CN104364297B - Carbon precursor composition - Google Patents
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- CN104364297B CN104364297B CN201380031660.XA CN201380031660A CN104364297B CN 104364297 B CN104364297 B CN 104364297B CN 201380031660 A CN201380031660 A CN 201380031660A CN 104364297 B CN104364297 B CN 104364297B
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- GXZQKSKXXFOTDE-UHFFFAOYSA-N C1OC1c1ccc(C2OC2)cc1 Chemical compound C1OC1c1ccc(C2OC2)cc1 GXZQKSKXXFOTDE-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
- C04B35/524—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite obtained from polymer precursors, e.g. glass-like carbon material
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/71—Ceramic products containing macroscopic reinforcing agents
- C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
- C04B35/80—Fibres, filaments, whiskers, platelets, or the like
- C04B35/83—Carbon fibres in a carbon matrix
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
- C08G59/687—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing sulfur
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/48—Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
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Abstract
Liquid carbon precursor composition, it comprises (a) at least one aromatic epoxy resin；(b) (i) at least one aromatics coreactivity firming agent or (b) (ii) at least one catalytic curing agent, or (b) (iii) its mixture；Wherein said fluid composition, before adding optional component and solidification, has when 25 DEG C less than 10, the clean viscosity of 000mPa s；And wherein said liquid precursor compositions is before adding optional component, before curing and before carbonization, has when 25 DEG C less than 10, the clean viscosity of 000mPa s；And the liquid precursor compositions wherein standing to solidify is not when having to measure in the case of optional components, has the carbon yield of at least 35wt%；The liquid carbon precursor composition of solidification；The char-forming material being made up of above-mentioned liquid carbon precursor composition；With the method producing above-mentioned composition.
Description
Technical field
The present invention relates to liquid carbon precursor formulation or compositions and prepare described liquid carbon precursor group
The method of compound.
Background technology
Up to now, have been disclosed for several for preparing various carbonization from carbonaceous precursor material
The method of end-product.The method of known preparation carbonization end-product is generally entered by following steps
OK: liquid carbon precursor is introduced porous body or prefabrication by such as impregnating or permeating by (i)
To form dipping prefabrication in (such as carbon strengthening material such as carbon fiber bundle), (ii) solidifies
The prefabrication of (such as by solidifying to form thermosetting material) described liquid carbon precursor dipping is with shape
Become solidification prefabrication, and solidify prefabrication described in (iii) carbonization to form carbonization end product.
Such as, GB 1343773A discloses by with comprising thermosetting resin such as asphalt mixtures modified by epoxy resin
Carbon fiber bundle that the liquid infiltration of fat arranges and prepare by carbon fiber-reinforced graphite system
Product.The viscosity of the described liquid disclosed in GB 1343773A increases with temperature over time；
Therefore, along with the viscosity of described epoxy thermoset increases, further limit described fibre
The amount of the epoxy resin absorbed in dimension.It addition, when at the liquid precursor for impregnation of carbon fibers
During middle use epoxy resin thermosetting resin, it is made up of such liquid-state epoxy resin precursor
Final carbonized product has low-down carbon yield, e.g., less than 20 weight % (wt%)
Carbon yield.
James Gary Pruett, " Carbon Matrices ", ASM handbook, volume 21,
Composites, Miracle etc. write, 164-168 page, and 2001；Describe well with
The liquid precursor known forms the problem of carbon matrix, as follows:
" all liquid precursor methods for producing carbon matrix all have a kind of problem: precursor material
Material always has the unit volume carbon content lower than the carbon matrix wanted.Therefore, when becoming
During final substrate, the volume of described precursor always has reduction.It addition, most of liquid precursors
Material loses some their carbon contents during carbonisation and their non-carbon all contain
Amount.... result, in described method, on carbon yield, surcharge is high.From polyester and ring
Carbon poor yields that oxide obtains (< 20%).Effectively yield is obtained from epoxy-novolaks
Resin, furan and phenolic resin (> 50%).”
Pruett list of references above discloses epoxy-novolaks and provides > carbon of 50% receives
Rate；But, epoxy-novolac resin has the drawback that very thickness.Public affairs in Pruett
The viscosity of the described epoxy-novolaks opened can be the highest (such as, 25 DEG C time 30,000
MPa-s), to such an extent as to such epoxy-novolac resin is difficult to by coating, film forming, filling
Note, spray and impregnate and process.Therefore, the epoxy-novolac resin of thickness needs solvent
Reduce the viscosity of described resin, so that described resin can be processed by above method.But,
Solvent tends to reduce products therefrom effective being made up of the resin formulation of described solvent dilution
Carbon yield.
Summary of the invention
One embodiment of the present invention relates to the liquid that can be used as producing the precursor of other material with carbon elements
State carbon precursor composition, wherein said liquid carbon precursor composition comprises (a) at least one virtue
Race's epoxy resin；(b) (i) at least one aromatics coreactivity firming agent or (b) (ii) at least
Plant catalytic curing agent or (b) (iii) its mixture；Wherein said liquid precursor compositions is being added
Before optional component, before curing and before carbonization, have when 25 DEG C and be less than
The clean viscosity of 10,000mPa-s；And before wherein standing (being cured) liquid of solidification
Body compositions is not when having to measure in the case of optional components, and the carbon with at least 35wt% is received
Rate.
Another embodiment of the invention relates to the side preparing above-mentioned liquid carbon precursor composition
Method.
Another embodiment of the present invention relates to the carbon precursor composition of solidification, and it comprises solid
Change curable liquid preparation product, described curable liquid preparation comprises: (a) extremely
Few a kind of aromatic epoxy resin；(b) (i) at least one aromatics coreactivity firming agent, (b) (ii)
At least one catalytic curing agent or (b) (iii) its mixture；(c) at least one porogen；
Wherein said fluid composition is before adding optional component, before curing with in carbonization
, have when 25 DEG C less than 10, the clean viscosity of 000mPa-s before；And it is wherein said solid
The carbon precursor composition changed, when not having to measure in the case of optional components, has at least
The carbon yield of 35wt%.
The another embodiment of the present invention relates to the liquid carbon combination of precursors preparing above-mentioned solidification
The method of thing.
Another embodiment of the present invention relates to by solidification and carbonization above-mentioned liquid carbon precursor
Compositions and the carbonized product prepared.
The another embodiment of the present invention relates to the method preparing carbonized product, described method
Comprise the following steps:
(I) mixing (a) at least one aromatic epoxy resin；(b) (i) at least one aromatics
Coreactivity firming agent or (b) (ii) at least one catalytic curing agent or (b) (iii) its mixture；
Wherein said liquid precursor compositions before adding optional component, before curing and
Before carbonization, have when 25 DEG C less than 10, the clean viscosity of 000mPa-s；And wherein warp
The liquid precursor compositions solidified do not have in the case of optional components measure time, have to
The carbon yield of few 35wt%；
(II) the described curable liquid carbon precursor composition of curing schedule (I) is solid to be formed
Change product；Wherein said solidification compositions, when not having to measure in the case of optional components, has
There is the carbon yield of at least 35 weight %；With
(III) the described cured product of carburising step (II) is to form carbonization compositions.
Utilize the carbonization group that said method is prepared from the liquid carbon precursor composition of the invention described above
The various final use carbonizations that compound can be advantageously used for comprising described carbonization compositions are produced
Product, such as carbon-carbon composite goods or parts.
It addition, when producing for the carbonization end product of final use as above, institute
State can carbonization liquid carbon precursor composition it solidify before show low clean viscosity, its permit
Permitted described liquid precursor flowing and fully moistening in various final uses with described liquid before
The material with carbon element (such as carbon fiber or carbon felt) that body is applied in combination.Such as, in solidification and carbonization
After the combination of liquid carbon precursor composition/material with carbon element, the carbonized product generated had compared with the beginning
The higher carbon density of material with carbon element；And the carbon density of the carbonized product generated increases sufficiently to
Level enough for its intended end use.
Some the most described carbonized product of the character improved can be provided to final carbonized product
The thermal conductance of parts and/or the carbon precursor composition of structural strength (such as maximum compressibility),
To be that technical staff is desired.Additionally, in some applications, it may be desirable to described carbon combination of precursors
Thing effectively can be evenly dispersed in whole another kind of material with carbon element (such as carbon fiber bundle or carbon
Fiber felt) in, thus reduce or minimize the inhomogeneities in described final carbonized product or
Inhomogeneity so that the reliability of the parts being made up of described final carbonized product is because more
Consistent bulk properties and improve.
It is an object of the invention to by with experiencing solidification and carbonization finally to produce carbonization
The low viscosity wettability liquid carbon precursor composition of substrate carrys out impregnated carbon substrate, thus provides use
In manufacturing the form of the molding structure with even compact and there is the thick high property of high-carbon yield
The fast and low-cost high efficiency method of energy carbon composite.
Advantageously, the wettable various material with carbon elements of low viscosity liquid carbon precursor composition of the present invention,
Such as carbon fiber；And described liquid carbon precursor composition can easily impregnated carbon substrate i.e.
Make the space of minimum.Once inside carbon matrix, just cause and be solidificated in inside described carbon matrix
Described liquid carbon precursor composition, produce solidification precursor, described solidification precursor and then can carbon
Change to form outstanding substrate.
It addition, the low viscosity liquid carbon precursor composition of the present invention provides in contrast to the prior art
Beyond thought and surprising result.Such as, United States Patent (USP) No.6,309,703
4th hurdle 14-19 row teaching is as follows:
" for rigidity prefabrication is formed, reach the target of the highest composite property
There is situation of facing a difficult choice: use low viscosity liquid matrix precursor and obtain good dipping, but
Pyrolysis inefficient；Or use high viscosity liquid matrix precursor and obtain the dipping of difference, but
Pyrolysis efficiency is high.”
United States Patent (USP) No.6,309,703 explains high molecular polymerization at the 4th hurdle 14-19 row
Thing (i.e. high viscosity liquid matrix precursor) is better than low-molecular weight polymer (i.e. low viscosity liquid
Matrix precursor) reason, as follows:
" the liquid binder used in all of carbon matrix and some ceramic matrix composites
The total basic chemical characteristic of both agent and liquid matrix precursor be they be polymer.This
Facts explain low viscosity adhesive and precursor have low pyrolysis efficiency and produce ropy base
The reason of matter.In order to have low viscosity, polymer must have a limited number of repetitive,
During fluid flows, otherwise there is the entanglement between polymer chain, limit quality transmission.?
Formed during substrate by pyrolysis, it is desirable to reaction be not occur between repetitive
In the case of cracking, from polymer repeat unit, lose some light composed atom, such as hydrogen.
But, in practice, but always there is undesired inevitably side reaction, wherein exist
Single repetitive is cleaved completely from the end of described polymer molecule, thus is formed relatively
The gas of high molecular.Because the end of the chain departs from (i.e., in extremely rapid succession one in a circulating manner
Individual connect one), the pyrolysis yield of low-molecular weight polymer is more much lower than heavy polymer.
It is starting point that heavy polymer only has the end of the chain of much less, so the end during being pyrolyzed
End fracture and associated gas escape much less.Gas effusion is harmful, because it is passing through
Pyrolysis is formed before substrate occurs and evicts liquid matrix precursor from rigidity prefabrication, and reduces heat
Solve yield.”
Therefore, according to the present invention, it is provided that show the liquid carbon combination of precursors of low clean viscosity
Thing.Described low viscosity liquid precursor, before solidification and carbonization, it is possible to flowing is also fully moistened
Wet material with carbon element (such as carbon fiber or carbon felt)；And simultaneously, after solidification and carbonization, it is possible to
Produce high-carbon yield (for example, at least 35wt% and the higher carbon receipts runed counter in prior art
Rate).
Accompanying drawing explanation
In order to the present invention is described, accompanying drawing shows the form of the currently preferred present invention.But,
It should be understood that the present invention is not limited in described figure the particular implementation of display.
Fig. 1 is to illustrate, it is shown that compared with the cure formulations of prior art, the present invention
Cure formulations develops (evolution) relative to the weight of temperature.
Fig. 2 is the photo of the drop of the liquid carbon precursor composition of the present invention.
Detailed description of the invention
In its widest range, the present invention relates to curable liquid carbon precursor composition, its
Comprise (a) at least one aromatic epoxy resin；(b) (i) at least one aromatics coreactivity is solid
Agent, (b) (ii) at least one catalytic curing agent or (b) (iii) its mixture；Wherein said liquid
State precursor composition before adding optional component, before curing and before carbonization,
There is the clean viscosity less than 10,000mPa-s when 25 DEG C；And wherein stand the liquid of solidification
State precursor composition, when not having to measure in the case of optional components, has at least 35wt%'s
Carbon yield.
" carbonization " or " pyrolysis " herein refer to by under inert atmosphere such as nitrogen with 10 DEG C
/ minute compositions being heated to 1 from 25 DEG C, the temperature of 000 DEG C, to remove from described compositions
The non-carbon of sizable part (significant portion).
" carbon yield " about solidification compositions herein refers under inert atmosphere such as nitrogen
With 10 DEG C/min of remaining weight from the solidified sample of 25 DEG C to the 1,000 DEG C of compositionss processed
Percentage ratio, it is measured in the case of there is not optional components.
Can be used for the aromatic epoxy resin compound of curable liquid carbon precursor composition of the present invention,
Component (a), can be the group of a kind of aromatic epoxy resin or two or more epoxy resin compounds
Closing, epoxy resin compound described at least one of which is aromatic epoxy resin.Such as, can be used for
A kind of preferred implementation of the aromatic epoxy resin of the present invention can be divinyl arenes dioxy
Compound.
In one embodiment, can be used in the curable liquid carbon precursor composition of the present invention
Divinylarene can include in the U.S. Patent application of serial number 13/133510
Any divinylarene described.
In another embodiment, can be used for preparing the curable liquid carbon precursor group of the present invention
The described divinylarene of compound can include, such as, carries in any ring position
There are any replacement of one or more vinyl or unsubstituted aromatic hydrocarbons core.Such as, described divinyl
The aromatic moiety of aromatic hydrocarbons dioxide can be by benzene, substituted benzene, (replacement) ring-cyclisation benzene or same
(replacement) benzene of system's bonding or its mixture composition.Described divinylarene
Divinylbenzene portion can be ortho position, meta or para position isomer or its any mixture.Its
His substituent group can be by resistance to H2O2Group constitute, described group include saturated alkyl, aryl,
Halogen, nitro, isocyanates or RO-(wherein R can be saturated alkyl or aryl).Ring
-cyclisation benzene can be made up of naphthalene and naphthane.Homology bonding (replacement) benzene can by biphenyl with
Diphenyl ether forms.
The divinylarene being used for preparing invention formulation generally can be by following
Chemical constitution I-IV illustrates:
The above structure I of the divinylarene that can be used for the present invention, II, III and
In IV, each R1、R2、R3And R4Hydrogen, alkyl, cycloalkyl, aryl or aralkyl can be individually
Base；Or resistance to H2O2Group includes such as halogen, nitro, isocyanates or RO group, wherein R
Can be alkyl, aryl or aralkyl；X can be the integer of 0 to 4；Y may be greater than or
Integer equal to 2；X+y can be less than or equal to the integer of 6；Z can be 0 to 6 whole
Number；Z+y can be less than or equal to the integer of 8；It is aromatic hydrocarbons fragment with Ar, including such as 1,3-
Phenylene.Additionally, R4Can be reactive group, including epoxy radicals, isocyanates or any
Reactive group, and Z is according to the integer that substitute mode can be 0 to 6.
In one embodiment, can be used for the described divinylarene of the present invention
Can be by the serial number 61/141457 such as submitted to for 30th in December, 2008 by Marks etc.
U.S. Provisional Patent Application (it is incorporated herein by) described in method produce.Separately
In a kind of embodiment, the described divinylarene that can be used for the present invention is disclosed in example
In United States Patent (USP) No.2,924,580 (it is incorporated herein by).
In another embodiment, can be used for the described divinyl arenes titanium dioxide of the present invention
Thing can include, such as, and divinylbenzene dioxide (DVBDO), divinyl naphthalene two
Oxide, divinyl biphenyls dioxide, divinyl diphenyl ether dioxide or its mixing
Thing.
In the preferred embodiment of the present invention, before the curable liquid carbon of the present invention
Described divinylarene in body compositions can be such as DVBDO.Divinyl
Base aromatic hydrocarbons dioxide such as DVBDO is a class diepoxide, and it has than relatively low liquid
Viscosity, but rigidity and crosslink density are higher than conventional epoxy.
In another kind of preferred implementation, can be used for the described divinyl arenes two of the present invention
Oxide compound includes, such as, and the DVBDO as shown in the chemical formula of following structure V:
The chemical formula of above DVBDO compound can be such that C10H10O2；Described DVBDO
Molecular weight be 162.2；The elementary analysis of described DVBDO is: C, 74.06；H, 6.21；
And O, 19.73, epoxide equivalent is 81g/mol.
Structures below VI shows the preferably chemistry knot of the described DVBDO that can be used for the present invention
Another embodiment of structure:
Structures below VII shows the preferably chemistry knot of the described DVBDO that can be used for the present invention
The further embodiment of structure:
When preparing DVBDO by methods known in the art, it is possible to obtain three kinds possible
One of isomer: ortho position, meta, and para-position.Therefore, the present invention includes appointing by above structure
What a kind of DVBDO illustrated individually or as its mixture.Structure VI above and VII
Respectively illustrate meta (1,3-DVBDO) isomer and the para-position (1,4-DVBDO) of DVBDO
Isomer.Ortho isomer is rare；The DVBDO generally produced in most cases typically exists
Meta (structure VI) and the scope that ratio is 9:1 to 1:9 of para-position (structure VII) isomer
In.As a kind of embodiment, the ratio that present invention preferably comprises structure VI and structure VII exists
In the range of 6:1 to 1:6, and in other embodiments, structure VI and structure VII
Ratio can be in the range of 4:1 to 1:4 or 2:1 to 1:2.
In another embodiment of the present invention, described divinylarene is permissible
Substituted arene containing a certain amount of (e.g., less than 20 weight %) and/or arene oxidizing thing.With two
The described substituted arene of vinyl-arene dioxide compositions mixing and/or the amount of arene oxidizing thing
Depend on the method for preparing described divinyl arenes precursor with structure, and described precursor and then
For preparing described divinylarene.Such as, divinyl arenes precursor such as two
Vinyl benzene (DVB) can be prepared by the dehydrogenation of diethylbenzene (DEB), and is given birth to
The product compositions become can contain a certain amount of vinyl xylene, ethyl vinyl benzene (EVB) and DEB.?
During the dehydrogenation reaction of DEB, wherein oxidant such as hydrogen peroxide, is present in reactant mixture
EVB can with hydroperoxidation to produce ethyl vinyl phenoxide, and DEB keep
Constant.In divinylarene, there is ethyl vinyl phenoxide and DEB can
The epoxide equivalent of described divinylarene is increased to more than pure divinyl arenes
The epoxide equivalent value of dioxide compound.
In one embodiment, can be used for the described divinylarene of the present invention
(such as DVBDO) comprises low viscous liquid-state epoxy resin.Such as, for the institute of the present invention
State the divinylarene range of viscosities when 25 DEG C the most in one embodiment
From 0.001Pa-s to 0.1Pa-s, in another embodiment from 0.01Pa-s to 0.05Pa-s,
From 0.01Pa-s to 0.025Pa-s in another embodiment.
A kind of favorable property of the described divinylarene that can be used for the present invention is it
Rigidity.The rigid nature of described divinylarene utilizes at Prediction of
Polymer Properties, Dekker, New York, the method for the Bicerano described in 1993,
Measured by the described dioxide that the calculates rotary freedom number in addition to side chain.The present invention
The rigidity of the divinylarene used by the most in one embodiment can be 6
To 10 rotary freedoms scope, in another embodiment from 6 to 9 rotary freedoms,
From 6 to 8 rotary freedoms in another embodiment.
Can be used for the described aromatic epoxy resin in curable liquid carbon precursor composition of the present invention can
To include the multiple aromatic ring in addition to described divinylarene known in the art
Epoxy resins.Described aromatic epoxy resin can be substituted or unsubstituted.Described aromatic ring oxygen tree
Fat can be monomer or polymerization.Described aromatic epoxy resin can include single aromatic ring oxygen tree
Fat maybe can include the combination of two or more aromatic epoxy resins.
Such as, the described aromatic epoxy resin that can be used for the present invention can include, in following documents
One or more aromatic epoxy resin compounds described: Pham, H.Q. and Marks, M.J.,
Epoxy Resins, the Kirk-Othmer Encyclopedia of Chemical Technology；
John Wiley&Sons, Inc.:2004 December is reached the standard grade and list of references therein on the 4th；Lee,
And Neville, K., Handbook of Epoxy Resins, McGraw-Hill Book H.
Company, New York, the 1967, the 2nd chapter, 2-1 to 2-33 page, and therein with reference to literary composition
Offer；May, C.A. write, Epoxy Resins:Chemistry and Technology, Marcel
Dekker Inc.:New York, 1988 and list of references therein；And United States Patent (USP) No.
3,117,099；So document is incorporated herein by.
Some the described aromatic epoxy resin compounds that can be used for the present invention include, such as, based on
The epoxide of the product of multifunctional phenol, aromatic amine or amino phenols and chloropropylene oxide.Some are non-
Restricted embodiment includes, such as, bisphenol A diglycidyl ether, Bisphenol F two are shunk sweet
Oil ether, resorcinolformaldehyde resin and the triglycidyl ether of p-aminophenol.This area is
Other the suitable epoxides known include such as chloropropylene oxide and o-cresol novolak, hydrocarbon phenolic aldehyde
Varnish and the product of phenol novolacs.Described epoxide is also selected from commercially available
Product, such as, be available from the D.E.R. of The Dow Chemical Company
D.E.R.332, D.E.R.354, D.E.R.580, D.E.N.425, D.E.N.431 or D.E.N.
438 epoxy resin.
As it was previously stated, described curable liquid carbon precursor composition can by mixing as mentioned above
At least one aromatic epoxy resin and (b) (i) at least one aromatics coreactivity firming agent or (b) (ii)
At least one catalytic curing agent or (b) (iii) described at least one aromatics coreactivity firming agent and institute
State the mixture of at least one catalytic curing agent and prepare.
" aromatics coreactivity firming agent " herein refers to the aromatic compounds with functional group,
Described functional group and the epoxy reaction of described aromatic epoxy resin, thus by described aromatics epoxy
The epoxide group of resin realizes solid with the condensation of the functional group of described aromatics coreactivity firming agent
Change and/or polymerization.
" catalytic curing agent " herein refers to a kind of compound, itself and described aromatic epoxy resin
Epoxide group reaction, thus cause described aromatic epoxy resin to solidify by epoxide homopolymerization
And/or polymerization.
Described at least one aromatics coreactivity firming agent or institute of the carbon precursor composition of the present invention
State at least one catalytic curing agent can include one of the most above-mentioned firming agent or two or more
Combination.Can be used for the aromatics coreactivity firming agent in the described carbon precursor composition of the present invention and urge
Changing firming agent can be solid selected from any aromatics coreactivity for epoxy resin known in the art
Agent or any catalytic curing agent.
Such as, can be used for described aromatics coreactivity firming agent (the also referred to as sclerosing agent of the present invention
Or cross-linking agent) can be any aromatic compounds of active group, described active group and institute
State the responding property of reactive epoxy groups of epoxy resin.The chemical property of such firming agent is front
Described in the handbook of epoxy resin.The described aromatics coreactivity that can be used for the present invention is solid
Agent includes nitrogen-containing compound, such as amine and their derivant；Oxygenatedchemicals, such as, hold carboxylic
Polyester, anhydride, phenolic resin, amino-formaldehyde resins, phenol, bisphenol-A and the cresol phenol of acid
Novolac and the epoxy resin of phenol end-blocking.
In a preferred embodiment, such as, DADPS and they isomer,
Aminobenzoate, various anhydride, phenol-novolac resin and cresol-novolak resin can
For the present invention, but the present invention is not limited to use these compounds.
The selection of described aromatics coreactivity firming agent can depend on the aromatics for described preparation
Epoxy resin.Generally, the described aromatics coreactivity firming agent that can be used for the present invention can be selected from,
Such as, but not limited to, phenol, benzimidazole dihydrochloride class, aromatic anhydride, aromatic amine, aromatic carbodiimide,
Aromatic polyester, aromatic polyisocyanate and mixture thereof.Use in divinylarene
In the case of making aromatic epoxy resin, described aromatics coreactivity firming agent can also include phenol, two
Phenol or polyphenol.
In one embodiment, at least one aromatics coreactivity firming agent described can include
Following one or more: aromatic amine such as methylene dianiline (MDA) (MDA), toluenediamine
(TDA), diethyl toluene diamine (DETDA), DADPS (DADS), many
Phenol such as bisphenol-A, Bisphenol F, 1,1-double (4-hydroxy phenyl)-ethane, hydroquinone, resorcinol, youngster
Tea phenol, tetrabromobisphenol A, novolaks such as phenol novolacs, bisphenol A novolac, hydrogen
Quinone novolaks, resorcinol novolaks, naphthol novolac varnish, anhydride such as phthalic acid
Acid anhydride, trimellitic anhydride, and its mixture.
In a preferred embodiment, in the curable liquid carbon precursor composition of the preparation present invention,
Described in the blending of described at least one aromatic epoxy resin such as divinylarene
Aromatics coreactivity firming agent can include, such as, is suitable for when compound is by carbonization or pyrolysis
In any compound providing the carbon yield more than 35 weight %.In one embodiment, suitable
Can include together in the described aromatics coreactivity firming agent providing high-carbon yield, such as phenol is the most right
Cresol or metacresol or other phenol, and mixture.One preferred embodiment includes can be used for
Phenolic compounds in the curable compositions of the present invention, such as paracresol.
Generally, the described aromatic epoxy resin of high-carbon yield used by the present invention it is adapted to provide for
Epoxide equivalent number (epoxide equivalents) and the coreaction of described aromatics coreactivity firming agent
The ratio r of property group, can be such as, in one embodiment from 0.1 to 10, at another
Plant in embodiment from 0.2 to 8；From 0.4 to 6 in another embodiment；With at another
From 1 to 5 in embodiment.When r is more than 1.0, after solidification, excess epoxy compound can
To keep unreacted maybe can be reacted in thermoset network.When described aromatic epoxy resin is two
When vinyl-arene dioxide and described aromatics coreactivity firming agent are phenol, the definition of r is such as
As co-pending U.S. Provisional Patent Application No.61/660,397 is explained.
The described catalytic curing agent that can be used for the present invention can include, such as, and Bronsted acid
(Bronsted acids), Louis (Lewis) acid, lewis base, alkali formula alkali, Louis
Acid-Lewis base complexes, quaternary ammonium compound, quaternary compound or its mixture.Suitably
The example of Bronsted acid include sulphuric acid, sulfonic acid, perchloric acid, phosphoric acid, the partial ester of phosphoric acid and
Its mixture.A lewis acidic suitable example includes boron trifluoride.Lewis base suitable
Example includes tertiary amines, imidazoles, amidine class, substituted urea and mixture thereof.One conjunction of alkali formula alkali
Suitable example includes potassium hydroxide.One suitable example of lewis acid-Lewis base complexes
Including boron trifluoride-ethylamine complex.One suitable example of quaternary ammonium compound is benzyl front three
Base ammonium hydroxide.One suitable example of quaternary compound is tetrabutylammonium hydroxide.
It addition, when using aromatic epoxy resin such as divinylarene, available
Described catalytic curing agent in the present invention can include co-pending U.S. Provisional Patent Application No.
Resting form catalyst described in 61/660,403.
In the curable liquid carbon precursor composition of the preparation present invention, can be to described curable liquid
State carbon precursor composition adds optional compound, including for example, at least a kind of curing catalysts.
" curing catalysts " herein refers to for promoting that at least one aromatic epoxy resin described is with described
The compound of the reaction of aromatics coreactivity curative compound.Described curing catalysts can be based on
Epoxy resin used in the present composition and the aromatics coreactivity firming agent used add
To select.
In a kind of illustrated embodiment, when described epoxy resin is such as divinyl arenes
When dioxide and described firming agent are such as phenol, the described optional solidification that can be used for the present invention is urged
Agent can include that curing catalysts that at least one acid compound is relevant is to promote described divinyl
Base aromatic hydrocarbons dioxide compound and the reaction of described phenol.In one embodiment, can be used for this
The described catalyst of invention can include, such as, and the US provisional patent of serial number 61/556979
Catalyst described in application any one or more of, such as Bronsted acid (such as can be from
Cytec is purchased600), lewis acid and mixture thereof.Another kind of embodiment party
In formula, described catalyst can include such as resting form alkylation ester, such as, WO 9518168
Described in catalyst any one or more of.
In another embodiment, described resting form alkylation ester curing catalysts can include
Such as, the ester of sulfonic acid, such as methyl tosylate (MPTS), ethyl p-toluenesulfonate
And methyl mesylate (MMS) (EPTS)；The ester of alpha-halogenated carboxylic acids, such as trichloroacetic acid
Methyl ester and trifluoro-acetate；With the ester of phosphonic acids, such as tetraethyl methylene-bisphosphonates；Or
Its any combination.A preferred implementation for the described curing catalysts of the present invention can be wrapped
Include such as MPTS.Other curing catalysts that can be used for the present invention can include the most co-pending
U.S. Provisional Patent Application No.61/660,397 described in those.
Generally, the catalytic curing agent used in the present invention or the amount of optional curing catalysts are permissible
It is such as, in one embodiment from 0.01wt% to 20wt%, in another embodiment
From 0.1wt% to 10wt%；From 0.1wt% to 5wt% in another embodiment；With further
Plant in embodiment from 0.1wt% to 3wt% catalyst.Use lower level catalytic curing agent or
Optional curing catalysts is by reduction reactivity and cross-linked network will be caused to reduce；And use more Gao Shui
Flat catalytic curing agent or optional curing catalysts will be uneconomic.
Other the optional chemical combination in the curable liquid carbon precursor composition of the present invention can be made an addition to
Thing can include chemical combination well known by persons skilled in the art, that be generally used in curable resin preparation
Thing.Such as, described optional components can include can making an addition in described compositions to improve screening characteristics
Can (such as surface tension modifier or fluidizer), reliability (such as adhesion promoter), reaction speed
The compound of rate, reaction selectivity and/or catalyst life.
Other the optional chemical combination in the curable liquid carbon precursor composition of the present invention can be made an addition to
Thing can include, such as, at the beginning of dropping to the viscosity of described preparation even than described compositions
The solvent that beginning viscosity is the lowest；It is different from other epoxy resin of described aromatic epoxy resin (such as
Aliphatic series glycidyl ether or cycloaliphatic epoxy resin)；It is different from aromatics coreactivity firming agent and urges
Change other firming agent of firming agent；Filler；Pigment；Fiber；Toughener；Flow ability modifying agent；Help
Stick；Diluent；Stabilizer；Plasticizer；Curing catalysts；HP catalyst killer；Fire retardant；
Coal tar asphalt；Asphalt；Aromatic resins；CNT；Graphene；White carbon black；Carbon fiber；
Or its mixture.
Generally, other optional compound amounts as used in this application described can be such as,
0wt% to 90wt% in one embodiment, in another embodiment from 0.01wt% to
80wt%；From 0.1wt% to 65wt% in another embodiment；With in another embodiment
In from the firming agent of 0.5wt% to 50wt%.
One embodiment of the present invention relates to preparing foregoing curable liquid carbon precursor composition
Method, described compositions is resin formulation or the compositions of the low clean viscosity of curable high-carbon yield.System
The method of the curable liquid carbon precursor composition of the standby present invention comprises the following steps: mixing (a) is at least
A kind of aromatic epoxy resin and (b) (i) at least one aromatics coreactivity firming agent, (b) (ii) are at least
A kind of catalytic curing agent or (b) (iii) its mixture；(c) optional, at least one
Curing catalysts or other optional member as required.Described liquid precursor compositions is being added
Before optional component, before curing and before carbonization, have less than 10,000 when 25 DEG C
The clean viscosity of mPa-s；And when not having to be measured by thermogravimetric analysis in the case of optional components,
Liquid precursor compositions when standing solidification advantageously has the carbon yield of at least 35wt%.
For being low viscosity with manufacturing the compound advantageous of described curable liquid carbon precursor composition
Material, their mixing need not special effort.Such as, before the curable liquid carbon of the present invention
The preparation of body compositions is easily by blending described with magnetic stirring bar blender or tub blender
The composition of compositions completes.Such as, described curable liquid carbon precursor composition available standards
Tub blender mixes with 1rpm to 200rpm.
Required for the curable liquid carbon precursor composition of the present invention or preparation and optional component
Or composition generally has the most curable of balance of properties required by concrete application can prepare
Mix at a temperature of compositions and disperse.Such as, the temperature during the mixing of described component is real in one
Execute in mode generally can from-10 DEG C to 100 DEG C, and in another embodiment from 0 DEG C to
50℃.Relatively low mixing temperature contributes to the reaction minimizing described resin with hardener component, from
And the storage phase of described preparation is maximized.
As a kind of illustrated embodiment and be not limited except as, divinylbenzene dioxide,
Paracresol, curing catalysts and other desired and optional additives, such as other asphalt mixtures modified by epoxy resin
Fat, can mix to be formed the curable liquid carbon precursor composition of the present invention.
The preparation of the curable liquid carbon precursor composition of the present invention and/or its any step, can
To be method in batches or continuously.Mixing apparatus for described method can be those skilled in the art
Known any container and auxiliary equipment.
The described curable liquid carbon precursor composition of the present invention, is adding any optional chemical combination
Before thing, before curing and before carbonization, have less than 10,000mPa-s at 25 DEG C
Clean viscosity.Such as, there is no the described curable liquid carbon precursor composition of optional compound,
Before solidification and carbonization, the clean viscosity having when 25 DEG C is typically smaller than in one embodiment
10,000mPa-s, in another embodiment from 1mPa-s to 10,000mPa-s, another
Plant in embodiment from 1mPa-s to 5,000mPa-s, from 5 in another embodiment
MPa-s to 3,000mPa-s, and from 10mPa-s to 1,000 in another embodiment
mPa-s.In other embodiments, described curable liquid carbon precursor composition is before curing
Clean viscosity can include 1mPa-s or higher, 5mPa-s or higher, or 10mPa-s or higher.
In other embodiments, described curable liquid carbon precursor composition clean viscosity before curing
Can include 10,000mPa-s or lower, 5,000mPa-s or lower, 3,000mPa-s or lower,
Or 1,000mPa-s or lower..
A low viscous advantage of the curable liquid carbon precursor composition of the present invention is described low
Viscosity makes it possible to be absorbed by described carbon matrix such as carbon fiber can the resin of processing capacity.
Additionally, utilize adding before any optional compound, before curing with in carbonization
Clean viscosity is less than 10 before, the curable liquid carbon precursor composition of the present invention of 000mPa-s, it is provided that
There is the cured product of high-carbon yield, as with reference to Fig. 1 will described in.
In addition to having low viscosity, described curable liquid carbon precursor composition, in solidification
Before, the surface tension having when 25 DEG C in one embodiment can from 10mN/m to
70mN/m, in another embodiment from 20mN/m to 60mN/m and real at another
Execute in mode from 30mN/m to 60mN/m.In other embodiments, described curable liquid
State carbon precursor composition surface tension before curing can include 10mN/m or higher, 20
MN/m or higher, or 30mN/m or higher.In other embodiments, described curable
Liquid carbon precursor composition surface tension before curing can include 70mN/m or lower or
60mN/m or lower.
Additionally, the curable liquid carbon precursor composition of the present invention can have be enough to easily and
The wettability of the surface energy of moistening carbon substrate or component effectively, say, that described liquid precursor
Having the affinity between liquid and surface, described affinity changes into described liquid dissemination to institute
State the ability on substrate surface.
Such as, in a kind of embodiment with reference to Fig. 2, which show and be still in substrate surface
Top on, the photo of the drop of the curable liquid carbon precursor composition of the present invention, totally by
Numeral 20 instruction, including the drop 21 of the described curable liquid carbon precursor composition of the present invention,
It has been placed on the flat surface of substrate 22 such as graphite substrate under ambient temperature (about 25 DEG C)
On, so that the wettability of described drop 21 to be described.The contact angle of described drop is by arrow 23 and 24
And angle 25 shows.As known in the art, angle 25 is the least, and substrate surface 22 is by liquid
Drip 21 moistening the best.
Generally, according to contact angle on the surface of a substrate, described curable liquid carbon combination of precursors
The drop of thing, such as Fig. 2 display wettability at ambient temperature, i.e. wettability, can be at least
Less than 90 degree, preferably from zero degree to 90 degree, more preferably from 5 degree to 90 degree, even more preferably
From 10 degree to 60 degree, and most preferably from 15 degree to 40 degree, it is according to ASTM method D5725-99
Disclosed in method measure on substrate or fiber surface.In other embodiments, described consolidate
Change liquid carbon precursor composition contact angle before curing and can include 0 degree or higher, 5 degree or more
Height, 10 degree or higher, or 15 degree or higher.In other embodiments, described curable liquid
State carbon precursor composition contact angle before curing can include 90 degree or less, 60 degree or less,
Or 40 degree or less.
Wherein contact angle can measure according to described fluid composition, can for the substrate of the present invention
With change, and such as graphite, glass, pottery and metal can be included.
The method of the present invention includes solidifying foregoing curable liquid carbon precursor composition with shape
Become curing materials or the step of cured product.The solidification of described curable liquid carbon precursor composition can
To carry out the scheduled time slot that be enough to solidify described liquid carbon precursor composition at a predetermined temperature.Example
As, the temperature solidifying described curable liquid carbon precursor composition or preparation generally can be real in one
Execute in mode from 10 DEG C to 350 DEG C；In another embodiment from 25 DEG C to 200 DEG C,
From 100 DEG C to 190 DEG C in another embodiment；With in another embodiment from 125 DEG C
To 175 DEG C.In other embodiments, described solidification temperature can include 10 DEG C or higher, 25 DEG C
Or higher, 100 DEG C or higher, or 125 DEG C or higher.In other embodiments, described solid
Change temperature and can include 350 DEG C or lower, 200 DEG C or lower, 190 DEG C or lower, or 175 DEG C
Or it is lower.
Generally, the hardening time of described curable liquid carbon precursor composition or preparation is solidified one
Kind of embodiment can be chosen as between 1 minute to 90 days, in another embodiment 2
Minute to 7 days, 3 minutes to 1 days, 5 minutes to 8 hours, between 7 minutes to 4 hours, and
In another embodiment between 10 minutes to 2 hours.In other embodiments, described
Can include 1 minute or longer hardening time, 2 minutes or longer, 3 minutes or longer, 5 minutes or
Longer, 7 minutes or longer, or 10 minutes or longer.In other embodiments, described solidification
Time can include 90 days or less, 7 days or less, 1 day or less, 8 hours or less, 4
Hour or less, or 2 hours or less.
The divinylarene of the present invention, such as DVBDO, be that the present invention is curable
A kind of embodiment of the epoxy resin ingredient of compositions, it can be at final curable liquid carbon
Precursor composition or preparation are used as to be formed unique resin of epoxy substrate；Or described divinyl
Aromatic hydrocarbons dioxide resin can be with other rings being different from described divinylarene
Epoxy resins is applied in combination, as the epoxy in final curable liquid carbon precursor composition or preparation
Component.
The clean viscosity when the being solidificated in 25 DEG C described curable liquid carbon less than 10,000mPa-s
After precursor composition, the solidification compositions generated is suitable for being carbonized or being processed further.Solidification
After described curable liquid carbon precursor composition, described solidification compositions comprises solid body (solid
Body), described solid body can form or be shaped to desired preformed configuration, then carbonization institute
State structure.
Having of curing materials is produced from solidifying curable liquid carbon precursor composition as above
Benefit one of result includes the cured product producing carbon yield typically at least 35wt%, and it is appointed not existing
Measure in the case of selecting component.Such as, the carbon yield of described cured product, passes through thermogravimetric analysis
(TGA) measure, gross weight based on described solidification compositions, the most generally
Can be from 35wt% to 95wt%, in another embodiment from 40wt% to 90wt%,
From 45wt% to 85wt% in another embodiment, or from 50wt% in another embodiment
To 80wt%.In other embodiments, the carbon yield of described cured product can include 35wt% or
Higher, 40wt% or higher, 45wt% or higher, or 50wt% or higher.Other embodiment party
In formula, the carbon yield of described cured product can include 95wt% or lower, 90wt% or lower,
85wt% or lower, or 80wt% or lower.
The final solidification produced from the solidification of curable liquid carbon precursor composition as above
Material (i.e. cross-linking products) forms the preform precursor of solidification, and it can be according to carbonization of the present invention to enter
One step is formed has the some improved properties relative to the conventional epoxy having cured with carbonization
Carbonization compositions or carbonized product.
In one embodiment, curing schedule as above can be completely or partially with described
Carburising step is carried out simultaneously.In another embodiment, described carburising step can be as with described
The separate step of curing schedule is carried out.
Such as, the method for the present invention can comprise the steps: at inert atmosphere such as nitrogen or true
The scheduled time slot that curing materials described in aerial carbonization at a predetermined temperature is enough, to solidify described in carbonization
Material, and the carbonization compositions with the carbon yield more than 35wt% is provided.Such as, described in carbonization
The temperature of curing materials the most generally can be from 350 DEG C to 4,000 DEG C；Separately
From 400 DEG C to 3,500 DEG C in a kind of embodiment；In another embodiment from 500 DEG C to
3,000℃；From 800 DEG C to 2000 DEG C in another embodiment.
Generally, the time of curing materials described in carbonization can depend on the amount of material with carbon element, carbon goods
Size and the complexity of carbon goods.In a kind of illustrated embodiment, solidify described in carbonization
The time of material may be selected to be the most in one embodiment in the range of 1 minute to 90 day,
In another embodiment from 30 minutes to 7 days and little from 1 in another embodiment
Up to 24 hours.
Curing materials described in carbonization provides to have and is better than the some excellent of prior art as described above
The carbonization compositions of point or carbonized product.Such as, an advantage of the carbonization compositions of the present invention is
The impurity level of described carbonization compositions is few.Described impurity can include such as metal and nonmetal.Institute
State carbonization compositions exists impurity can be to its property in the various application of the char-forming material generated
Matter introduces ill-effect, and therefore the impurity in carbonized product should be avoided.
In one embodiment, the curable liquid composition precursors of the present invention can be cured
And carbonization, to form the preforming material of carbonization for the application in various final uses subsequently.?
In another embodiment, the curable liquid composition precursors of the present invention can be by such as to lining
Bottom application adds described fluid composition and is used as epoxy adhesive；Then solidification and/or carbonization are to be formed
Preforming material is for the application in various final uses subsequently.
Such as, the char-forming material of the present invention may be used for aerospace applications, electronic application and height
In the composite of temperature processing.Such as, the carbonization final products of carbonized product of the present invention are used to wrap
Include fuel cell, heat exchanger, carbon fiber, needle coke, graphite anode and structural conductive carbon-to-carbon
Composite product or parts
Embodiment
Following example and the comparative example further description present invention, but the limit of should not be construed as
Make its scope.
Various terms and title used by following example are described as follows at this:
" DVBDO " represents divinylbenzene dioxide.
" MPTS " represents methyl tosylate.
" EPTS " represents ethyl p-toluenesulfonate.
" MMS " represents methyl mesylate.
" DDS " represents 4,4-DADPS.
" TGA " represents thermogravimetric analysis.
600 is DBSA (70wt% in isopropanol) can be from
Cytec is purchased.
3000 is phenol formaldehyde novolac resin aromatics firming agent, can be from SI
Group, Inc. are purchased.
Embodiment uses following standard analytical equipment and method:
The viscosity measurement of precursor composition
The viscosity of the described curable liquid carbon precursor formulation of the present invention is at torque rheometer TA
Measuring on Instruments AR 2000, described flow graph is equipped with on the smooth rustless steel of 50mm diameter
Plate and Peltier bottom deck assembly control the temperature of liquid sample and act on described Peltier plate surface
Both normal force.Described base plate deposits preparation described in about 2mL, then described top board is dropped
On described liquid formulation, until the gap between two plates reaches 300 microns.Top board is right
After rotate with the nominal rate of 0.001 radian per second, the temperature of base plate is with 10 DEG C/min of speed simultaneously
It is increased to 65 DEG C from 25 DEG C.Viscosity is automatically calculated by TA software and is reported as the function of temperature.
The measurement of liquid-drop contact angle
Measure the contact angle of liquid sample firstly the need of the surface tension measuring described liquid.Cahn
Dynamic Contact Angle Analyzer is for measuring the surface tension of described liquid.Cahn dynamic contact angle divides
Analyzer is for measuring the surface tension of described liquid.The oxidation blue-flame with propane welding torch is used to clean five
Secondary " Wilhelmy " glass plate.The method used is in ZDOI (zero soaking depth) position
The step " reading weight/time until weight is stable ".Described liquid is at described Wilhelmy glass
Captivation on plate is automatically converted to surface tension value by Cahn software.
Cahn Dynamic Contact Angle Analyzer is additionally operable to the contact measured in the second configuration, Qi Zhong
Deposit drop on substrate and automatically calculated described drop over the substrate during 200 second period
Contact angle.Between the tangent line at the edge that described angle is defined as described plane and liquid formulation drips
Gap, angle.
Carbon yield is measured
Carbon yield (%C) is by utilizing TA Instruments Q5000 thermogravimetric analyzer at nitrogen
Under rise to 1 with 10 DEG C/min from 25 DEG C, the temperature of 000 DEG C, and being measured by thermogravimetric analysis.
The wt% that " %C " is defined as carbon when above-mentioned analysis completes is remaining.
Embodiment 16 and Comparative examples A and B
Merge the formulation components of display in Table I and form the solution of homogenizing, at sky in aluminum dish or mould
Gas circulation baking oven utilize indicated program curing to solidify, and by TGA carbonization.Implementing
In example 3, described component be heated to before curing 120 DEG C with formed homogenizing solution, be cooled to
100 DEG C, and pour in the mould being preheating to 100 DEG C.When being cooled to 25 DEG C, this mixture becomes
Slurry.
Table I
(1)The program curing pointed out in table I above is as follows:
A. at 60 DEG C and 80 DEG C each 15 minutes, at 100 DEG C 30 minutes, and 110 DEG C, 120 DEG C, 130 DEG C, 140 DEG C,
At 150 DEG C, 160 DEG C, 175 DEG C, 200 DEG C and 220 DEG C each 15 minutes..
B. at 60 DEG C, 80 DEG C, 90 DEG C, 100 DEG C, 105 DEG C, 110 DEG C, 115 DEG C, 120 DEG C and 150 DEG C each 30 minutes, Yi Ji
At 200 DEG C and 225 DEG C each 60 minutes.
C. at 120 DEG C 60 minutes, and at 160 DEG C, 200 DEG C, 240 DEG C, 260 DEG C and 280 DEG C each 30 minutes.
D. each at 60 DEG C, 70 DEG C, 80 DEG C, 90 DEG C, 100 DEG C, 105 DEG C, 110 DEG C, 115 DEG C, 120 DEG C, 120 DEG C and 150 DEG C
30 minutes.
E. at 80 DEG C 60 minutes, at 100 DEG C 30 minutes, and at 200 DEG C 90 minutes..
F. for the program of this plate manufacture amendment:.
Add DEN 438 and DDS to round-bottomed flask, be heated slowly to 120 DEG C.After DDS has been completely dissolved, solution is placed in vacuum
Lower degassing (5mmHg) also progressively cools to 100 DEG C.Pour in the mould of preheating (100 DEG C) and mould is placed in preheating oven
At 220 DEG C 120 minutes.
G. at about 160 DEG C, melt CHTP, then add DVBDO and mix.It is allowed to cool until remaining fluid.Add catalyst, mixed
About 15 seconds, it is subsequently poured in dish and heats 30 minutes at 250 DEG C.
(2)Said composition becomes solid and unmeasured viscosity at 25 DEG C.
Fig. 1 is that the figure of the weight change of solidification carbon precursor formulation represents, initial weight is in y-axis
On be expressed as 100% and be generally between 10mg and 20mg.Fig. 1 shows, along with temperature
1 is increased to from 25 DEG C with the speed of 10 DEG C/min, 000 DEG C, described solidification carbon precursor composition
Relative weight reduces, until relative weight is 1, the maximum temperature of 000 DEG C is issued to described solidification carbon
Till the carbon yield of precursor composition.Preparation shown in Fig. 1 includes as above basis described by Table I
The cure formulations of invention such as embodiment 1 (), embodiment 2 (◇) and embodiment 3 (),
With the cure formulations such as Comparative examples A of prior art (▲), comparative example C (◇) and comparing
Example D (●) is compared, and it develops (evolution) relatively relative to the weight of temperature.
Claims (16)
1. curable liquid carbon precursor composition, it comprises (a) and includes divinyl arenes two
At least one aromatic epoxy resin of oxide；(b) (i) at least one aromatics coreactivity is solid
Agent, (b) (ii) at least one catalytic curing agent or (b) (iii) its mixture；Wherein said liquid
State precursor composition before adding optional component, before curing and before carbonization,
There is the clean viscosity less than 10,000mPa-s when 25 DEG C；And wherein stand the liquid of solidification
State precursor composition, when not having to measure in the case of optional components, has at least 35wt%'s
Carbon yield.
2. the compositions of claim 1, the carbon yield of wherein said compositions is 35 weight %
To 95 weight %.
3. the compositions of claim 1, wherein said compositions includes solvent-free composition.
4. the compositions of claim 1, the clean viscosity of wherein said compositions is at 25 DEG C
From 1mPa-s to 10,000mPa-s.
5. the compositions of claim 1, wherein said divinylarene includes two
Vinyl benzene dioxide.
6. the compositions of claim 1, wherein said firming agent includes phenolic compound；And
Wherein said phenolic compound includes single phenol, diphenol, polyphenol or its mixture.
7. the compositions of claim 6, wherein said single phenol includes paracresol.
8. the compositions of claim 1, it comprises (c) at least one curing catalysts.
9. the compositions of claim 1, it comprises other that be different from described aromatic epoxy resin
Epoxy resin, it is different from its of described aromatics coreactivity firming agent and described catalytic curing agent
His firming agent, filler, reactive diluent, increasing scratch agent, processing aid, toughener or
Its mixture.
10. the method preparing liquid carbon precursor composition, described method includes mixing (a) bag
Include at least one aromatic epoxy resin of divinylarene；(b) (i) at least
Kind of aromatics coreactivity firming agent or (b) (ii) at least one catalytic curing agent or (b) (iii) its
Mixture；Wherein said liquid precursor compositions is before adding optional component, in solidification
Before and before carbonization, have when 25 DEG C less than 10, the clean viscosity of 000mPa-s；And
And wherein stand solidification liquid precursor compositions measure in the case of there is no optional components
Time, there is the carbon yield of at least 35wt%.
The liquid carbon precursor composition of 11. solidifications, before it comprises the liquid carbon of cure curable
The product of body preparation, described preparation comprises (a) and includes divinylarene
At least one aromatic epoxy resin；(b) (i) at least one aromatics coreactivity firming agent,
(b) (ii) at least one catalytic curing agent or (b) (iii) its mixture；Wherein said liquid precursor
Compositions is before adding optional component, before curing and before carbonization, at 25 DEG C
Time there is the clean viscosity less than 10,000mPa-s；And the compositions of wherein said solidification exists
When measuring in the case of there is no optional components, there is the carbon yield of at least 35wt%.
The method of the liquid carbon precursor composition of 12. preparation solidifications, described method includes solidification
Curable liquid carbon precursor formulation, described preparation comprises (a) and includes divinyl arenes two
At least one aromatic epoxy resin of oxide；(b) (i) at least one aromatics coreactivity is solid
Agent, (b) (ii) at least one catalytic curing agent or (b) (iii) its mixture；Wherein said liquid
State precursor formulation before adding optional component, before curing and before carbonization,
There is when 25 DEG C the clean viscosity less than 10,000mPa-s；And the combination of wherein said solidification
Thing, when not having to measure in the case of optional components, has the carbon yield of at least 35wt%.
13. methods preparing carbonized product, said method comprising the steps of:
(I) mixing (a) includes at least one aromatics epoxy of divinylarene
Resin；(b) (i) at least one aromatics coreactivity firming agent or (b) (ii) at least one catalysis
Firming agent or (b) (iii) its mixture, to form fluid composition；Wherein said liquid precursor
Compositions is before adding optional component, before curing and before carbonization, at 25 DEG C
Time there is the clean viscosity less than 10,000mPa-s；And wherein stand the liquid precursor of solidification
Compositions, when not having to measure in the case of optional components, has the carbon yield of at least 35wt%；
(II) the described fluid composition of curing schedule (I) is to form cured product；Wherein
Described solidification compositions, when not having to measure in the case of optional components, has at least 35 weight
The carbon yield of %；With
(III) the described cured product of carburising step (II) is to form carbonization compositions.
The method of 14. claim 13, wherein said method is entered in the absence of a solvent
OK.
The method of 15. claim 13, wherein step (I) is from-10 DEG C to 100 DEG C
At a temperature of carry out；Wherein step (II) is being carried out at a temperature of 10 DEG C to 350 DEG C；With
Wherein step (III) is being carried out at a temperature of 350 DEG C to 4,000 DEG C.
The 16. carbonization compositionss prepared by the method for claim 13.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201261660417P | 2012-06-15 | 2012-06-15 | |
| US61/660,417 | 2012-06-15 | ||
| PCT/US2013/041567 WO2013188052A1 (en) | 2012-06-15 | 2013-05-17 | A carbon precursor composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104364297A CN104364297A (en) | 2015-02-18 |
| CN104364297B true CN104364297B (en) | 2016-08-24 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201380031660.XA Expired - Fee Related CN104364297B (en) | 2012-06-15 | 2013-05-17 | Carbon precursor composition |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP2861653A1 (en) |
| JP (1) | JP2015525274A (en) |
| CN (1) | CN104364297B (en) |
| RU (1) | RU2015101136A (en) |
| TW (1) | TWI582060B (en) |
| WO (1) | WO2013188052A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017515771A (en) * | 2014-03-27 | 2017-06-15 | ブルー キューブ アイピー エルエルシー | Method for producing carbon / carbon composite material |
| EP3356311A1 (en) * | 2015-09-30 | 2018-08-08 | Blue Cube IP LLC | Precursors for carbon-carbon composites |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6465100B1 (en) * | 1993-06-15 | 2002-10-15 | Alliant Techsystems Inc. | Densification of composite preforms by liquid resin infiltration assisted by rigid-barrier actinic gelation |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2924580A (en) | 1957-08-08 | 1960-02-09 | Union Carbide Corp | Divinyl benzene dioxide compositions |
| NL298323A (en) | 1959-12-24 | |||
| GB1135816A (en) * | 1966-05-12 | 1968-12-04 | Union Carbide Corp | Carbonaceous articles |
| GB1343773A (en) | 1970-05-05 | 1974-01-16 | Atomic Energy Authority Uk | Graphite structures |
| GB2151221B (en) * | 1983-12-14 | 1987-09-23 | Hitco | High strength oxidation resistant carbon/carbon composites |
| GB9326427D0 (en) | 1993-12-24 | 1994-02-23 | Dow Deutschland Inc | Kinetically controlled in-situ generation of catalytic species for the curing of epoxy/amine compositions |
| US6309703B1 (en) | 1998-06-08 | 2001-10-30 | The United States Of America As Represented By The Secretary Of The Air Force | Carbon and ceramic matrix composites fabricated by a rapid low-cost process incorporating in-situ polymerization of wetting monomers |
| KR101381483B1 (en) * | 2006-10-20 | 2014-04-04 | 에아.워타 가부시키가이샤 | Non-thermofusible granular phenol resin, method for producing the same, thermosetting resin composition, sealing material for semiconductor, and adhesive for semiconductor |
| BR112012011527A2 (en) * | 2009-12-03 | 2019-09-24 | Dow Global Technologies Llc | polyamide adduct, curable epoxy resin composition, process for preparing an amine adduct and process for preparing a curable epoxy resin composition |
| CN105175688A (en) * | 2010-02-19 | 2015-12-23 | 陶氏环球技术有限责任公司 | Divinylarene dioxide resin compositions |
| CN102939314B (en) * | 2010-06-15 | 2016-07-06 | 巴斯夫欧洲公司 | Cyclic carbonate purposes in composition epoxy resin |
-
2013
- 2013-05-17 WO PCT/US2013/041567 patent/WO2013188052A1/en active Application Filing
- 2013-05-17 RU RU2015101136A patent/RU2015101136A/en unknown
- 2013-05-17 JP JP2015517268A patent/JP2015525274A/en active Pending
- 2013-05-17 EP EP13726956.9A patent/EP2861653A1/en not_active Withdrawn
- 2013-05-17 CN CN201380031660.XA patent/CN104364297B/en not_active Expired - Fee Related
- 2013-06-14 TW TW102121019A patent/TWI582060B/en not_active IP Right Cessation
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6465100B1 (en) * | 1993-06-15 | 2002-10-15 | Alliant Techsystems Inc. | Densification of composite preforms by liquid resin infiltration assisted by rigid-barrier actinic gelation |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2015525274A (en) | 2015-09-03 |
| TWI582060B (en) | 2017-05-11 |
| WO2013188052A1 (en) | 2013-12-19 |
| RU2015101136A (en) | 2016-08-10 |
| EP2861653A1 (en) | 2015-04-22 |
| TW201412682A (en) | 2014-04-01 |
| CN104364297A (en) | 2015-02-18 |
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