bipolar plates, adopts the manual operations of wasting time and energy to be unlikely cracking or broken to guarantee the thin bipolar plates of crisp, frangible carbon-to-carbon then in the assembling process of fuel cell.
Another relevant problem of class formation body is the potentiality cracking problem relevant with not possessing enough cracking resistance flexible thin-wall construction bodies therewith.For example, generally all quite crisp with the bipolar plates that carbon-carbon composite is made, thereby in fuel cell environment, can produce cracking and/or broken.
Also have one therewith the relevant problem of class formation body be, owing to can not in structure, mixing the decline that abundant conductive material causes thermal conductivity and specific conductivity.For example, the known moulding compound that is mixed with conductive material, common feature is that its resistivity (being the inverse of specific conductivity) all is not less than 0.005 Ω-cm.
Therefore, need a kind ofly to have good thermal conductivity and specific conductivity and to have thin-wall construction and the better novel texture body of enough cracking resistance processing characteristicies, this structure has low ion seepage, low manufacturing cost and good processability.In addition, also need some to make the better novel method of low manufacturing of having of this class formation body and tooling cost.Moreover, also need a class to make new, the better starting raw material of this structure, and make better method this class starting raw material, new.
Summary of the invention
According to the present invention, have now found that, the filler that the aathermoset resin system available rates is cheap is fully filled making a kind of moulding compound, and said composition can be made into to be had excellent conductivity and thermal conductivity, low ion seepage, low manufacturing cost, strengthen processing characteristics and strengthen the structure of anti-cracking performance.Also developed some kinds simultaneously and made this moulding compound with the specific conductivity that improves the structure made from this moulding compound and the method for thermal conductivity.
Therefore, a first aspect of the present invention is to have developed the low viscosity thermosetting adhesive resin system that comprises about 10～about 30wt% and the thermoset molding composition of about 70～about 90wt% filler.
A second aspect of the present invention is also to have developed some kinds of methods making thermoset molding composition, described method comprises mixes with filler low viscosity thermosetting adhesive resin system under following selected condition, these conditions comprise the integrity that keeps filler and make this conductive filler be subjected to the fully wetting of binder resin system.
A third aspect of the present invention is also to have developed by the electroconductibility of above-mentioned thermoset molding composition manufacturing and the structure of thermal conductivity.
A fourth aspect of the present invention is the Several Methods of having developed by above-mentioned thermoset molding composition manufacturing structure body, these methods comprise above-mentioned thermoset molding composition are molded as required shape, make this required shape be subjected to the effect of some condition then, these conditions are enough to make above-mentioned thermoplastic composition to be solidified basically to form structure.
The present invention has following some superiority.Structure physical efficiency provided by the present invention improves thin-wall construction body anti-cracking performance, can improve processing characteristics, has low ion seepage, low manufacturing cost simultaneously, and improves its specific conductivity and thermal conductivity.Moreover moulding compound of the present invention is inactive in corrosive fuel cell environment, thereby helps reducing the ion seepage.In addition, moulding compound of the present invention comprises and has enough low viscous thermosetting resin, and this helps improving the processing characteristics of this moulding compound under moderate temperature and pressure condition, thereby helps making the thin-wall construction body so that use in fuel cell.Also have, the method that the present invention makes moulding compound can optionally improve the thermal conductivity (being that thermal conductivity is not less than 3 (w/m) K) of the structure of being made by this moulding compound and specific conductivity and (be that resistivity is not higher than 0.01 Ω-cm), thereby help this structure (promptly as bipolar plates) is applied in the fuel cell.
The invention provides a kind of moulding compound, said composition can be used for making the bipolar plates that is used for fuel cell.This moulding compound can be made into a kind of thin-wall construction body, and this structure has the suitable toughness of cracking resistance and has the performance of resisting the ion seepage in charging, corrosion and the sour environment that is able to take at fuel cell.This moulding compound also has high electroconductibility and thermal conductivity.Because the manufacturing of said moulding compound can adopt cheap starting material, have short process for processing cycle and set time fast, so said composition can be used to make the fuel cell cogeneration than lower volume, higher cost economically, and manufacturing is applicable to the higher capacity of automotive industry, the fuel cell of lower cost.
Detailed Description Of The Invention
According to the present invention, provide the moulding compound that comprises a kind of low viscosity thermosetting adhesive resin system and a kind of filler.
Said low viscosity thermosetting adhesive resin system can the different concns form exist, and this will depend on the end-use of moulding compound of the present invention.For example, this low viscosity thermosetting adhesive resin system preferred concentration range is the about 10～about 30wt% that accounts for present composition weight, and more preferably concentration range for example is about 15～about 25wt%, and preferred concentration range is about 19～about 23wt%.
Similarly, said filler can the different concns form exist, and this will depend on the purposes that moulding compound of the present invention is final.For example, the filler preferred concentration range is the about 70～about 90wt% that accounts for present composition weight, and more preferably concentration range is about 75～85wt% for example, and preferred concentration range is about 77～81wt%.
" weight percentage " used herein refers to 100% of composition total weight is the content that benchmark is present in a certain specific components in the composition when calculating.Therefore, term " filler of about 70～about 90wt% " for example, when this term is used to represent the components contents of a kind of electroconductibility and thermal conductivity compositions of thermosetting resin, just mean that the filler content that is present in this conductivity thermoset composition can be the interior arbitrary numerical value of about this scope of 70～about 90wt% of this conductivity thermoset molding composition.Similarly, term " content of this filler is the wt% of the present composition (in the scope of concrete regulation) " just means that the filler content that is present in the conductivity thermoset composition can be the interior arbitrary numerical value of weight range of conductivity thermoset molding composition concrete regulation.
Filler of the present invention comprises the filler of natural graphite flake, synthetic graphite and other any kind of, as long as this class filler mixes time generation thermoset molding composition under keeping the selected condition of filler integrity with low viscosity thermosetting adhesive resin system, then all to can be used for making thermal conductivity be that 3 (watt/meter) Kelvin's thermodynamic scale ((W/m) K)～50 (W/m) K and/or resistivity are electric conductivity and the heat conductance structure of about 0.0001 Ω cm～about 0.01 Ω cm to such filler; Filler of the present invention also comprises the mixture of above-mentioned these fillers.Preferred filler comprises natural graphite flakes.Randomly, filler can be the conduction with heat conduction.
Filler can have different shapes, size, thickness and purity level.
Optional is, the mean size specification of filler (order number) is about 20 μ m～about 4.75mm, and the preferably about 200 μ m of reality～about 400 μ m.
In addition, the optional mean thickness of filler is about 5 μ m～100 μ m, preferably about at present 10 μ m～about 50 μ m.
In addition, the carbon back conductive filler (for example, natural graphite flakes, synthetic graphite etc.) optional average purity (is the percentage composition of carbon, is that benchmark is measured with the weight percentage) preferable range be about 90% purity～about 100% purity, actual preferred range is about 95% purity～about 100% purity.The carbon back conductive filler of low-purity can cause made structure to produce to be directly proportional the conductivity that descends and be easy to produce the ion seepage.
Be used to implement low viscosity thermosetting adhesive resin system of the present invention and comprise following precursor: epoxy vinyl ester resin system, low-molecular-weight phenolic resin system (the optional amine hardener that contains), and the assembly thing of low viscosity epoxy resin and pf resin of low molecular weight solidifying agent, wherein phenolic resin curative is optional for predetermined phenol-epoxy metering ratio to the stoichiometric ratio of Resins, epoxy, also has suitable assembly thing of above-mentioned these resin systems or the like.
According to the present invention, the precursor that comprises low viscosity thermosetting adhesive resin system comprises the epoxy vinyl ester resin system.Be used to implement epoxy vinyl ester resin system of the present invention and comprise epoxy vinyl ester resin etc.The epoxy vinyl resin comprises bisphenol type epoxy vinyl ester resin, phenolic varnish type epoxy vinyl ester resin, their suitable assembly thing, or the like.
" bisphenol type epoxy vinyl ester resin " is the resin with following general structure:
N=0 in the formula～5,
R
1And R
2Be selected from independently of one another:
Wherein each R is independently selected from hydrogen and methyl.
" phenolic varnish type epoxy vinyl ester resin " is the resin with following general structure:
The mean value of n is 0～4 in the formula, and each R is independently selected from hydrogen and methyl.
Plan is used for the range of viscosities of epoxy vinyl ester resin of the present invention under 25 ℃ can be about 200 centipoises～about 500 centipoises, and preferred range of viscosities is about 250 centipoises～about 350 centipoises under 25 ℃.
The viscosity that constitutes arbitrary precursor of low viscosity thermosetting adhesive resin system can adopt mensuration as known in the art to measure to any method of viscosity under the fixed temperature.For example, can adopt the rotational viscosimeter method to measure viscosity.The rotational viscosimeter method is published in the year of ASTM standard in (1997) handbook, and its appointment codes is D2196-86, and its title is " with the ortho-test of rotation (Brookfield) viscometer determining non-newtonian substance rheological property ".The whole associated visceras of annual handbook that relate to the ASTM standard of rotational viscosimeter method are incorporated this paper into as a reference.
The example of epoxy vinyl ester resin comprises Derakane 470-300
TM, Derakane 411-350
TM, Derakane 441-400
TM, Derakane 510A-40
TM, and Derakane 510C-350
TM(these trade mark products all can be available from Dow Chemical Company, the state of Mississippi, Midland), and the like the suitable groups compound of product and they.
According to the present invention, the precursor that constitutes low viscosity thermosetting adhesive resin system comprises the optional pf resin of low molecular weight system that contains amine hardener.
The pf resin of low molecular weight system that is adopted in the invention process comprises phenolic varnish base resin, first rank phenolic group resin, their suitable assembly thing, or the like.
" phenolic varnish base resin " is the resin with following general structure:
The mean value of n is 0～4 in the formula.
The softening temperature that plan is used to implement " phenolic varnish base resin " of the present invention can be about 60 ℃～about 140 ℃, is preferably about 60 ℃～about 90 ℃.
The softening temperature that constitutes arbitrary precursor of low viscosity thermosetting adhesive resin system is that specific precursor produces temperature of remollescent.Any method that softening temperature can adopt this area to measure softening temperature is measured.For example, softening temperature can adopt ring-and-ball method to measure.Ring-and-ball method is published in the year of ASTM standard in (1997) handbook, and its appointment codes is E28-97, and its title is " ortho-test of deciding softening temperature with global instrumentation ".The whole associated visceras of annual handbook that relate to the ASTM standard of this ring-and-ball method are incorporated this paper into as a reference.In many cases, softening temperature can be used as the indirect measurement of specific precursor molecular-weight average.
" first rank phenolic group resin " to be formaldehyde and phenol be not less than the product that reaction forms under 100% the condition in formaldehyde Pyrogentisinic Acid's mol ratio, and this reaction and product thereof are known in the art." first rank phenolic group resin " comprises the resinoid with following general structure, wherein can contain, also can not contain existing repeating unit:
R is independently selected from the condensation product of hydrogen, formaldehyde, phenol, formaldehyde and phenol and their suitable condensation product in the formula.
Plan is used to implement " first rank phenolic group resin " of the present invention viscosity under 25 ℃ (this viscosity as the function of solid content and change) can be about 100 centipoises～about 40000 centipoises (being equivalent to solid content is 50%～90%), and the viscosity under preferred 25 ℃ is about 180 centipoises～about 300 centipoises (being equivalent to solid content is 60%～64%).
The example of first rank phenolic group resin comprises SC 1008 (available from Borden chemical company, the Kentucky State, Louisville city) and other.
Amine hardener can be chosen wantonly and join in the low viscosity resin binding system that comprises phenolic varnish base resin.This class amine hardener comprises vulkacit H etc.Vulkacit H has following structure:
The consumption of vulkacit H can be about 4～about 12wt% of the present composition, and the consumption of preferred vulkacit H is about 7wt% of the present composition.
According to the present invention, the precursor that constitutes low viscosity thermosetting adhesive resin system comprises the mixture of low viscosity epoxy resin and pf resin of low molecular weight solidifying agent, wherein phenolic resin curative can be about 60%～about 110% to the stoichiometric ratio of Resins, epoxy, for example be about 65%～about 100%, and be preferably about 65%～about 90%.
Low viscosity epoxy resin of the present invention comprises phenolic varnish base resin, first rank phenolic varnish base resin, epoxidised phenolic varnish base resin, epoxidised first rank phenolic varnish base resin, xenyl Resins, epoxy, dicyclopentadiene basic ring epoxy resins, bisphenol f type epoxy resin, bisphenol A type epoxy resin, with above-mentioned any resin solid-state or that liquid form provides, and their mixture.Preferred low viscosity epoxy resin comprises epoxidised phenolic varnish base resin, and preferred low viscosity epoxy resin is DEN431
TMAnd DEN438
TM(available from Dow Chemical Company, the state of Mississippi, Midland).
" phenolic varnish base resin " is the resin with the defined general structure in front.
" first rank phenolic varnish base resin " is the resin with following general structure:
The mean value of n is 0～3 in the formula, and wherein each X is independently selected from hydrogen and methyl.
" epoxidised phenolic varnish base resin " is the resin with following general structure:
The mean value of n is 0～2 in the formula.
" epoxidised first rank novolac resin " is the resin with following general structure:
The mean value of n is 0～2 in the formula, and wherein each X is independently selected from hydrogen and methyl.
" xenyl Resins, epoxy " is the resin with following general structure:
" dicyclopentadiene basic ring epoxy resins " is the resin with following structure:
The mean value of n is 0～1 in the formula.
" bisphenol-f type Resins, epoxy " is the resin with following structure:
" bisphenol A type epoxy resin " is the resin with following structure:
The mean value of n is 0～5 in the formula.
Viscosity under optional 52 ℃ of the low viscosity epoxy resin that is adopted is about 1400 centipoises～about 50000 centipoises in the embodiment of this invention.For example the viscosity under its 52 ℃ is 2000 centipoises～about 15000 centipoises, and the viscosity under 52 ℃ is preferably 4000 centipoises～12000 centipoises.
In addition, the epoxy equivalent (weight) weight (EEW) of intending being used to implementing low viscosity resin of the present invention can be about 165～about 250.The preferred EEW of preferred low viscosity epoxy resin (being epoxidised phenolic varnish base resin) is 170～190, and preferred EEW is 172～181.
Moreover the second-order transition temperature of said low viscosity epoxy resin (Tg) can be-40 ℃～170 ℃ approximately.
The example of low viscosity epoxy resin of the present invention comprises DEN 431
TM, DEN438
TM(each all available from Dow Chemical Company, the state of Mississippi, Midland), DER661
TM(available from Dow Chemical Company, the state of Mississippi, Midland), and Epon 828
TM(available from shell Development Co., Ltd, Texas, Houston city).
Be used to implement pf resin of low molecular weight solidifying agent of the present invention and comprise phenolic varnish base resin.
The softening temperature that plan is used to implement pf resin of low molecular weight solidifying agent of the present invention can be about 60 ℃～about 90 ℃, for example is about 75 ℃～about 85 ℃, and preferably about 80 ℃～about 85 ℃.
Moreover that the molecular weight of pf resin of low molecular weight solidifying agent of the present invention can be is about 200～about 600, for example be about 300～about 500, and preferably about 370～about 420.
In addition, that the hydroxyl equivalent weight (HEW) of the pf resin of low molecular weight solidifying agent that is adopted in the present invention practice can be is about 95～and about 115, for example HEW is 100～110, and preferred HEW is 102～106.
The example of the pf resin of low molecular weight solidifying agent that the present invention is used comprises HRJ 1166
TMWith HRJ 1583
TM, each is available from Schenectady international corporation (New York, Schenectady city).
According to the present invention, the pf resin of low molecular weight solidifying agent to the stoichiometric ratio of low viscosity epoxy resin optional for about 60%～about 110%, for example be about 65%～about 100%, and preferably about 65%～about 90%.
Term used herein " stoichiometric ratio " refers to the several ratios to obtainable resin functional group (for example epoxy-functional) of institute number from the precursor that constitutes low viscosity thermosetting adhesive resin system of solidifying agent functional group (for example hydroxy functional group).Particular functional group's number can adopt methods known in the art to be measured.For example, the measuring method of the epoxy-functional number in the low viscosity thermosetting adhesive resin system is, with the weight of the epoxy group(ing) precursor component (for example low viscosity epoxy resin) of the low viscosity thermosetting adhesive resin system epoxy equivalent (weight) weight (EEW) divided by its epoxy group(ing) precursor component." epoxy equivalent (weight) weight " refers to the weight (is unit with the gram) of the precursor (for example low viscosity epoxy resin) that contains 1 gram equivalent of epoxy-functional.Similarly, the measuring method of the hydroxy functional group number in the low viscosity thermosetting adhesive resin system is, with the weight of the hydroxyl based precursor thing component of low viscosity thermosetting adhesive resin system (for example pf resin of low molecular weight, pf resin of low molecular weight solidifying agent) hydroxyl equivalent weight (HEW) divided by this hydroxyl based precursor thing component." hydroxyl equivalent weight " refers to the weight (is unit with the gram) of the precursor (for example pf resin of low molecular weight solidifying agent) that contains 1 gram equivalent of hydroxy functional group.
Be used to implement low viscosity thermosetting adhesive resin system of the present invention and also can contain other optional components.
For example, low viscosity thermosetting adhesive resin system can comprise a kind of suitable catalyst system, and its consumption is about 0.001～about 3wt% of resin combination of the present invention.Suitable catalyst system can change according to resin Composition and/or the curing agent component in the said low viscosity thermosetting adhesive resin system.
The appropriate catalyst system that is applicable to the epoxy vinyl ester resin system comprises methylethyl ketone peroxide, cumene hydroperoxide, xylidine etc., and their mixture.
Be applicable to that the optional suitable catalyst system that contains the pf resin of low molecular weight (for example phenolic varnish base resin) of amine hardener comprises the acid (having corresponding pH value) such as toluenesulphonic acids, sulfocarbolic acid etc. and their mixture.
For low viscosity epoxy resin and pf resin of low molecular weight solidifying agent are merged use, should select the appropriate catalyst system to promote the crosslinked action between low viscosity epoxy resin and the pf resin of low molecular weight.This class catalyzer comprises urea groups catalyzer, imidazole catalyst, triphenyl phosphine, phosphonium salt catalyzer, tertiary amine catalyst, amine salt catalyzer etc., and the assembly thing of above-mentioned arbitrary catalyzer.The example of urea groups catalyzer comprises Diuron Tech (diuron), monuron (monuron), grand (phenuron) their the suitable assembly thing of powder grass etc.The example of imidazole catalyst comprises 2-phenyl-4-methylimidazole (2P4MZ), glyoxal ethyline, 2-phenylimidazole, reaches their suitable assembly thing etc.The example of tertiary amine catalyst comprises benzyldimethylamine (BDMA) etc.The example of amine salt catalyzer comprises benzyl trimethyl ammonium chloride etc.
Also can use various mixture of catalysts.Therefore, the preferred suitable catalyst system that is applicable to the low viscosity thermosetting adhesive resin system that comprises low viscosity epoxy resin and pf resin of low molecular weight solidifying agent assembly thing comprises urea groups catalyzer (for example Diuron Tech), its consumption is about 0.001～about 1.5wt% of the present composition, and imidazole catalyst (for example 2-phenyl-4-methylimidazole), its consumption is about 0.001～about 0.5wt% of the present composition.The example of catalyst mixture comprises the preferred mixture of being made up of 2-phenyl-4-methylimidazole of the Diuron Tech of about 0.5～about 0.7wt% and about 0.03～about 0.1wt%.
When in enforcement of the present invention, using catalyzer, the appropriate catalyst system can make the conductivity thermoset molding composition, under suitable condition of cure, basically solidified being no more than in about 90 seconds, for example solidified basically being no more than in about 60 seconds, solidified basically and preferably be no more than in about 45 seconds.
Term used herein " solidifies " curing that refers to said moulding compound basically and fully carries out, so that produced reaction from the available functional group of at least 50% in the adherent resin component with low stoichiometry utilization ratio.
The percentage ratio of the state of cure of certain material can adopt methods known in the art to be measured, and for example, differential scanning calorimetry (DSC) can be used for measuring state of cure.In dsc measurement, the solidified test substance stands elevated temperature test to uncured material within a certain period of time with reaching basically, measures the heat output valve from this material as this intensification function then.Because the polyreaction of Resins, epoxy-resol is a kind of thermopositive reaction,, the respective area of this DSC curve (as the hot-fluid of temperature function) has estimating than the uncured substances content that hangs down stoichiometry utilization ratio (being the residual solidified degree) resin Composition so just becoming.Therefore, when the relevant area (being total state of cure) of the relevant area (being the residual solidified degree) of the DSC curve that will reach basic solidified measured matter and the DSC curve of uncured material when comparing, the residual solidified degree just provides the percentage ratio that has the utilized functional group that does not react as yet in the low stoichiometry utilization ratio resin Composition in the test substance after the ratio process of total state of cure is calculated the normalization method of measured matter weight.Whether this percentage ratio of deduction has just provided the percentage ratio of aitiogenic available functional groups from 100%, solidified basically thereby also just measured test substance.
Suitable condition of cure comprises that promotion generates those conditions of derivative (promptly solidifying) by low viscosity binder resin system precursor, for example the combination of temperature, pressure, other reaction conditions (for example the existence of high-energy photon etc.) and these conditions.Under suitable condition of cure, the derivative that low viscosity thermosetting adhesive resin system precursor generates, its chemical general formula is: (precursor) m deducts can be with the required specific group that removes of derivative, wherein m＞1 for generating this precursor.These derivatives comprise any in the following available reaction product of said precursor: oligopolymer, glycidyl group amine, ethoxylation chemical species, crosslinked chemical species (adduct for example, comprise etherificate product and condensation product), and the chemical species of chain extension (for example adduct comprises etherificate product and condensation product) etc.Those skilled in the art can be easy to judge which type of reaction product is applicable to specific precursor.
Provide the example of the whole bag of tricks of this suitable condition of cure to comprise jet molding, transfer molding method and compression molding, each method all has its suitable molding temperature and pressure.Suitable molding temperature comprises about 250～about 450 temperature, for example about 300 °F～about 375 °F, and preferably about 325 °F～about 350 °F.Suitable molding pressure comprises about 100psi (pound/in2)～about 3000psi, for example about 400psi～about 1500psi, and preferably about 500psi～about 1000psi.
In addition, low viscosity thermosetting adhesive resin system also can be chosen wantonly and comprise a kind of inner pattern releasing agent applicable, and its consumption is about 0.001～about 2wt% of the present composition.Term used herein " inner pattern releasing agent applicable " refers to can avoid the sticking any composition that bonds on the die surface of thermoset molding composition, and thermoset molding composition can be formed as required shape to make structure in this mould.The example of inner pattern releasing agent applicable comprises Camuba wax, Zinic stearas, calcium stearate, lipid acid (and derivative), their suitable assembly thing etc.
Moreover low viscosity thermosetting adhesive resin system can be chosen the solvent that comprises a kind of binder resin system wantonly, and its consumption is about 0.001～about 15wt% of the present composition, for example is about 7～about 11wt% of the present composition.Term used herein " solvent of binder resin system " comprises that this low viscosity thermosetting adhesive resin system can be partly dissolved at least or mix mutually in wherein and any solvent that the viscosity of this thermoset molding composition is further reduced.The example of binder resin system solvent comprises acetone, methylethylketone, methylene dichloride, their suitable assembly thing etc.
According to the present invention, the method of some manufacturing thermoset molding compositions also is provided, comprise binder resin system and conductive filler, under for the selected condition that keeps the filler integrity and be enough to make under the condition of the wetting conductive filler of binder resin system and mix.Optional is, the thermoset molding composition of making thus can be heated to certain temperature range, this temperature range for the boiling temperature of this binder resin system solvent to being lower than about this binder resin system solidification value, heat the enough time so that make the content of binder resin system solvent be reduced to the 3wt% that is lower than said conductivity thermoset composition.
For the selected condition that keeps the filler integrity comprises some conditions like this, wherein binder resin system and conductive filler suffer the shearing force of (being in these two kinds of component mixing processes of the present composition) enough low, so that make the resistivity of the structure of being made by prepared moulding compound be no more than 0.005 Ω-cm.
Have now found that, in the process of hybrid bonding resin system and conductive filler, (promptly mix in the process of these two kinds of components of the present composition) applying the integrity that too big power can reduce filler particles, thereby cause the resistivity of the structure made by prepared moulding compound to be not less than about 0.005 Ω-cm.Therefore, for the selected condition that keeps the filler integrity also comprises some conditions like this, promptly the power that hybrid bonding resin system and conductive filler (promptly in the process of these two kinds of components of mixing the present composition) are applied is enough low, so that make the resistivity of the structure of being made by prepared moulding compound be no more than 0.005 Ω-cm.Adopt to measure under special reaction condition, be used for the method (being methods known in the art) of the mixing machine input electric energy of hybrid process, can measure this power in certain hour (being normalized into the time in batches) introversion.In the present invention, being implemented, for keeping the required power of filler integrity will surpass Hobart No.V-1401 type mixing machine scarcely (available from Hobart company, the Ohio, the Te Luoyi city) power that is produced, its operational condition is: temperature is about 70 °F, speed setting is third gear (promptly being about 150 rpm), and mixing time is about 30 minutes; The stirring rake that is adopted be configured as T 68064 (flat stirring rake) (available from Hobart company, Ohio, Te Luoyi city); Mix with batch mode, and adopt the various components of the thermoset molding composition of embodiment 6.
In addition, for the example that keeps the selected condition of filler integrity comprises the binder resin system is sprayed on the conductive filler, this method is as the integral part of a kind of continuous processing mechanism (for example continuous conveyor); Also comprise with binder resin system dip-coating conductive filler (for example in rotary drum), or the like.
Term used herein " wetting " refers to and makes the binder resin system fully mix with filler or make it to be scattered in fully among the filler, thereby can't see the conductive filler fragment that (with the naked eye) do not apply.When wetting, the conductive filler fragment can become glutinous (owing to having coated resin), and these conductive filler fragments no longer form a kind of pourable solution.Promote the example of the processing condition of wetting action to comprise the prolongation mixing time, improve mixing velocity, in the mixture of binder resin system and conductive filler, add optional binding system solvent, and will mix with processing temperature and bring up on a certain temperature that is lower than the binder resin solidification value.
Another aspect of the present invention also provides the electric conductivity made by above-mentioned thermoset molding composition and the structure of heat conductance.Optional is that a kind of like this structure can comprise at least a any required polygonal or curved thin walled that is.A kind of shape of preferred thin walled is to help the Any shape that this structure is used, comprising the thin walled of using as bipolar plates.
The thickness of thin walled can be about 0.003 inch～about 0.200 inch, and preferred thickness range is about 0.012 inch～about 0.060 inch.Such thickness can adopt methods known in the art (being micrometer, slide calliper rule etc.) to measure.
The thin walled of said structure body also can have other optional character.For example, the thin walled of this structure is when that flexural stress that it suffered is no more than the limit flexural strength of this structure is about 50% the time, and optional should have the intensity that is enough to cracking resistance (being macroscopic cracking and/or tiny crack).Optional is, the thin walled of this structure should have the intensity that is enough to cracking resistance (being macroscopic cracking and/or tiny crack) when that its stress that suffers is no more than this structure limit flexural strength is about 95% the time.The example of flexural stress is about 2500 pounds/inch
2～about 7200 pounds/inch
2
A kind of limit flexural strength of structure can adopt any method of measuring flexural strength in this area to be measured.For example, can adopt the flexural properties assay method measuring limit flexural strength of ASTM.Said ASTM flexural properties assay method is published in the year of ASTM standard in (1997) handbook, and its appointment codes is D790-97, and its title is " ortho-test of the flexural properties of non-enhancing and reinforced plastics and electrically insulating material ".The whole associated visceras that relate in the annual handbook of ASTM standard of this ASTM flexural properties assay method are all incorporated this paper into as a reference.
In addition, the optional resistivity that has of the thin walled of this structure is no more than about 0.0025 Ω-cm.Optional is that the resistivity that the thin walled of this structure should have is for being not less than about 0.0001 Ω-cm.For example, the permissible value of this resistivity is about 0.0002 Ω-cm～about 0.0025 Ω-cm, and preferred permissible value is about 0.00035 Ω-cm～about 0.001 Ω-cm.
Any currently known methods that resistivity can adopt this area to measure resistivity is measured.For example, a kind of resistivity of structure can adopt the resistivity measurements of ASTM to be measured.The resistivity measurements of this ASTM is published in the year of ASTM standard in (1997) handbook, and its appointment codes is B 193-95, and its title is " ortho-test of electrical conductor material resistivity ".The whole associated visceras that relate in the annual handbook of ASTM standard of this ASTM resistivity measurements are all incorporated this paper into as a reference.
Moreover the thin walled of this structure can have the thermal conductivity that is not less than about 3 (watt/meter) K (at the mean value of about 20 ℃～about 120 ℃ temperature range build-in test).Optional is, the thermal conductivity of the thin walled of this structure for example is not less than about 50 (watt/meter) K, and the permissible value of thermal conductivity is about 4.5 (watt/meter) K～about 20 (watt/meter) K, and preferred permissible value is about 6 (watt/meter) K～about 15 (watt/meter) K.
Any currently known methods that thermal conductivity can adopt this area to measure thermal conductivity is measured.For example, a kind of thermal conductivity of structure can adopt flash burn method (flash method) to be measured.The flash burn method is published in the year of ASTM standard in (1997) handbook, and its appointment codes is E 1461-92, and its title is " ortho-test that the flash burn method is measured the solid material thermal diffusivity ".The whole associated visceras of annual handbook that relate to the ASTM standard of this flash burn method are all incorporated this paper into as a reference.
Another aspect of the present invention provides the Several Methods by above-mentioned thermoset molding composition manufacturing structure body, this method comprises above-mentioned thermoset molding composition is molded as required shape, and makes this required shape be subjected to the work of suitable condition of cure in order to make structure.
The molding of structure can adopt and anyly the thin-wall construction body resistivity of being made by the present composition is elevated to surpass the method for about 0.005 Ω-cm to be finished, and this method comprises injection moulding, transfer molding method, compression molding and any other moulding method that can keep finishing under the selected condition of filler integrity.
Randomly, the required shape method that can adopt above-mentioned manufacturing structure body under suitable condition of cure, be no more than to make it to reach in about 60 seconds time basically and solidifying.Optional is, basically the solidified moulding compound can be at suitable condition of cure (for example in about 350 stove, baking) down by handling the sufficiently long time (for example about 1～about 10 minutes) continuously thus make the complete basically polymerization of adherent resin component of moulding compound of the present invention make it further curing.
Whole bibliographys that this paper quoted are all incorporated this paper into as a reference.
The present invention does more detailed explanation with reference to following non-limiting example.Those skilled in the art in this area can find when it obtains instructing of this description, also have other embodiment of the present invention in the application of the present invention time limit, and these schemes all comprise within the scope of the appended claims.
Embodiment 1
Make the method for thermoset molding composition
In embodiment 2～5 and the thermoset molding composition of in embodiment 6 (in embodiment 6 indicate done some corrections), being admitted be prepared as follows.
(for example DEN 431 with the low viscosity epoxy resin of specified amount
TM, DEN 438
TMOr its mixture) joins in the hybrid chamber of Hobart mixing machine (No.A200 type, available from Hobart company, Ohio, Te Luoyi city).In the required whole mixing process of the thermoset molding composition of making electric conductivity and heat conductance, the running speed of this mixing machine is set in the 3rd retaining all the time.
The pf resin of low molecular weight (for example HRJ-1166, HRJ-1583 or its mixture) of specified amount is dissolved in the solvent of binder resin system of specified amount.The solution of this resol/solvent is joined in the low viscosity epoxy resin in the mixing machine lentamente.
First inner pattern releasing agent applicable (for example Carnuba wax), urea groups catalyzer (for example Diuron Tech), second inner pattern releasing agent applicable (for example Zinic stearas) and imidazole catalyst (for example 2-phenyl-4-methylimidazole) slowly joined in the mixture in the above-mentioned mixing machine separately once go.
With the mixture that obtains, complete low viscosity thermosetting adhesive resin system is provided, after it mixes fully, promptly from this mixing machine, take out and place on one side.
The conductive filler (for example natural graphite flakes) of specified amount is joined in the hybrid chamber of this mixing machine.
With aforesaid, from this mixing machine, take out and place specified amount low viscosity thermosetting adhesive resin system, that prepared on one side and join lentamente in the conductive filler in this mixing machine.Thermoset molding composition with gained in this mixing machine mixes, until the bonded resin system institute of this conductive filler wetting (for example, the batch mixed of every 2500g is 1～3 minute).
The wet thermoset molding composition of gained is placed (for example in the stove) carries out drying in the pallet of 180 temperature, be lower than the 3wt% of this moulding compound until solvent (for example acetone) content of tackiness agent; Can adopt the method that this moulding compound sample was measured the residual volatilisation loss amount of this sample in 20 minutes 325 following heating to measure this solvent.
Embodiment 2
DEN 431
TMThe thermoset molding composition of base
Method according to embodiment 1 prepares 2500g DEN 431 in batches
TMThe thermoset molding composition of base, said composition comprise the various components listed as following table 1:
Table 1
| Component | Wt% (to acetone normalization method) |
| DEN?431 TMLiquid epoxies | ????13．08(±2％) |
| HRJ 1166 phenolic varnish | ????3．41(±1％) |
| Carnuba wax | ????0．51(±0．1％) |
| Diuron Tech | ????0．51(+0．01％) |
| Zinic stearas | ????0．34(±0．1％) |
| Acetone (carriers/diluents) | ????8．68(±0．5％) |
| Natural graphite flakes | (73.06 5% to+15%) |
Embodiment 3
DEN431
TM/ 438
TM/ low levels imidazolyl thermoset molding composition
Method according to embodiment 1 prepares 2500g DEN431 in batches
TM/ 438
TMThe thermoset molding composition of/imidazoles (2P4MZ) (0.044 wt%) base, said composition comprise the various components listed as following table 2:
Table 2
| Component | ????wt％ |
| DEN?431 TMLiquid epoxies | ????6．25％ |
| DEN?438 TMResins, epoxy | ????6．25％ |
| HRJ-1166 TMPhenolic varnish | ????5．35％ |
| Acetone | ????8．94％ |
| Carnuba wax | ????0．54％ |
| Diuron Tech | ????0．55％ |
| Zinic stearas | ????0．36％ |
| Imidazoles (2P4MZ) | ????0．044％ |
| Natural graphite flakes (Asbury 3562 graphite flakes) (300 μ m sieve meshes; 96.5% purity) | ????71．72％ |
Embodiment 4
DEN431
TM/ 438
TM/ high-content imidazolyl thermoset molding composition
Method according to embodiment 1 prepares 2500g DEN431 in batches
TM/ 438
TMThe thermoset molding composition of/imidazoles (2P4MZ) (0.065 wt%) base, said composition comprise the various components listed as following table 3:
Table 3
| Component | ????wt％ |
| DEN?431 TMLiquid epoxies | ????6．25％ |
| DEN?438 TMResins, epoxy | ????6．25％ |
| HRJ-1166 TMPhenolic varnish | ????5．35％ |
| Acetone | ????8．92％ |
| Carnuba wax | ????0．54％ |
| Diuron Tech | ????0．55％ |
| Zinic stearas | ????0．36％ |
| Imidazoles (2P4MZ) | ????0．065％ |
| Natural graphite flakes (Asbury 3562 graphite flakes) (300 μ m sieve meshes; 96.5% purity) | ????71．72％ |
Embodiment 5
DEN431
TM/ 438
TM/ non-imidazolyl thermoset molding composition
Method according to embodiment 1 prepares 2500g DEN431 in batches
TM/ 438
TM/ non-imidazoles (2P4MZ) based thermoset moulding compound, said composition comprise the various components listed as following table 4:
Table 4
| Component | ????wt％ |
| DEN?431 TMLiquid epoxies | ????6．25％ |
| DEN?438 TMResins, epoxy | ????6．25％ |
| HRJ-1166 TMPhenolic varnish | ????5．35％ |
| Acetone | ????8．98％ |
| Carnuba wax | ????0．54％ |
| Diuron Tech | ????0．55％ |
| Zinic stearas | ????0．36％ |
| Natural graphite flakes (Asbury 3562 graphite flakes) (300 μ m sieve meshes; 96.5% purity) | ????71．72％ |
Embodiment 6
For keeping the selected condition upper limit-large batch of thermoset molding composition of filler integrity
The EPON828 for preparing 50 pounds of batches according to the method for embodiment 1
TM/ DER661
TMThe based thermoset moulding compound; The method of embodiment 1 is done following correction, and said composition comprises the various components listed as following table 5.The method that is adopted as described in example 1 above, different is to do following correction:
1. in the required whole mixing process of preparation composition, the running speed of mixing machine (Hobart mixing machine, No.V-1401 type, available from Hobart company, Ohio, Te Luoyi city) is set in the 3rd retaining (promptly about 150rpm; On different mixing machines, set identical speed and can produce different rotating speeds);
2. the binder resin system component with this thermoset molding composition mixed 30 minutes with the conductive filler component, and
3. be in batches 50 pounds (as above being indicated).
Table 5
| Component | ????wt％ |
| DEN?431 TMResins, epoxy | ????12．5％ |
| HRJ-1166 TMPhenolic varnish | ????5．35％ |
| Acetone | ????8．98％ |
| Carnuba wax | ????0．54％ |
| Diuron Tech | ????0．55％ |
| Zinic stearas | ????0．36％ |
| Natural graphite flakes (80 μ m sieve meshes; 96% purity) | ????71．72％ |
Embodiment 7
Measure the flexural strength of structure
Adopt the on-gauge plate (6 inches * 6 inches * 0.1 inch) of three thin-wall constructions of mould pressing technology preparation, by respectively making an on-gauge plate according to embodiment 2 (plate 1), embodiment 5 (plate 2) and the made thermoset molding composition of embodiment 6 (plate 3).Every on-gauge plate is cut into three specimen (0.75 inch * 2.25 inches * 0.01 inch).
According in the year that is published in the ASTM standard (1997) handbook, to be D790-97, title measured the limit flexural strength (for example structure be about to the preceding stress that breaks) of every specimen for the ASTM flexural properties method of testing of " ortho-test of non-enhancing and enhanced plastics and electrically insulating material flexural properties " to appointment codes.
The result of the limit flexural strength of three specimen of each on-gauge plate is averaged, so that obtain the limit-in-mean flexural strength of a certain specific criteria plate.The measurement result of the limit-in-mean flexural strength of each on-gauge plate is listed in the table below in 6:
Average flexural strength (pound/the inch of table 6 on-gauge plate sequence number
2) 1 3,727 2 5,130 3 4670
Embodiment 8
Measure the resistivity of structure
Adopt mould pressing technology preparation three thick disks of thin-wall construction (4 inch diameters * 0.1 inch thickness), each each freedom of thick disk is made according to the thermoset molding composition that embodiment 2 (disk 1), embodiment 5 (disk 2) and embodiment 6 (disk 3) make.
According in the year that is published in the ASTM standard (1997) handbook, appointment codes is B 193-95, the title ASTM resistivity measurements for " ortho-test of electrical conductor material resistivity ", by applying the known magnitude of current and measuring the resistivity (for example inverse of specific conductivity) that the volts lost that produces has recorded disk 1～3.
The measurement result of resistivity is listed in the table below in 7.
(Ω-cm) 1 0.00095 2 0.0005 3 0.0045 for table 7 disk sequence number resistivity
Embodiment 9
Measure the thermal conductivity of structure
Adopt mould pressing technology to make the on-gauge plate (6 inches * 6 inches * 0.1 inch) of two thin-wall constructions, every each freedom of on-gauge plate is made according to the thermoset molding composition that embodiment 5 (plate 1) and embodiment 3 (plate 2) make.With machine every block of plate is processed into test sample (0.5 inch * 0.5 inch * 0.080 inch).
According in the year that is published in the ASTM standard (1997) handbook, appointment codes is E1461-92, the title flash burn method for " the flash burn method is measured the ortho-test of solid material thermal diffusivity ", under the alternating temperature condition, measured respectively thermal conductivity by the made test sample of plate 1 and plate 2
Determination of Thermal Conductivity the results are shown in the following table 8.
Table 8 thermal conductivity calculate sample temperature density than thermal diffusivity thermal conductivity thermal conductivity (sequence number) (℃) (gm cm
-3) (W-a-gm
-1K
-1) (cm
2Sec
-1) (W-cm
-1K
-1) (BTU
*) plate 1 23.0 1.546 0.7250 0.04050 0.04538 31.49 40.0 1.546 0.8150 0.03720 0.04686 32.51 60.0 1.546 0.9110 0.03400 0.04787 33.22 80.0 1.546 1.0010 0.03160 0.04889 33.92 100.0 1.546 1.0820 0.02900 0.04850 33.65 120.0 1.546 1.1550 0.02640 0.04713 32.70 plates 2 23.0 1.670 0.7620 0.04820 0.06132 42.54 40.0 1.670 0.8490 0.04400 0.06237 43.27 60.0 1.670 0.9430 0.04050 0.06376 44.24 80.0 1.670 1.0340 0.03740 0.06456 44.79 100.0 1.670 1.1150 0.03460 0.06441 44.69 120.0 1.670 1.1820 0.03130 0.06177 42.85*(unit of BTU is hour
-1Foot
-2Fahrenheit degree
-1)
Claims (29)
1. thermoset molding composition comprises:
The low viscosity thermosetting adhesive resin system of about 10～about 30wt% and
The filler of about 70～about 90wt%.
2. according to the thermoset molding composition of claim 1, wherein said filler is electroconductibility and thermal conductivity.
3. according to the thermoset molding composition of claim 2, wherein said filler is a natural graphite flakes.
4. according to the thermoset molding composition of claim 2, wherein said filler is the synthetic graphite of electroconductibility and thermal conductivity.
5. according to the thermoset molding composition of claim 2, wherein said low viscosity thermosetting adhesive resin system comprises a kind of epoxy vinyl ester resin system.
6. according to the thermoset molding composition of claim 1, wherein said low viscosity thermosetting adhesive resin system comprises a kind of low-molecular-weight resol and randomly a kind of amine hardener.
7. according to the thermoset molding composition of claim 1, wherein said low viscosity thermosetting adhesive resin system comprises a kind of mixture of a kind of low viscosity epoxy resin and a kind of pf resin of low molecular weight solidifying agent, and the stoichiometric ratio of this phenolic resin curative and this Resins, epoxy is about 60%～about 110% in this mixture.
8. according to the thermoset molding composition of claim 7, wherein said low viscosity epoxy resin is selected from phenolic varnish base resin, first rank phenolic varnish base resin, epoxidised phenolic varnish base resin, epoxidised first rank phenolic varnish base resin, xenyl Resins, epoxy, dicyclopentadiene basic ring epoxy resins, bisphenol f type epoxy resin, bisphenol A type epoxy resin and their the suitable mixture of solid or liquid form.
9. according to the thermoset molding composition of claim 7, the viscosity of wherein said low viscosity epoxy resin under about 52 ℃ is about 1400 centipoises～about 50000 centipoises.
10. according to the thermoset molding composition of claim 7, wherein the epoxy equivalent (weight) weight (EEW) of said low viscosity epoxy resin is about 165～about 250.
11. according to the thermoset molding composition of claim 7, the softening temperature of wherein said pf resin of low molecular weight solidifying agent is about 60 ℃～about 90 ℃.
12. according to the thermoset molding composition of claim 7, the molecular weight of wherein said pf resin of low molecular weight solidifying agent is lower than about 600.
13. according to the thermoset molding composition of claim 7, the hydroxyl equivalent of wherein said pf resin of low molecular weight solidifying agent (HEW) is about 95～about 115.
14. according to the thermoset molding composition of claim 7, wherein said low viscosity epoxy resin is the mixture of bisphenol f type epoxy resin, the epoxy equivalent (weight) weight (EEW) of its each component is about 172～about 181; The hydroxyl equivalent of said pf resin of low molecular weight solidifying agent (HEW) is about 103～about 107; And this phenolic resin curative is about 70% to the stoichiometric ratio of this Resins, epoxy.
15. according to the thermoset molding composition of claim 7, said composition also comprises the suitable catalyst system of about 0.001～about 3 wt%.
16. thermoset molding composition according to claim 7, said composition also comprises the suitable catalyst system of about 0.001～about 3wt%, and wherein this suitable catalyst system comprises the urea groups catalyzer of about 0.001～about 1.5wt% and the imidazole catalyst of about 0.001～about 0.5wt%.
17. according to the thermoset molding composition of claim 16, wherein said urea groups catalyzer is Diuron Tech (diuron), and the imidazolyl catalyzer is 2-phenyl-4-methylimidazole.
18. according to the thermoset molding composition of claim 16, wherein this thermoset molding composition under suitable condition of cure, be no more than to reach in about 60 seconds time basically and solidifying.
19. according to the thermoset molding composition of claim 1, said composition also comprises the inner pattern releasing agent applicable of about 0.001～about 2wt%.
20. according to the thermoset molding composition of claim 1, said composition also comprises the solvent of the binder resin system of about 0.001～about 15wt%.
21. a method of making moulding compound comprises:
For keeping under the selected condition of filler integrity and being enough to make under the wetting condition of the bonded resin system of conductive filler, low viscosity thermosetting adhesive resin system is mixed with filler.
22. by a kind of electroconductibility made according to the thermoset molding composition of claim 2 and the structure of thermal conductivity.
23. according to the electroconductibility and the thermal conductivity structure of claim 22, wherein this structure comprises at least one thin-walled portion.
24. according to the structure of claim 23, wherein the thickness of said thin-walled portion is about 0.012 inch～about 0.200 inch.
25. according to the structure of claim 23, wherein said thin-walled portion is when being subjected to being no more than about 2500 pounds/inch
2Flexural stress is done the time spent, and its intensity is enough to avoid cracking.
26. according to the structure of claim 23, wherein the resistivity of said thin-walled portion is about 0.0001 Ω-cm～about 0.01 Ω-cm.
27. according to the structure of claim 23, wherein the thermal conductivity of said thin-walled portion is not less than about 3 (watt/meter) K.
28. the method by thermoset molding composition manufacturing structure body, this method comprises:
To be molded as required shape according to the thermoset molding composition of claim 1, and
Make this required shape be subjected to the work of suitable condition of cure in order to make structure.
29. according to the method for claim 28, wherein said desired shape under suitable condition of cure, be no more than to reach basically in time of 60 seconds and solidifying.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US6192097P | 1997-10-14 | 1997-10-14 | |
| US60/061,920 | 1997-10-14 |
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| CN1282349A true CN1282349A (en) | 2001-01-31 |
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| CN98812178A Pending CN1282349A (en) | 1997-10-14 | 1998-10-14 | Conductive thermoset molding composition and method for producing same |
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| EP (1) | EP1023374A1 (en) |
| JP (1) | JP2001520245A (en) |
| KR (1) | KR20010031139A (en) |
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| AU (1) | AU757196B2 (en) |
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| US20020134969A1 (en) * | 2001-02-14 | 2002-09-26 | Chervinko Jeremy R. | Internal mold release agent for low cost composite bipolar plates |
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| CN100343297C (en) * | 2003-03-10 | 2007-10-17 | 大日本油墨化学工业株式会社 | Conductive resin composition, process for production thereof, and fuel cell separators |
| JP5138239B2 (en) * | 2007-02-22 | 2013-02-06 | ニチアス株式会社 | Resin composition for fuel cell separator and fuel cell separator |
| JP5509709B2 (en) | 2009-07-24 | 2014-06-04 | 日清紡ケミカル株式会社 | Fuel cell separator |
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| US4360485A (en) * | 1980-08-25 | 1982-11-23 | United Technologies Corporation | Method for making improved separator plates for electrochemical cells |
| JPS5898378A (en) * | 1981-12-08 | 1983-06-11 | Nippon Light Metal Co Ltd | Joint filler for prebaked carbon anode |
| US4670300A (en) * | 1985-07-03 | 1987-06-02 | International Fuel Cells Corporation | Carbon-graphite component for an electrochemical cell and method for making the component |
| JPH0751660B2 (en) * | 1986-05-29 | 1995-06-05 | 杉郎 大谷 | Impermeable carbon material and method for producing the same |
| JPH03239752A (en) * | 1990-02-16 | 1991-10-25 | Nitto Denko Corp | Epoxy resin composition for cast molding |
| EP0651602B1 (en) * | 1993-10-29 | 1999-04-07 | Matsushita Electric Industrial Co., Ltd. | Conductive paste compound for via hole filling, printed circuit board which uses the conductive paste, and method of manufacturing the same |
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1998
- 1998-10-14 CA CA002306144A patent/CA2306144A1/en not_active Abandoned
- 1998-10-14 JP JP2000515954A patent/JP2001520245A/en not_active Withdrawn
- 1998-10-14 WO PCT/US1998/021748 patent/WO1999019389A1/en not_active Application Discontinuation
- 1998-10-14 CN CN98812178A patent/CN1282349A/en active Pending
- 1998-10-14 KR KR1020007004038A patent/KR20010031139A/en not_active Application Discontinuation
- 1998-10-14 AU AU10875/99A patent/AU757196B2/en not_active Ceased
- 1998-10-14 BR BR9814819-2A patent/BR9814819A/en not_active IP Right Cessation
- 1998-10-14 EP EP98953530A patent/EP1023374A1/en not_active Withdrawn
-
2000
- 2000-04-13 NO NO20001925A patent/NO20001925L/en not_active Application Discontinuation
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| CN100385722C (en) * | 2002-07-03 | 2008-04-30 | 本田技研工业株式会社 | Fuel cell separator and method of manufacturing the separator |
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| US8450254B2 (en) | 2005-02-14 | 2013-05-28 | L.B. Foster Rail Technologies, Corp. | Solid stick compositions comprising thermosetting plastic |
| CN101679723A (en) * | 2007-01-26 | 2010-03-24 | 凯尔森技术公司 | Solid stick compositions comprising vinyl ester |
| CN101809055B (en) * | 2007-09-27 | 2013-10-23 | 株式会社日本触媒 | Curable resin composition for molded bodies, molded body, and production method thereof |
| US8674038B2 (en) | 2007-09-27 | 2014-03-18 | Nippon Skokubai Co., Ltd. | Curable resin composition for molded bodies, molded body, and production method thereof |
| CN106414600B (en) * | 2014-05-19 | 2019-07-26 | 大赛璐优越涂层株式会社 | The manufacturing method of resin film, laminated body and its manufacturing method and fuel cell |
| CN105633419A (en) * | 2016-03-11 | 2016-06-01 | 常州博能新能源有限公司 | Bipolar plate used for hydrogen fuel battery pack and manufacturing process therefor |
| CN109119641A (en) * | 2018-09-07 | 2019-01-01 | 米库玻璃纤维增强塑料泰州有限责任公司 | A kind of conductive plastic bi-polar plate manufacturing process |
| CN109167072A (en) * | 2018-09-07 | 2019-01-08 | 米库玻璃纤维增强塑料泰州有限责任公司 | A kind of graphite bi-polar plate manufacturing process |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2001520245A (en) | 2001-10-30 |
| BR9814819A (en) | 2001-11-13 |
| WO1999019389A1 (en) | 1999-04-22 |
| AU1087599A (en) | 1999-05-03 |
| NO20001925D0 (en) | 2000-04-13 |
| AU757196B2 (en) | 2003-02-06 |
| KR20010031139A (en) | 2001-04-16 |
| CA2306144A1 (en) | 1999-04-22 |
| EP1023374A1 (en) | 2000-08-02 |
| NO20001925L (en) | 2000-06-13 |
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