CN101661809B - Granular carbon electrode material and its manufacturing method - Google Patents

Granular carbon electrode material and its manufacturing method Download PDF

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Publication number
CN101661809B
CN101661809B CN2009101734092A CN200910173409A CN101661809B CN 101661809 B CN101661809 B CN 101661809B CN 2009101734092 A CN2009101734092 A CN 2009101734092A CN 200910173409 A CN200910173409 A CN 200910173409A CN 101661809 B CN101661809 B CN 101661809B
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phenol resin
granular
electrode material
granular phenol
carbon electrode
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CN101661809A (en
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吉永直人
若山善治
茨木敏
下村淳
村外荣己
盐见仁郎
小谷善信
池田孝臣
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Air Water Inc
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Air Water Inc
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Priority claimed from JP2007174033A external-priority patent/JP2009013224A/en
Priority claimed from JP2007214781A external-priority patent/JP4949971B2/en
Priority claimed from JP2007251605A external-priority patent/JP5496448B2/en
Application filed by Air Water Inc filed Critical Air Water Inc
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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
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Abstract

Disclosed is a non-thermofusible phenol resin powder having an average particle diameter of not more than 20 [mu]m and a single particle ratio of not less than 0.7. This non-thermofusible phenol resin powder preferably has a chlorine content of not more than 500 ppm. This non-thermofusible phenol resin powder is useful as an organic filler for sealing materials for semiconductors and adhesives for semiconductors. The non-thermofusible phenol resin powder is also useful as a precursor of functional carbon materials such as a molecular sieve carbon and a carbon electrode material.

Description

Granular carbon electrode material and manufacturing approach thereof
The application is 200780034852.0 (international application no: dividing an application PCT/JP2007/069927); The applying date of original application is on October 12nd, 2007, and the denomination of invention of original application is non-thermofusible granular phenol resin and manufacturing approach and compositions of thermosetting resin, sealing material for semiconductor and adhesive for semiconductor.
Technical field
The present invention relates to a kind of non-thermofusible granular phenol resin and manufacturing approach thereof.More specifically; The present invention relates to be used as organic filler; The perhaps precursor of functional material with carbon element such as molecular-sieve carbon, carbon electrode material etc., safe non-thermofusible granular phenol resin and the manufacturing approach thereof can be well used as the additive of the material in the various industrial circles such as moulding material, coating, refractory material, papermaking, high-abrasive material, whetstone, adhesive.In addition, the sealing material for semiconductor and the adhesive for semiconductor that the invention still further relates to the compositions of thermosetting resin that contains this non-thermofusible granular phenol resin and use this compositions of thermosetting resin.
Background technology
Phenolic resins is the outstanding material of the balance of thermal endurance, mechanical property and electrical characteristics and cost, is used to various industrial circles.Especially the granular or pulverous phenolic resins of discovered in recent years or its solidfied material go for various fields, and as multi-purpose material, existing several kinds of goods are sold.
For example; Open the spy and to disclose the granular or Powdered phenolic resin curing thing that the condensation product by phenols and formaldehyde forms in the clear 57-177011 communique (patent documentation 1), it is sold as trade name " Bellpearl (registered trade mark) R type " (Air Water Inc.'s system).This phenolic resin curing thing for example can be used as to be given thermal endurance or improves the organic filler of sliding properties or use as the filler that is used to reduce the gas flow that produces when uncured phenolic resins etc. is solidified.In addition, the resin that phenolic resins is high carbon residue rate owing to its chemical constitution is so for example can be used as activated carbon or the precursor that burns till of the powder formed carbon material that is suitable for using as carbon electrode material uses.And then the granular or Powdered phenolic resin curing thing of record does not contain harmful phenol monomer or low molecule condensation composition in patent documentation 1, has safe characteristics.
At this; Under with aforesaid granular phenolic resins or the situation of its solidfied material as the precursor of organic filler or powder formed carbon material; In order to bring into play performance, must suitably control the shape and the form of this particle as the precursor needs of organic filler or powder formed carbon material.Promptly; For be implemented in high fillibility in the goods, high specific area during as the powder formed carbon material and the low viscosity property during as the water-based slip etc.; Preferably the average grain diameter of (i) particle is enough little, and (ii) must almost not have 2 agglutinators producing owing to the aggegation between the predecessor.In addition, except said (i) and (ii), more preferably (iii) the particle size distribution of particle shape enough narrow and/or (iv) particle approaches spherical shape.And then if consider the fail safe of the goods that are suitable for this granular phenol resin or the fail safe when making, then best (v) the remaining quantity of the phenol monomer (free phenol) in the granular phenol resin still less.At this, described enough little particle diameter is meant if consider granular phenol resin or its solidfied material being suitable in various industrial uses, then must be at least below the 20 μ m, more preferably below the 10 μ m.
But; For granular phenolic resins or its solidfied material; Although carried out a lot of researchs at present, present situation is granular phenol resin or the unknown still of its solidfied material that possesses said characteristic, and the mass-produced manufacturing approach that is suitable for such granular phenol resin or its solidfied material is also unknown.
For example; Synthesis conditions such as amount ratio through rationalizing the formaldehyde, phenol, hydrochloric acid and the aqueous medium that use, temperature conditions in said patent documentation 1, have been put down in writing; Thereby obtain granular or pulverous non-thermofusible phenolic resins, but the non-thermofusible phenolic resins that obtains have (i) initial size more greatly, (ii) because 2 agglutinators that the aggegation of predecessor forms are more, (iii) particle size distribution wide, (iv) contain the point that the particle etc. of the shape beyond the more sphere remains to be improved.
In addition, open in the 2000-239335 communique (patent documentation 2) the spy and to disclose, make after phenol and the formolite reaction, be cured reaction with acid catalyst, the spherical phenolic resin curing thing that obtains thus with base catalyst through in the presence of suspending agent.But the average grain diameter of concrete record is 100～800 μ m in an embodiment.
Open in the presence of at least a and catalyst of having put down in writing in the clear 50-98537 communique (patent documentation 3) in acidic catalyst and base catalyst that contains compound nitrogen series the spy; Make the reaction of phenols and aldehydes; In the initial stage condensation product that obtains, add cellulose-based compound, further continue reaction, spheroidizing thus; Dehydrate afterwards, obtain the granular phenol resin of non-thermofusible.But the average grain diameter of this granular phenol resin is about 700 μ m.In addition, also contain the free phenol of the 6000ppm that has an appointment, so, room for improvement is arranged from the viewpoint of fail safe.
Open in the 2001-114852 communique (patent documentation 4) the spy and to have put down in writing in the presence of condensation catalyst and emulsifying dispersant, at temperature more than 105 ℃ below 200 ℃, pressure 1.3kg/cm 2Above 15kg/cm 2Under the following condition, make phenols and aldehydes carry out condensation reaction, obtain spherical phenolic resins thus.Shown in embodiment, this spherical phenolic resins has the average grain diameter about 2～about 200 μ m.But the problem of existence is, with numerous and diverse program of using pressure cooker (autoclave) to react and so on, because stirring means or mixing speed difference and particle diameter greatly changes.And then think that reactive mode is identical with said patent documentation 3 in itself, the chemical constitution of the phenolic resins that obtains is also identical, so think and contain more free phenol.
Open in the clear 59-6208 communique (patent documentation 5) in the presence of water-soluble high-molecular compound the spy; Use the nitrogen-containing compound catalyst; Make the reaction of phenols and aldehydes; Utilize acidic catalyst, make the dispersion of the spherical phenolic resins of solvable type that obtains take place solidify the spherical phenolic resins that forms and put down in writing.But the average grain diameter of utilizing the spherical phenolic resins that this method obtains is greatly to 350～520 μ m.
Open the manufacturing approach that discloses a kind of spherical resin fine particles in the 2002-226534 communique (patent documentation 6) the spy; It is the method from resorcinol and aldehydes manufacturing spherical resin fine particles; It is characterized in that; Making the resorcinol and the ratio (weight ratio) of water is 1: 5～1: 100, and the pH of reaction system is adjusted to 5～7.Shown in embodiment, this spherical resin fine particles has the average grain diameter of 500nm～2 μ m.But existence can only be used the problem of resorcinol as the phenol source, thereby, think and compare that the carbon residue rate of the phenolic resins that obtains is low with the situation of using other phenols such as phenol.
Open the manufacturing approach of having put down in writing a kind of spherical phenolic resin curing thing in the flat 10-338728 communique (patent documentation 7) the spy; Wherein, From the homogeneous mixed liquor that contains phenolic resins and cellulose derivative and solvent, remove and desolvate; Phenolic resins and cellulose derivative are separated, make phenolic resin curing, remove cellulose derivative from the complex of phenolic resin curing thing and cellulose derivative then.Utilize such method, can obtain having 28nm～the spherical phenolic resin curing thing of the average grain diameter of 5 μ m.But this method has to use the organic solvent to the security presence problem of environment or human body.And then, owing to utilize the reaction that is separated in the solid phase, thus generation extractions of particle needs 21 hours～114 hours such for a long time.
Open the spy and to disclose in the flat 7-18043 communique (patent documentation 8) in the mixed solvent of the water of specified quantitative or water/water Combination organic solvent; In the presence of acid catalyst; The limit concentrates this solvent limit and makes oxybenzene compound and formolite reaction; The reaction of utilization and curing agent is solidified the novolaks spherical particle of separating out, thereby is made the method that spherical P-F is a resin.If utilize this method, then can obtain the spherical phenolic resins of the particle diameter about 9 μ m for example or 15 μ m.But this spherical phenolic resins that utilizes this method to obtain can not satisfy particle size distribution fully.And then, think that reactive mode is identical with said patent documentation 3 in itself, the chemical constitution of the phenolic resins that obtains is also identical, so think and contain more free phenol.
So; Though the past is as the gimmick that obtains the particulate of phenolic resins; Having proposed to use additives such as suspending agent or emulsifying dispersant or the polymerizing condition of phenolic resins etc. rationalized and waited the whole bag of tricks, is phenolic resins particle and the manufacturing approach thereof that 20 μ m are following, be preferably the following nominal particle size of 10 μ m and almost do not have the content of 2 agglutinators, monomer phenols considerably less, have high security but there not be to propose to have average grain diameter.And then, do not propose yet except these characteristic, granular phenol resin and manufacturing approach thereof that the particle size distribution that is shaped as spherical shape, particle of this particle is enough narrow.
Even under the situation of polymerizing condition that for example rationalizes phenolic resins etc.; Polymerizing condition self when making phenols with the aldehydes polymerization and normally used polymerizing condition become and in the phenolic resins that obtains, contain and the high monomer phenols of past same degree in itself under the identical situation.In addition, low whipping speed influences in the manufacturing approach of granular phenol resin of particle diameter and so on, owing to can not continue equably in the stirring reaction container, particle size distribution must broaden.
Usually IC apparatus such as IC (integrated circuit (Integrated Circuit)), memory are made up of semiconductor element, insulating properties supporting substrate, lead frame and lead-in wire etc., for their sealings and joint, use encapsulant or adhesive.The main flow in past is to use the resin combination of inorganic fillers such as containing spherical silicon dioxide, epoxy resin and curing agent as such encapsulant or adhesive.
But, in recent years, for 1) and the electronic component that guarantees of high temperature actions such as the rising of the solder temperature that causes to the transfer of no lead welding of reply and essential vehicle mounted electronic component suitable, require encapsulant or adhesive to have thermal endurance.And then the further miniaturization for the internal wiring of tackling integrated circuit needs the miniaturization of the filler in encapsulant or the adhesive or the lowering viscousity of encapsulant and adhesive, and in cooperation in the past, is difficult to satisfy this two new demand characteristics.
Promptly; As organic epoxy resin and as the spherical silicon dioxide (fused silica) of inorganic matter because coefficient of linear expansion has very big difference; So when following the manufacturing of soldering operation etc. or the heating and cooling in when use; Stress takes place in the interface at epoxy resin and spherical silicon dioxide, thereby the deterioration of generation crackle etc. becomes problem.
The spy open put down in writing in the flat 11-172077 communique (patent documentation 9) for the mechanical property that improves solidfied material encapsulating semiconductor with composition in mating reaction be silane coupling agent in the amino of silica surface.But,, lower so the thermal endurance of encapsulant also depends on the thermal endurance of silane coupling agent because the thermal endurance of silane coupling agent self is low.
As being used to eliminate said interface at epoxy resin and spherical silicon dioxide one of means of stress taking place, has considered inorganic fillers such as replacement spherical silicon dioxide, and used as organic organic filler.This is because through using organic filler, diminishes with the difference of the coefficient of linear expansion of epoxy resin.For example, opening 2000-269247 communique (patent documentation 10), spy the spy opens 2002-226824 communique (patent documentation 11) and spy and opens to have put down in writing in the 2004-168848 communique (patent documentation 12) and can use organic filler as sealing material for semiconductor or adhesive for semiconductor.But, do not mention and possess the said concrete organic filler that requires characteristic.
At this, phenolic resins is the outstanding material of thermal endurance, mechanical property and electrical characteristics, is used as electronic material and various industrial materials such as uses.If can the solidfied material of phenolic resins be used as organic filler, then can give the good characteristic that this phenolic resins has to sealing material for semiconductor or adhesive.
But, propose at present to have high-fire resistance as yet and realized the miniaturization of resin particle simultaneously and become encapsulant or the phenolic resin curing thing of the lowering viscousity during adhesive.In addition; As the organic filler of in sealing material for semiconductor or adhesive for semiconductor, using; Preferred ion property impurity content, especially content of halide ions is little; But phenolic resins is original normally to be used ionic catalyst and is able to polymerization in aqueous medium, so be difficult to obtain ionic impurity content is reduced to the phenolic resin curing thing that goes for semiconductor applications.
Open flat 10-60068 communique (patent documentation 13) the spy, the spy opens in the flat 2-245011 communique (patent documentation 14) and has put down in writing the phenolic resins that utilizes specific carrying out washing treatment to reduce ionic impurity, narrated this phenolic resins and can be used for purposes such as semi-conductive encapsulant.But the phenolic resins of in these documents, putting down in writing is uncured phenolic resins, is not the phenolic resins as organic filler.In addition, can not the washing methods of in these documents, putting down in writing be used for removing the ionic impurity of phenolic resin curing thing.
Patent documentation 1: the spy opens clear 57-177011 communique
Patent documentation 2: the spy opens the 2000-239335 communique
Patent documentation 3: the spy opens clear 50-98537 communique
Patent documentation 4: the spy opens the 2001-114852 communique
Patent documentation 5: the spy opens clear 59-6208 communique
Patent documentation 6: the spy opens the 2002-226534 communique
Patent documentation 7: the spy opens flat 10-338728 communique
Patent documentation 8: the spy opens flat 7-18043 communique
Patent documentation 9: the spy opens flat 11-172077 communique
Patent documentation 10: the spy opens the 2000-269247 communique
Patent documentation 11: the spy opens the 2002-226824 communique
Patent documentation 12: the spy opens the 2004-168848 communique
Patent documentation 13: the spy opens flat 10-60068 communique
Patent documentation 14: the spy opens flat 2-245011 communique
Summary of the invention
The present invention proposes in view of such situation just, and its purpose is to provide granular phenol resin and the manufacturing approach thereof that a kind of average grain diameter is small, do not contain being shaped as spherical shape, having narrow particle size distribution of 2 agglutinators, particle, non-thermofusible that free phenol content is few, safe.
In addition, another object of the present invention is to provide a kind of small, the granular phenol resin and manufacturing approach thereof that when becoming encapsulant or adhesive, can realize the non-thermofusible that lowering viscousity and ionic impurity content reduce of average grain diameter when having high-fire resistance.
Another object of the present invention is to provide a kind of resin combination of the granular phenol resin with non-thermofusible that high-fire resistance and low-viscosity while ionic impurity content reduces and sealing material for semiconductor and the adhesive for semiconductor that uses this resin combination.
The inventor etc. concentrate on studies; The result finds through in the presence of colloid protective agent; In aqueous medium, use the acidic catalyst of high concentration, make the reaction of aldehydes and phenols; Reacting by heating liquid then can obtain having the granular phenol resin of the non-thermofusible of aforesaid good characteristic.
In addition; The inventor etc. also find, in containing the phenol resin composition of granular phenol resin, in order to realize lowering viscousity; Must make the containing ratio of 2 agglutinators that the aggegation between the enough little and particle of the average grain diameter of this granular phenol resin causes little; And, for the ionic impurity that reduces the granular phenol resin solidfied material, content of halide ions especially, as long as wash granular phenolic resin curing thing with alcohols and/or alkaline aqueous solution.That is, the present invention is described below.
Non-thermofusible granular phenol resin of the present invention is characterised in that average grain diameter is below the 20 μ m, and the simple grain rate is more than 0.7.Average grain diameter is preferably below the 10 μ m.Wherein, state the definition that term " non-thermofusible ", " average grain diameter " is reached " simple grain rate " after.
In non-thermofusible granular phenol resin of the present invention, preferably the coefficient of alteration by the particle size distribution of following formula [1] expression is below 0.65.
The coefficient of alteration of particle size distribution=(d 84%-d 16%)/(2 * average grain diameter) [1]
At this, d 84%, d 16%It is respectively the particle diameter of expression cumulative frequency 84%, 16% in the frequency distribution that utilizes the laser diffraction and scattering method to obtain.
In addition, in non-thermofusible granular phenol resin of the present invention, the sphericity of preferred particle is more than 0.5.
And then in non-thermofusible granular phenol resin of the present invention, preferred free phenol content is below the 500ppm.Wherein, state the definition that said term " sphericity " is reached " free phenol content " after.Non-thermofusible granular phenol resin of the present invention more preferably average grain diameter is below the 10 μ m, is below 0.65 by the coefficient of alteration of the particle size distribution of above-mentioned formula [1] expression, and sphericity is more than 0.5, and free phenol content is below the 500ppm.
In addition, in non-thermofusible granular phenol resin of the present invention, preferred chlorinity is below the 500ppm, more preferably below the 100ppm.
In addition; The present invention also provides a kind of manufacturing approach of non-thermofusible granular phenol resin; Wherein, comprising: (1) through the molar concentration in reactant liquor be more than the 2.0mol/L acidic catalyst and colloid protective agent in the presence of, in aqueous medium; Make the reaction of aldehydes and phenols, the granular phenol resin that forms granular phenol resin forms operation; (2) heating contains the reactant liquor of granular phenol resin, thereby forms the non-heat fusing operation of the granular phenol resin of non-thermofusible; (3) from reactant liquor, separate the granular phenol resin of said non-thermofusible and the separating, washing operation of washing.This method can be suitable for as the method for making said non-thermofusible granular phenol resin of the present invention well.
At this, preferred said acidic catalyst is a hydrochloric acid, and said aldehydes is formaldehyde, paraformaldehyde or their mixture.
In addition, the adding mol ratio of the said relatively aldehydes of preferred said phenols is below 0.9.Preferred said colloid protective agent is the water-soluble polysaccharide analog derivative.
In addition, the separating, washing operation also can comprise: use to be selected from the operation that the fluidity medium washs the granular phenol resin of said non-thermofusible more than a kind in alcohols and the alkaline aqueous solution.Like this, can obtain chlorinity is the non-thermofusible granular phenol resin below the 500ppm.
Preferably under the temperature more than the glass transition temperature of the granular phenol resin of said non-thermofusible, used the washing of alcohols.
And then the present invention also provides a kind of compositions of thermosetting resin, and wherein, containing chlorinity is non-thermofusible granular phenol resin of the present invention, epoxy resin and the curing agent below the 500ppm.Compositions of thermosetting resin of the present invention also can further contain inorganic filler.
And then the present invention also provides a kind of sealing material for semiconductor and adhesive for semiconductor that is formed by said compositions of thermosetting resin.
If utilize the present invention, it is promptly to have very small particle diameter below the 20 μ m and contain 2 agglutinators that the aggegation of this small predecessor causes, the granular phenol resin of the non-thermofusible that promptly the simple grain rate is high hardly that average grain diameter then can be provided.Non-thermofusible granular phenol resin of the present invention like this can be used as the additive of the material in the various industrial circles such as moulding material, coating, refractory material, papermaking, high-abrasive material, whetstone, adhesive well, especially can be used as the precursor of functional material with carbon elements such as organic filler or carbon electrode material, activated carbon, molecular-sieve carbon etc.
In addition; If utilize the present invention, it is the granular phenol resin of the non-thermofusible that reduces significantly of 2 agglutinators promptly having very small particle diameter below the 20 μ m and contain hardly that the aggegation of this small predecessor causes and content of halide ions that average grain diameter then can be provided.Non-thermofusible granular phenol resin of the present invention so also can be used as the additive of the material in the various industrial circles well.Especially the granular phenol resin of this non-thermofusible is extremely useful as sealing material for semiconductor and adhesive for semiconductor as the compositions of thermosetting resin of organic filler.
And then the present invention also provides and makes the preferred manufacturing approach of non-thermofusible granular phenol resin institute possess aforesaid outstanding characteristic.If utilize the manufacturing approach of non-thermofusible granular phenol resin of the present invention, the non-thermofusible granular phenol resin that then can utilize easier method manufacturing to have outstanding characteristic, method of the present invention is to be fit to mass-produced method.
Description of drawings
Fig. 1 is the SEM photo of a preference of non-thermofusible granular phenol resin of the present invention.
Fig. 2 is the optical microscope photograph of the non-thermofusible granular phenol resin that in embodiment 2, obtains.
Fig. 3 is the optical microscope photograph of the non-thermofusible granular phenol resin that in embodiment 3, obtains.
Fig. 4 is the optical microscope photograph of the granular phenol resin that in comparative example 1, obtains.
Fig. 5 is the curve chart of the relation between the average grain diameter of concentration (weight (ppm) of the colloid protective agent of relative response liquid total weight) and granular phenol resin of expression colloid protective agent.
Fig. 6 is the scanning electron microscope photo (SEM photo) (500 times) of the granular phenol resin 12A-c that in embodiment 12, obtains.
Fig. 7 is the SEM photo (3500 times) of the further amplification of granular phenol resin 12A-c.
Fig. 8 is the SEM photo of a preference of granular carbon electrode material of the present invention.
Fig. 9 is the optical microscope photograph of the granular carbon electrode material that in reference implementation example 9, obtains.
Figure 10 is the optical microscope photograph of the granular carbon electrode material that in reference implementation example 11, obtains.
Figure 11 is the optical microscope photograph of the granular carbon electrode material that in reference to comparative example 1, obtains.
Figure 12 is the curve chart of the relation between the average grain diameter of concentration (weight (ppm) of the colloid protective agent of relative response liquid total weight) and granular carbon electrode material of expression colloid protective agent.
Figure 13 is the summary sectional view that is illustrated in the electric double layer capacitor of trial-production in the reference implementation example 15.
Figure 14 is the summary ideograph of a preference of expression PSA formula nitrogen generator unit of the present invention.
Figure 15 is the surperficial SEM photo of molecular-sieve carbon that in reference implementation example 18, obtains.
Figure 16 is the summary ideograph of the device of the expression characterization of adsorption that is used to measure molecular-sieve carbon.
Figure 17 is the figure of the relation of the expression purity and the goods nitrogen flow that have used the goods nitrogen in the PSA formula nitrogen generator unit of the different molecular-sieve carbon of yield.
Among the figure, 101a, 101b-adsorption tower, 102-compressor, 103-air dryer, 104-goods groove; 105,106a, 106b, 109a, 113a, 113b, 115a, 115b, 116,305-electromagnetically operated valve, 107a, 107b, 108a, 108b, 110,112,114,117,317-pipe arrangement, 111-pressure regulator, 301-vacuum pump, 302,303,308, the 316-valve; 304,307-pressure gauge, 306-constant pressure valve, 309-gas conditioner, 310-gas bomb, 311-measuring cell; The 312-sample room, 313, the 314-pressure sensor, 315-register, the carbon electrode material of 601-pulpous state; The 602-collector body, 603-dividing plate, 604-distance piece, 605-terminal board.
Embodiment
< non-thermofusible granular phenol resin >
Non-thermofusible granular phenol resin of the present invention is the phenolic resins of the non-thermofusible that forms of the product by phenols and aldehydes, it is characterized in that (term as relative 2 agglutinators is also referred to as predecessor to particle.) average grain diameter be below the 20 μ m, the simple grain rate that becomes to the index of the content of 2 agglutinators is more than 0.7.Like this; Be below the 20 μ m, be preferably below the 10 μ m through the average grain diameter that makes the phenolic resins particle; The simple grain rate is more than 0.7, for example this granular phenol resin is being used as under the situation of organic filler, and filling with higher filling rate becomes possibility; And be filled with being filled thing and being in a ratio of low viscosity in the past of resin combination etc. of this granular phenol resin, handle easily so become.The lowering viscousity of such resin combination meets in recent years the characteristic that requires at the encapsulant of semiconductor applications needs or adhesive.
In addition, granular phenol resin of the present invention can also be well as the for example precursor of functional material with carbon elements such as activated carbon, carbon electrode material, molecular-sieve carbon.Be below the 20 μ m, be preferably below the 10 μ m through the average grain diameter that makes the phenolic resins particle, the simple grain rate is more than 0.7, can improve the space fillibility of utilizing the carbon dust that is fired into significantly.Thereby the granular phenol resin of the application of the invention can improve performance or the surface area of per unit weight of the per unit volume of this functional material with carbon element significantly.And then, have and in the high concentration field, also be low viscous characteristic even will be scattered in the dispersion liquid that forms the fluidity medium such as water for example from the functional material with carbon element that granular phenol resin of the present invention obtains.Have the dispersion liquid of such characteristic and can be well use such as for example making when applying carbon electrode.This non-thermofusible granular phenol resin of the present invention not only can be used for above-mentioned purposes, but also can in the industrial circle of wide regions such as moulding material, coating, refractory material, papermaking, high-abrasive material, whetstone, adhesive, be suitable for.
In addition,, can enumerate the method for the phenolic resins that pulverizing solidified, but in the method, be shaped as unsettingly, can not obtain the good shot-like particle of fillibility as the method in the past of the micropowder that obtains non-thermofusible phenolic resins.
Fig. 1 represent a preference of non-thermofusible granular phenol resin of the present invention the scanning electron microscope photo (below be called the SEM photo.)。As shown in Figure 1, non-thermofusible granular phenol resin of the present invention is the small granular phenol resin of particle diameter, and 2 agglutinators that the aggegation of this particle (predecessor) causes are few.Wherein, the granular phenol resin of Fig. 1 be 5 μ m with undefined average grain diameter, the simple grain rate is 1.0.
Non-thermofusible granular phenol resin of the present invention is elaborated.Non-thermofusible granular phenol resin of the present invention is the phenolic resins of the non-thermofusible that forms of the product by phenols and aldehydes.At this, the product of phenols and aldehydes is the product that utilizes their generation addition reactions and condensation reaction to obtain basically, but comprises that also only the product of addition reaction takes place for some.As phenols, not special qualification, the phenol of can giving an example out, naphthols, quinhydrones, resorcinol, xylenols, pyrogallol etc.Phenols can be a kind, also can make up and use more than 2 kinds.Wherein, if the performance of the phenolic resins that consideration obtains and the balance of cost, then preferred phenols is a phenol.
As aldehydes, not special restriction, the formaldehyde of can giving an example out, paraformaldehyde, glyoxal, benzaldehyde etc.Aldehydes can be a kind, also can make up and use more than 2 kinds.Wherein, aldehydes is preferably formaldehyde, paraformaldehyde or their mixture.
At this; In this manual, " non-thermofusible " is meant that granular phenol resin does not fuse under specific high-temperature pressurizing condition; Particularly; About 5g granular phenol resin sample is inserted between 2 thick corrosion resistant plates of 0.2mm, utilize heat in advance to 100 ℃ forcing press with the total load punching press of 50kg in the time of 2 minutes, do not take place to form the character that is bonded to each other between flat board or distortion of phenolic resins particle or phenolic resins particle because of fusion and/or fusion granular phenol resin.Such character can after utilizing the reaction novolak resin of phenols and aldehydes, give this phenolic resins crosslinking curing through in the manufacturing of granular phenol resin.Crosslinking curing for example can carry out through heating the reactant liquor that has carried out the reaction of phenols and aldehydes.
Non-thermofusible granular phenol resin of the present invention boil the dissolve with methanol degree preferably less than 30%, more preferably less than 20%.In this manual, " boiling the dissolve with methanol degree " is meant the content that boils the solvable composition of methyl alcohol in the granular phenol resin, particularly, is defined as the value of utilizing the test be described below to calculate.That is, the about 10g of precision weighing phenolic resins sample, in the about 500mL of in fact anhydrous methyl alcohol, heating under refluxing in 30 minutes, the glass filter with No.3 filters then, and then with the residue on the absolute methanol cleaning glass filter of about 100mL.Then, with the residue on the glass filter after the washing in 5 hours of 40 ℃ of dryings, this residue of precision weighing then.To utilize the value of calculating with following formula [2] as " boiling the dissolve with methanol degree ".
Boil dissolve with methanol degree (weight %)=(phenolic resins example weight and dried residue weight poor)/(phenolic resins example weight) * 100 [2]
" boiling the dissolve with methanol degree " is not to judge directly whether this phenolic resins has the standard of " non-thermofusible ", and can become an index of the degree of the hot melt of understanding phenolic resins.That is, exist " boiling the dissolve with methanol degree " low more, then the also low more trend of hot melt.If boil the dissolve with methanol degree is more than 30%, then under in use the effect of heating or pressurization sometimes, hot melt is shown, and particle may be out of shape or fuse.
As stated, the average grain diameter that constitutes the particle (predecessor) of non-thermofusible granular phenol resin of the present invention is below the 20 μ m, is preferably below the 10 μ m.Through making average grain diameter is below the 10 μ m, can further improve fillibility or low viscosity property, the low viscosity property when being applicable to dispersion liquid when granular phenol resin of the present invention is applicable to organic filler or functional material with carbon element.At this, in this manual, " average grain diameter " is meant that the assay method that utilize to use laser diffraction formula granulometry machine is cumulative frequency 50% value of the frequency distribution that obtains of laser diffraction and scattering method (Microtrac method).As laser diffraction formula granulometry machine, can use day machine dress (strain) system MicrotracX100 well.
At this, surpass under the situation of 20 μ m in the average grain diameter of non-thermofusible phenolic resins particle, the manufacturing approach chlorinity of the non-thermofusible granular phenol resin of stating after utilizing sometimes of the present invention can not reduce fully.On the basis of this sense, the average grain diameter of non-thermofusible phenolic resins particle is preferably below the 20 μ m, more preferably below the 10 μ m.
In addition, the simple grain rate of non-thermofusible granular phenol resin of the present invention is more than 0.7, to be preferably more than 0.8.The simple grain rate less than 0.7 situation under, fillibility when having the organic filler be applicable to sealing material for semiconductor or adhesive for semiconductor etc. or functional material with carbon element or low viscosity property, the low viscosity property when the being applicable to dispersion liquid inadequate trend that becomes.At this; In this manual; " simple grain " is meant the predecessor that does not form 2 agglutinators because of aggegation, and " simple grain rate " is meant and in water droplet, disperses granular phenol resin, carry out observation by light microscope; In the visual field of selecting at random that contains 300 predecessors of having an appointment, this when the total number of counting predecessor and the number of simple grain is than the total number of simple grain number/predecessor.
In addition, non-thermofusible granular phenol resin of the present invention preferably has narrow particle size distribution.Particularly, the coefficient of alteration of particle size distribution that constitutes the particle (predecessor) of non-thermofusible granular phenol resin of the present invention is preferably below 0.65.The coefficient of alteration of particle size distribution and then be preferably below 0.6.In this manual, " coefficient of alteration of particle size distribution " is the value of utilizing following formula [1] to calculate.
The coefficient of alteration of particle size distribution=(d 84%-d 16%)/(2 * average grain diameter) [1]
At this, in said formula [1], d 84%, d 16%Be respectively the particle diameter of representing cumulative frequency 84%, 16% in the frequency distribution that utilizes the laser diffraction and scattering method to obtain, average grain diameter is the average grain diameter in above-mentioned definition.Become below 0.65 through the coefficient of alteration that makes average grain diameter; The further raising of fillibility and low viscosity property the when organic filler that for example can realize as sealing material for semiconductor or adhesive for semiconductor etc. can be provided or the space fillibility when being applicable to functional material with carbon element, the granular phenol resin that can in the industrial circle of wide regions such as moulding material, coating, refractory material, papermaking, high-abrasive material, whetstone, adhesive, be suitable for simultaneously.As laser diffraction formula granulometry machine, can use day machine dress (strain) system Microtrac X100 well.
In order to improve the performance of sealing material for semiconductor etc., the preferred filling rate that improves the filler of in adhesive resin, filling.As the method for the filling rate that improves Ball-type packing, can enumerate the method that cooperates the different filler of granularity.That is get into the method for littler filler in the closeest filling gap of the filler that, matching design Cheng Zaigeng is big just.For example, used fused silica usually in the past, but, mix fused silica and use with different average grain diameters in order to improve filling rate as the sealing material use filler.When being suitable for such gimmick, must have the average grain diameter that needs, filler with narrow particle size distribution.If utilize the present invention, the organic filler that then can provide the sealing material for semiconductor that goes for such matching design to use.And then; For example in the specific fields such as adhesive that are used for the IC die bonding is used in substrate, even exist average grain diameter little, if but have the filler (being that particle size distribution is wide) of the big trace of particle diameter; Bring harmful effect then can for the thickness of adhesive layer, thereby use the field that becomes difficulty.If utilize the present invention, even the non-thermofusible granular phenol resin that in this field, also can be suitable for well then can be provided.
The shape of particle of non-thermofusible granular phenol resin of the present invention is good more near spherical shape more.Particularly, sphericity is preferably more than 0.5, more preferably more than 0.7, is preferably more than 0.9 especially.Shape of particle is more near spherical shape; Promptly; Sphericity is more near 1.0; The further raising of fillibility and low viscosity property the when organic filler that for example can realize as sealing material for semiconductor or adhesive for semiconductor etc. then can be provided or the space fillibility when being applicable to functional material with carbon element, the granular phenol resin that can in the industrial circle of wide regions such as moulding material, coating, refractory material, papermaking, high-abrasive material, whetstone, adhesive, be suitable for simultaneously.At this; In this manual; " sphericity " is meant in observation by light microscope, selects to contain the visual field of 300 predecessors of having an appointment randomly, selects the minimum predecessor of 10 asperratios (being the ratio of minor axis/major diameter); To these 10 predecessors, the mean value of these 10 asperratios when measuring the asperratio in its projected area respectively.
The free phenol content of non-thermofusible granular phenol resin of the present invention is preferably below the 500ppm.This free phenol content is more preferably below the 300ppm, and then is preferably below the 200ppm.Through making free phenol content is below the 500ppm, the fail safe of the goods in the time of can improving the fail safe when handling phenolic resins and be applicable to this phenolic resins in the various goods.At this, in this manual, " free phenol content " is defined as the value of utilizing the test be described below to calculate.That is, the about 10g of precision weighing phenolic resins sample in the methyl alcohol of 190mL, extracted 30 minutes under refluxing, and filtered with glass filter.Utilize the phenols concentration in the quantitative filtrating of liquid chromatogram, calculate the phenols weight in this filtrating.With the ratio of this phenols weight and example weight is that phenols weight/phenolic resins example weight is as " free phenol content ".
And then the chlorinity of non-thermofusible granular phenol resin of the present invention is preferably below the 500ppm.In semiconductor applications, to the viewpoint of environment or healthy fail safe or the raising of characteristic electron, the viewpoint of the corrosive improvement of fine rule, need the halogenization of electronic material, preferred chlorinity is lower.If chlorinity surpasses 500ppm, then can influence the permittivity of the resin combination that contains non-thermofusible granular phenol resin, becoming causes the corrosion of lead-in wire etc. easily, becomes and satisfies the characteristic that requires as sealing material for semiconductor, adhesive for semiconductor.Chlorinity is preferably below the 100ppm, if be this content, then can be used for sealing material for semiconductor and adhesive for semiconductor better.At this, in this manual, " chlorinity " is the chlorinity of calculating from following assay method.
Determinator: the system fluorescent x-ray analyzer ZSX100E of Co., Ltd. Neo-Confucianism
Assay method: working sample (non-thermofusible phenolic resins particle) and mensuration are pressurizeed with binder powders, become to measure and use particle, use said determinator then, utilize the EZ scan pattern to carry out x-ray fluorescence analysis.That utilizes the phenolic resin curing thing infers molecular formula (C 7H 6O 1) the Alpha-ray diffracted intensity measured value of standardization chlorine K, as chlorinity (wt/wt).Wherein, The determination object that fluorescent X-ray is measured not only comprises chloride ion; The chlorine atom that also comprises organochlorine compound etc., and make under the situation of non-thermofusible phenolic resins in the method for stating after the use of the present invention, owing to do not add organochlorine compound on the original idea; So we can say, utilize fluorescent X-ray to measure the chlorinity that obtains and equate in fact with chloride ion content.
Do not limit the method that is used to make the non-thermofusible granular phenol resin that possesses aforesaid outstanding characteristic is special, but can use the method shown in following well.Below shown in the manufacturing approach of non-meltbility granular phenol resin also be included among the present invention.
< manufacturing approach of non-thermofusible granular phenol resin >
Operation (1)～(3) shown in below the manufacturing approach of non-thermofusible granular phenol resin of the present invention preferably contains.Below each operation is elaborated.
(1) through the molar concentration in reactant liquor be more than the 2.0mol/L acidic catalyst and colloid protective agent in the presence of, in aqueous medium, make the reaction of aldehydes and phenols, the granular phenol resin that forms granular phenol resin forms operation;
(2) heating contains the reactant liquor of said granular phenol resin, thereby forms the non-heat fusing operation of the granular phenol resin of non-thermofusible;
(3) from reactant liquor, separate the granular phenol resin of said non-thermofusible and the separating, washing operation of washing.
(1) granular phenol resin forms operation
In this operation, through in the presence of acidic catalyst and colloid protective agent, in aqueous medium, make the reaction of aldehydes and phenols, form granular phenolic resins.As aldehydes, not special restriction, the formaldehyde of can giving an example out, paraformaldehyde, glyoxal, benzaldehyde etc.Aldehydes can be a kind, also can make up and use more than 2 kinds.Wherein, aldehydes is preferably formaldehyde, paraformaldehyde or their mixture.In addition, of the back, one of characteristic of method of the present invention is; Use the acidic catalyst of high concentration, and under paraformaldehyde the situation as aldehydes of use as the polymer of formaldehyde, under such condition; Paraformaldehyde is by depolymerization, so think that what in fact help to react is formaldehyde.Preferably kind and the use amount thereof with the aldehydes that uses is chosen to when reacting, in aqueous medium, dissolve.
As phenols, not special qualification, the phenol of can giving an example out, naphthols, quinhydrones, resorcinol, xylenols, pyrogallol etc.Phenols can be a kind, also can make up and use more than 2 kinds.Wherein, if consider the dissolubility in water and the performance and the balance of cost of the phenolic resins that obtains, then preferably phenols is a phenol.Preferably kind and the use amount thereof with the phenols that uses is chosen to when reacting, in aqueous medium, dissolve.
Particularly, for example using under the situation as phenols such as phenol, the concentration (weight ratio) that preferably use amount (addition) of phenols is chosen to the phenols of relative response liquid total weight is below the 10 weight %.Under the situation of using the lower phenols of solubility in water (for example naphthols etc.); For guarantee when reaction in the dissolving in the aqueous medium, realize characteristic (small average grain diameter and high simple grain rate etc.) outstanding for granular phenol resin, preferably adopt lower concentration.At this, " reactant liquor total weight " is the total weight of phenols, aldehydes, acidic catalyst, colloid protective agent and aqueous medium.The concentration of the phenols through making relative response liquid total weight is below the 10 weight %, can easily carry out forming from the reaction incipient stage to granular phenol resin the temperature treatment in stage.For example under near the situation that begins the normal temperature to react; If making the concentration of phenols is below the 10 weight %; Then because the excessive heating of not following runaway reaction etc. to cause in initial reaction stage; So almost do not carry out temperature treatment, just can form the granular phenol resin that average grain diameter is little, suppress 2 aggegations.In addition, also can make the concentration (weight ratio) of the phenols of relative response liquid total weight be higher than 10 weight %.In this case, the temperature treatment in the time of must suitably reacting mostly.
In addition, the adding mol ratio that preferably use amount (addition) of said aldehydes is chosen to the phenols of relative aldehydes is below 0.9.Relatively the adding of the phenols of aldehydes is than more preferably below 0.75, and then is preferably below 0.5.The adding mol ratio of the phenols through making relative aldehydes is below 0.9, can form average grain diameter little, suppress 2 aggegations and then more near spherical shape, narrow diameter distribution, the poor granular phenol resin of free phenol.In addition, the adding mol ratio of the phenols through making relative aldehydes is below 0.75, can further suppress 2 aggegations.Better for the characteristic that makes these granular phenol resins, the adding mol ratio that especially preferably makes the phenols of relative aldehydes is below 0.5.Lower limit to the adding mol ratio of the phenols of relative aldehydes; Not special restriction; For example can be through in being dissolved in the scope of aqueous medium, increasing the adding mol ratio that aldehydes reduces the phenols of relative aldehydes; If but the service efficiency of consideration raw material, the then preferred adding mol ratio of the phenols of aldehydes relatively is more than 0.1.
In this operation, aforesaid aldehydes and phenols are reacted in aqueous medium, but one of characteristic of manufacturing approach of the present invention is to use the acidic catalyst of high concentration to carry out this reaction.This acidic catalyst is preferably highly acid catalyst.As such catalyst, the hydrochloric acid of can giving an example out, phosphoric acid, sulfuric acid etc.Wherein, if easy degree of considering to remove or the side reaction when residual, then more preferably hydrochloric acid.In addition, the purposes that the strong acid of fixedness such as phosphoric acid or sulfuric acid also can corresponding granular phenol resin is used fully.In addition, " high concentration " specifically is meant under near the situation that begins the normal temperature to react, and the molar concentration of the acidic catalyst in the reactant liquor is more than the 2.0mol/L, more preferably more than the 3mol/L.Using under the situation of hydrochloric acid as acidic catalyst, " molar concentration of the hydrochloric acid in the reactant liquor " is meant the concentration of the hydrogen chloride in the reactant liquor.In order to obtain the granular phenol resin that average grain diameter is little, suppress 2 aggegations; And then for obtain in addition, more near spherical shape, narrow diameter distribution, the poor granular phenol resin of free phenol; Under near the situation that begins the normal temperature to react, the molar concentration that must make the acidic catalyst in the reactant liquor is more than the 2.0mol/L.In addition, from being suitable for the acid proof viewpoint of industrial reaction speed and attendant equipment, the molar concentration of acidic catalyst is preferably below the 6mol/L.In addition, be higher than normal temperature, and some to be lower than reaction beginning temperature be near the situation the normal temperature for the molar concentration that realizes the necessary acidic catalyst of equivalent responses speed becomes through the beginning temperature that makes reaction.
Another of manufacturing approach of the present invention is characterised in that, in the presence of colloid protective agent, carries out the reaction of aldehydes and phenols.At this, colloid protective agent is the material that helps to form granular phenolic resins.In order to form the granular phenol resin that average grain diameter is little, suppressed 2 aggegations, so for form in addition, more near spherical shape, narrow diameter distribution, the poor granular phenol resin of free phenol, essentially use such colloid protective agent.In the present invention, preferably use water miscible colloid protective agent as colloid protective agent.As water-soluble colloid protective agent, for example can use water miscible polysaccharide derivatives well.If enumerate the concrete example of the water miscible polysaccharide derivatives that can use well, then comprise the alkali metal salts or ammonium salt of carboxymethyl cellulose; It with Arabic gum (gum arabic), Arabic gum (acacia), guar gum (guar gum), carob water-soluble polysaccharide analog derivatives such as (locust bean gum) natural paste of main component etc.Under the situation of the alkali metal salts or ammonium salt that uses carboxymethyl cellulose, do not limit cellulosic carboxy methylation degree is special, the fiber of carboxy methylation degree about 75% have sale, can use well.In addition, obtaining as dried powder under the situation of colloid protective agent, can it directly added in reactant liquor, dissolve, perhaps, also can prepare the aqueous solution of colloid protective agent in advance, it is being added in reactant liquor.
To the not special restriction of the use amount of said colloid protective agent,, be preferably 0.01～3 weight % of the use amount of said phenols with the solid constituent Mass Calculation.Under the situation of use amount less than 0.01 weight % of colloid protective agent, deficiency is so that the average grain diameter of phenolic resins particle is below the 20 μ m, for example also must utilize other parameters such as phenols use amount or mixing speed to control granularity.For the average grain diameter that makes the phenolic resins particle is below the 10 μ m, the use amount of colloid protective agent is preferably more than the 0.04 weight % of use amount of phenols.In addition, under the situation of use amount more than 3 weight % of the use amount of phenols of colloid protective agent because the viscosity of reactant liquor rises, after in the separating, washing operation stated, the trend that exists separating rate to reduce should be noted that.At this; The point that is worth specifying is; In colloid protective agent is said scope, be under the situation of 0.02～1 weight % of use amount of phenols especially in the use amount of colloid protective agent, can control the average grain diameter of phenolic resins particle through the use amount of adjustment colloid protective agent.
As said aqueous medium, can enumerate the mixed solvent of water or water and water-miscible organic solvent, and in the present invention, preferably use aqueous solvent.The concentration that preferably use amount of aqueous medium is chosen to acidic catalyst becomes in the said scope, and then the concentration that preferably use amount of aqueous medium is chosen to phenols becomes in the said preferable range.
Then, the concrete grammar that is used to use described aldehydes, phenols, acidic catalyst and colloid protective agent to react is narrated.As the concrete grammar of reaction, can enumerate 2 following methods.(i) in aqueous medium, mix acidic catalyst, colloid protective agent and aldehydes and prepare mixed liquor, the method that stirs this mixed liquor then and add phenols simultaneously; (ii) colloid mixture protective agent, aldehydes and phenols and prepare mixed liquor in aqueous medium, the method that stirs this mixed liquor then and add acidic catalyst simultaneously.
At this, in said (i) and (ii) any means, all preferred said mixed liquor is the solution of homogeneous roughly.That is the solute that, preferably in aqueous medium, mixes fully dissolves or at least almost entirely dissolving.In the preparation of mixed liquor, to the not special restriction of the order of mixing.In addition, the not special restriction of the temperature the when reaction of this mixed liquor is begun is preferably about 10～50 ℃, and then is preferably about 20～40 ℃.
In said (i) method, stir said mixed liquor limit through the limit and add phenols, carry out the reaction of aldehydes and phenols.The interpolation of phenols can be carried out through directly in mixed liquor, adding phenols, perhaps also can in advance phenols be dissolved in the water, and in mixed liquor, adds this aqueous solution again.The reaction temperature of this reaction preferably is controlled to about 10～60 ℃, more preferably about 20～50 ℃.Reaction temperature less than about 10 ℃ situation under, thickization of particle diameter or the increase of 2 agglutinators if reaction temperature surpasses 60 ℃, then may take place in the trend that exists reaction speed to diminish.In addition; Temperature when beginning through the reaction that makes said mixed liquor is near the normal temperature about 20～30 ℃; The concentration of the phenols of relative response liquid total weight is below the 10 weight %; Owing to do not follow excessive heating,, can react in said preferred temperature range so carry out temperature treatment hardly.
In said (ii) method, stir said mixed liquor limit through the limit and add acidic catalyst, carry out the reaction of aldehydes and phenols.The interpolation of acidic catalyst can once be carried out, and perhaps also can instil with the regular hour and carry out.In addition, the interpolation of acidic catalyst can be carried out (for example using under the situation of hydrochloric acid as acidic catalyst, also can directly adding concentrated hydrochloric acid through directly in mixed liquor, adding acidic catalyst.), perhaps also can dilute with water acidic catalyst (for example concentrated hydrochloric acid), in mixed liquor, add this dilution and carry out.Reaction temperature is identical with the situation of said (i), preferably is controlled to about 10～60 ℃, more preferably about 20～50 ℃.
In said (i) and (ii) any means, along with the reaction progress, reactant liquor is gonorrhoeaization (suspensionizations) little by little, thus the formation granular phenol resin, but such gonorrhoeaization is typically in tens of second after the interpolation of phenols or acidic catalyst～generation after several minutes.Gonorrhoeaization is to have the (ii) method trend shorter than (i) method the needed time of separating out of phenolic resins particle.In addition, after the gonorrhoeaization, reactant liquor typically presents lightpink～deep pink, in the present invention, preferred continues reaction until visible so painted.The time that appears till the gonorrhoea after stain probably is about tens of minutes～several hours.In addition; In the method for in said patent documentation 1, putting down in writing; Become pie for fear of particle assembly; Must, the phenolic resins particle stop to stir after separating out, if but utilize the manufacturing approach of the present invention of using colloid protective agent, even then after the separating out of phenolic resins particle, also can continue to stir.Thereby, if utilize manufacturing approach of the present invention, then can control the temperature of reactant liquor tightlyer, and then can be under the state of homogeneous also in the degree of polymerization and the degree of cross linking of phenolic resins, be provided to next non-thermofusible operation.The homogenieity of the granular phenol resin that this can help finally to obtain.
(2) non-heat fusing operation
In this operation, contain the reactant liquor of said granular phenol resin through heating, make this granular phenol resin become non-thermofusible.The resin that such non-thermofusible also can cause through heating crosslinked, solidify and obtain.The heating-up temperature of the reactant liquor in this operation is preferably more than 60 ℃, more preferably more than 70 ℃.In addition, the heating-up temperature of reactant liquor is preferably below 100 ℃, more preferably below 90 ℃.Heating-up temperature less than 60 ℃ situation under, may not obtain enough non-thermofusibles.Wherein, said enough non-thermofusibles are meant " non-thermofusible " with above-mentioned definition.In addition, under heating-up temperature surpassed 100 ℃ situation, the acid resistance that must have reactor or the attendant equipment etc. of condenser (condenser) sometimes became problem.In addition, even lower in heating-up temperature, to about 60 ℃ situation, also can give enough non-thermofusibles through enough retention times are set.Through with heating-up temperature and be adjusted to said preferable range heating time, can corresponding purposes be adjusted to the desirable degree of polymerization and the degree of cross linking.
As long as can give enough non-thermofusibles heating time to granular phenol resin, not special the qualification, though different and different according to heating-up temperature, typically be several minutes～about several hours.In addition, finish the back in this heat treated, when next operation advances, can reactant liquor be cooled to suitable temperature, perhaps also cooling reaction liquid and directly get into next operation not.
(3) separating, washing operation
In this operation, from the non-thermofusible granular phenol resin that reactant liquor separates and washing obtains.As separation method, for example can use filtration or squeezing etc. well.As the device that is used to carry out such lock out operation, for example can use filter, centrifugal dehydrator, belt press (belt press), filter press (filter press) etc.Decompression is heated up in a steamer, the separation method of spray dryer utilizations such as (spray dryer) evaporation contains the acidic catalyst of high concentration and may damage machine owing to reactant liquor.When utilizing the lock out operation of filtration, also can use various filter aids or agglutinants such as diatomite.Wherein, the proportion of granular phenol resin of the present invention is about 1.2～1.3, carries out sedimentation owing to utilize to leave standstill, so also can before this lock out operation, carry out decant preparatory functions such as (decantation).
Then, the granular phenol resin of washing separation.Utilize this washing operation, reaction almost completely finishes.Concrete grammar as washing; For example can enumerate (i) adds cleaning solution in the phenolic resins filter cake that utilizes said lock out operation to separate method (for example inject cleaning solution in the phenolic resins filter cake on the filter that separates, utilize pressurization or decompression to remove cleaning solution etc.); The phenolic resins filter cake of separation is disperseed in cleaning solution, and then carry out the method for lock out operation.As cleaning solution, can make water well.Through using water washing, can remove the acid ingredient in the phenolic resins filter cake.
In addition,, perhaps replace the said washing operation that utilizes water, it is contacted with the aqueous solution that is alkalescence carry out neutralization reaction as the part of washing operation.Through carrying out neutralization reaction, can remove the acidic catalyst composition that contains in the phenolic resins filter cake effectively.As the aqueous solution that is alkalescence that in neutralization reaction, uses, preferably use the weak alkaline aqueous solution of organic or inorganic.If use alkaline fortified aqueous, then the phenolic resins particle may variable color or dissolving.As weak alkaline aqueous solution, for example can use the dilute aqueous solution of ammonia well.This is because under the situation of the dilute aqueous solution that uses ammonia, because the salt that generates is water-soluble, so possibly utilize washing to remove this salt, ammonia self can utilize heating sublimation to remove.
At this, the chloride ion that permeates in the granular phenol resin in order to utilize reaction, extraction to be separated in, the granular phenol resin that preferably uses the washing of alcohols and/or alkaline aqueous solution to separate.In order to carry out the extract and separate of chloride ion effectively, also can and be used to wash out the washing that utilizes water of the reactant liquor on aforesaid phenolic resins surface, or with in the alkaline aqueous solution and the operation of the surperficial chloride ion of phenolic resins.
As the cleaning solvent (cleaning solution medium) that uses for the extract and separate chloride ion, can be any one of alcohols, alkaline solution, also can use both sides.Utilize the washing of alcohols and/or alkaline aqueous solution, can reduce the chloride ion content in the non-thermofusible granular phenol resin effectively.Particularly, can make the chlorinity in the non-thermofusible granular phenol resin is below the 500ppm, and then it is following or lower also can to make it become 100ppm.
At this, the point that be worth to specify is, the chloride ion content that can utilize the washing of this alcohols and/or alkaline aqueous solution to reduce in the non-thermofusible granular phenol resin is that the simple grain rate is high because the average grain diameter of non-thermofusible granular phenol resin is enough small.That is, under the situation that average grain diameter is big or the simple grain rate is low of non-thermofusible granular phenol resin,, also be difficult to realize the minimizing of chlorinity even utilize the washing of alcohols and/or alkaline aqueous solution.Thereby even from this point, in the present invention, the average grain diameter that also needs non-thermofusible granular phenol resin is below the 20 μ m, and the simple grain rate is more than 0.7.
As the preference of the concrete grammar of the washing that utilizes alcohols and/or alkaline aqueous solution, can enumerate the non-thermofusible granular phenol resin that from reactant liquor, separates is scattered in this cleaning solvent (cleaning solution solvent), stir the method for certain hour.As stated, utilizing before alcohols and/or alkaline aqueous solution wash the non-thermofusible granular phenol resin that preparation washing such as water is separated from reactant liquor.As the method for preparation washing, can enumerate the non-thermofusible granular phenol resin that from reactant liquor, separates for example is scattered in the fluidity medium such as water, stirring method under normal temperature～less than 100 ℃ temperature.The preparation washing is more preferably used and is added hot water.But; Although can utilize this preparation washing to realize the minimizing to a certain degree of chlorinity; But can not only utilize this preparation washing to become below the 500ppm; Perhaps need in order to become below the 500ppm extremely long-time, so, preferably utilize the washing of alcohols and/or alkaline aqueous solution in order to reduce chlorinity fully.
As alcohols, not special restriction for example can be enumerated methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol, isobutanol, sec-butyl alcohol, the tert-butyl alcohol, ethylene glycol, diglycol, triethylene glycol, propane diols etc.Of the back, the glass transition temperature of the non-thermofusible granular phenol resin among the present invention is about about 80～200 ℃, if utilize the extracting operation of alcohols in the zone that surpasses this temperature, then rate of extraction improves significantly.Using lower boiling alcohols under the situation of the extraction of carrying out chlorine component under this preferred temperature province, the essential pressure cooker etc. that uses.In addition, under the situation of using high boiling alcohols, can under normal pressure, carry out said extracting operation under preferred temperature province, but the drying process after the washing (extraction) possibly become hard to tackle.If consider this point, then in illustrative alcohols, the balance of the boiling point of the glass transition temperature of the relative non-thermofusible phenolic resins of ethylene glycol is good, and washing (extraction) operation and drying process are easy, so can preferably use.In addition, alcohols can only use a kind, also can be also with more than 2 kinds.
To the not special restriction of the use amount of alcohols, for example can be relatively from solid constituent 100 weight portions of the non-thermofusible granular phenol resin of reactant liquor separation, be preferably more than 200 weight portions.
Wash temperature in the carrying out washing treatment of use alcohols is preferably more than the glass transition temperature of non-thermofusible granular phenol resin, more preferably surpasses the temperature of glass transition temperature.Through washing with the temperature more than the glass transition temperature, non-thermofusible granular phenol resin becomes rubbery state, so the chlorine component (especially chloride ion) that can in alcohols, contain in this granular phenol resin of extraction effectively.To the not special restriction of the upper limit of wash temperature,, be preferably below 250 ℃ for fear of the thermal decomposition of non-thermofusible granular phenol resin and alcohols.In addition, the glass transition temperature of the non-thermofusible granular phenol resin among the present invention is generally about 80～200 ℃.
The not special restriction of pressure condition when utilizing alcohols to wash can or add to depress under normal pressure and wash.For example,, become more than the glass transition temperature of non-thermofusible granular phenol resin, can wash adding to depress in order to make wash temperature using under the situation of more lower boiling alcohols.In addition, be the not special restriction of mixing time of non-thermofusible granular phenol resin dispersion liquid to washing time, for example can be several minutes～tens of hours.
The washing of said use alcohols can only be carried out 1 time, perhaps in order to become the chlorinity that needs, also can carry out repeatedly repeatedly.
As the alkaline aqueous solution in the washing of using alkaline aqueous solution, not special restriction is preferably weak alkaline aqueous solution.If use alkaline fortified aqueous, then the phenolic resins particle might variable color or dissolving.In addition, the hydroxide aqueous solution of alkali metal or alkaline-earth metal is except above-mentioned, and ion component is non-volatile, even utilize the drying process after the washing, and also might be residual.As weak alkaline aqueous solution, for example can use ammonia spirit, pyridine solution, dimethylamine agueous solution etc. well.Especially ammonia spirit is because chloride ion is removed the ability height, so more preferably.To the not special restriction of the ammonia concentration of ammonia spirit, be preferably the concentration～30 weight % that surpass 0.5 weight %, more preferably 1～25 weight %.In ammonia concentration is under the situation below the 0.5 weight %, effectively the chloride ion in the extraction granular phenol resin in ammonia spirit.In addition, if ammonia concentration surpasses 30 weight %, then the phenolic resins particle might variable color or dissolving.In addition, if ammonia concentration surpasses 30 weight %, then owing to vapour pressure is high, though and different and different according to wash temperature (extraction temperature), essential condenser maybe must use pressure cooker.
To the not special restriction of the use amount of alkaline aqueous solution, depend on the concentration of the alkaline matter that contains, solid constituent 100 weight portions of the non-thermofusible granular phenol resin that for example can from reactant liquor, separate relatively become more than 200 weight portions.
To the not special restriction of the wash temperature in the carrying out washing treatment of using alkaline aqueous solution,, also can from non-thermofusible granular phenol resin, remove chloride ion effectively even be temperature less than the glass transition temperature of non-thermofusible granular phenol resin.Certainly, also can under the temperature more than the glass transition temperature of non-thermofusible granular phenol resin, wash.Through under the temperature more than the glass transition temperature, washing, can more effectively, the short time extract chlorine component mostly.At high temperature use under the situation of washing of ammonia spirit, preferably use pressure cooker etc.To the not special restriction of the upper limit of wash temperature, but, be preferably below 250 ℃ for fear of the thermal decomposition of non-thermofusible granular phenol resin.More preferably below 100 ℃.
The not special restriction of pressure condition when utilizing alkaline aqueous solution to wash can or add to depress under normal pressure and wash.In addition, be the not special restriction of mixing time of non-thermofusible granular phenol resin dispersion liquid to washing time, for example can be several minutes～tens of hours.
The washing of said use alkaline aqueous solution can only be carried out 1 time, perhaps in order to become the chlorinity that needs, also can repeat repeatedly.
In the present invention, in order to reduce chlorinity fully, preferably use the both sides of alcohols and alkaline aqueous solution to wash non-thermofusible granular phenol resin.At this, " using the both sides of alcohols and alkaline aqueous solution " comprises i) mixed liquor that uses alcohols and alkaline aqueous solution is as cleaning solvent; Ii) after using the alcohols washing, use alkaline aqueous solution to wash; And, use alcohols to wash iii) using after alkaline aqueous solution washs.Wherein, preferably ii) reach iii) method, owing to can reduce chlorinity fully, can also remove the employed alkaline matter that derives from alkaline aqueous solution simultaneously, so more preferably iii) method.
In the present invention, preferably after the said washing that utilizes alcohols and/or alkaline aqueous solution, the operation (back washing procedure) that use and alcohols, the different fluidity medium of alkaline aqueous solution wash is set.This fluidity medium does not preferably contain ionic impurity in fact, as such fluidity medium, for example can enumerate pure water, ion exchange water etc.Utilizing should the back washing, can remove the alcohols that is attached on the non-thermofusible granular phenol resin, alkaline aqueous solution, because of the salt of the neutralization reaction generation of alkaline aqueous solution and acidic catalyst etc.Wherein, the granular phenol resin behind the washing procedure of after the washing of having used alcohols and/or alkaline aqueous solution or back and the Separation of Solid and Liquid of cleaning solution can likewise be carried out with said separation circuit.
Can not make the granular phenol resin drying and the use under the state that contains the fluidity medium of having washed, such non-thermofusible granular phenol resin that contains the fluidity medium also belongs to scope of the present invention.The granular phenol resin that for example contains water can be in the inferior use of situation of preparation aqueous dispersions.Perhaps, also drying process can be set after washing procedure.As under the situation of organic filler, preferably carry out drying.As the method for drying, not special the qualification for example can be enumerated the method for the standing and drying machine that uses the canopy type, pneumatic drier, fluid bed dryer etc.Through carrying out drying, can obtain fluidity medium containing ratio and be about the non-thermofusible granular phenol resin powder that good flowability is shown below 5%.If utilize method of the present invention, then can obtain the granular phenol resin of high simple grain rate through carrying out slight fragmentation as required, but also can be when said drying process or use disintegrating machine etc. further to improve the simple grain rate afterwards.
If utilize the manufacturing approach of aforesaid non-thermofusible granular phenol resin of the present invention, to make average grain diameter be below the 20 μ m, be preferably below the 10 μ m especially, the simple grain rate is 0.7 or more, preferably chlorinity is the non-thermofusible granular phenol resin below the 500ppm then can to utilize easier method and utilization to be suitable for mass-produced method.In addition, if utilize manufacturing approach of the present invention, then can make possess these characteristics simultaneously narrow diameter distribution, particle be spherical shape, the considerably less non-thermofusible granular phenol resin of free phenol content, and then can also to make chloride ion content be below the 100ppm.Non-thermofusible granular phenol resin of the present invention so for example can use in semiconductor applications well.
< compositions of thermosetting resin >
Compositions of thermosetting resin of the present invention contains said non-thermofusible granular phenol resin of the present invention, epoxy resin and curing agent.The preferred chlorinity of non-thermofusible granular phenol resin is below the 500ppm.Because this compositions of thermosetting resin contains the especially amount of chloride ions non-thermofusible granular phenol resin of the present invention that is able to reduce of chlorine component; So can give high-fire resistance that phenolic resins has, mechanical property etc., can be used as sealing material for semiconductor and adhesive for semiconductor well.At this, the high-fire resistance of compositions of thermosetting resin not only results from the high-fire resistance that non-thermofusible granular phenol resin himself is had, and forms complex but also result from non-thermofusible granular phenol resin and epoxy resin.That is, utilize the reaction of glycidyl of hydroxyl and the epoxy resin of the phenol skeleton that non-thermofusible granular phenol resin has, non-thermofusible granular phenol resin and epoxy resin form tough complex.Utilize the formation of this complex, the intensity at the interface of non-thermofusible granular phenol resin and epoxy resin increases, so compositions of thermosetting resin of the present invention has excellent in heat resistance.In addition, the difference of the coefficient of linear expansion of non-thermofusible granular phenol resin and epoxy resin is little also is a reason of high-fire resistance.
In compositions of thermosetting resin of the present invention; To as the not special restriction of the use level of the non-thermofusible granular phenol resin of organic filler; For example use under the situation of epoxy resin as adhesive resin; Total amount 100 weight portions of this epoxy resin and its curing agent can be 20～900 weight portions relatively.Under the situation as sealing material for semiconductor or adhesive for semiconductor, total amount 100 weight portions of this epoxy resin and its curing agent are preferably 60～500 weight portions, more preferably 300～400 weight portions relatively.At total amount 100 weight portions of relative this epoxy resin of use level and its curing agent, under situation, exist to be difficult to obtain stable on heating trend of giving effect less than 20 weight portions.In addition, if use level surpasses 900 weight portions,,, be defined to the not purposes of essential compactness mostly so be difficult to obtain dense microstructure then because the phenolic resins powder is a non-thermofusible.In addition, if total amount 100 weight portions of this epoxy resin and its curing agent add the non-thermofusible granular phenol resin of the amount that surpasses 500 weight portions relatively, then can not obtain good flowability as sealing material for semiconductor or adhesive for semiconductor sometimes.
As epoxy resin, can use known in the past epoxy resin, for example can use the epoxy resin of the glycidol ether type of phenol well.If enumerate concrete example, then for example glycidol ether, the glycidol ether of hydrogenation bisphenol A-type, the oxirane of bisphenol A-type (or AD type, S type, the F type) glycidol ether, the expoxy propane that add the adult bisphenol A-type adds the glycidol ether of adult bisphenol A-type, the glycidol ether of phenol novolac resin, the glycidol ether of cresols novolac resin, the glycidol ether of bisphenol-A phenolic varnish gum, the glycidol ether of naphthalene resin, the glycidol ether of 3 functional-type (or 4 functional-type), the glycidol ether of bicyclopentadiene phenolic resins, the glycidic ester of dimeric dibasic acid, the glycidyl amine of 3 functional-type (or 4 functional-type), the glycidyl amine of naphthalene resin etc.They can use separately, also can make up use two or more.
Curing agent is the material that adds in order to make said epoxy resin cure.As hardener for epoxy resin, not special the qualification can be used known in the past hardener for epoxy resin.If enumerate concrete example, then for example phenol system compound, aliphatic amine, cycloaliphatic amines, aromatic series polyamine, polyamide, aliphatic anhydride, alicyclic acid anhydrides, aromatic anhydride, dicyandiamide, organic acid dihydrazide, boron trifluoride amine complex, imidazoles, tertiary amine etc.
To the not special restriction of the use level of curing agent, can be normally used scope in this field, for example relative epoxy resin 100 weight portions can be 5～200 weight portions.Wherein, curing agent adds the weight of the epoxide equivalent that is equivalent to epoxy resin usually, but in the present invention, preferably adds some weight that are equivalent to epoxide equivalent that are less than.This be because, as stated because non-thermofusible granular phenol resin of the present invention is at its surface or the glycidol radical reaction of its near surface and epoxy radicals, so if add the curing agent that epoxide equivalent divides, the curing agent surplus that becomes then.Reduction or leakage harmful effects such as (bleed) that superfluous curing agent can bring hot rerum natura.Because the amount that should reduce depends on the kind of epoxy resin, the use level of non-thermofusible granular phenol resin, the kind of curing agent etc., thus cannot treat different things as the same, but can become the epoxide equivalent that is equivalent to epoxy resin weight about about 5～10%.
Compositions of thermosetting resin of the present invention also can further contain curing accelerator.As curing accelerator; Can use known in the past curing accelerator; For example can enumerate imidazoles, cyanoguanidine derivative, dicarboxyl acid dihydrazide, triphenylphosphine, tetraphenylphosphoniphenolate tetraphenyl borate, 2-ethyl-4-methylimidazole-tetraphenyl borate, 1,8-diazabicyclo [5.4.0] endecatylene-7-tetraphenyl borate etc.To the not special restriction of the use level of curing accelerator, for example relative epoxy resin 100 weight portions can be 0～30 weight portion.
Compositions of thermosetting resin of the present invention also can contain above-mentioned other additives in addition.As other additives, for example can enumerate antifoaming agent, levelling agent, colouring agent, diluent (organic solvent etc.), viscosity modifier, surfactant, light stabilizer, oxidation inhibitor, flame retardant, thermoplastic resin, epoxy resin thermosetting resin in addition etc.In addition, compositions of thermosetting resin of the present invention also can further contain other organic fillers or the inorganic filler beyond the non-thermofusible granular phenol resin of the present invention.As other organic fillers, for example can enumerate carbon, rubber is filler (acrylonitrile butadiene rubber filler, silicone rubber filler etc.) etc.In addition, as inorganic filler, can enumerate metallic stuffings such as silver powder, bronze, copper powder, nickel powder; Silicon dioxide (fused silica, broken silicon dioxide, aerosil (fumed silica) etc.), aluminium oxide, boron nitride, titanium oxide, glass, iron oxide, pottery, calcium silicates, mica etc.
Compositions of thermosetting resin of the present invention can be through using three-roller open mill (triple rollmill), ball mill (ball mill) etc., and mixing, mixing non-thermofusible granular phenol resin, epoxy resin, curing agent and other additives that add as required obtain.
In addition, with compositions of thermosetting resin of the present invention as under the situation of adhesive for semiconductor, the operability raisings when realizing that semiconductor is made etc. also preferably are shaped as film like with compositions of thermosetting resin.As the method for making adhesive film, for example can enumerate the layer of coating compositions of thermosetting resin formation resin combination on base material, make its drying, remove the method for base material then.To the not special restriction of baking temperature, for example can be about 50～200 ℃.
< granular carbon electrode material >
Utilize the present invention, can provide that a kind of to have very small particle diameter, narrow diameter distribution and contain 2 agglutinators that the aggegation of this small predecessor produces hardly be the high granular carbon electrode material of simple grain rate.Granular carbon electrode material of the present invention like this can be realized the raising of the electrostatic capacitance and the power density of per unit area, can be used as electric double layer capacitor, lithium ion battery and lithium-ion capacitor well and use electrode material.
Lithium ion battery is used as negative pole with carbonaceous material usually, and lithium-containing compound as anodal, is moved between positive pole and negative pole through making lithium ion, discharges and recharges.In addition, electric double layer capacitor uses the bigger carbonaceous material of specific area as positive pole and negative pole, utilizes the absorption of electrolyte ion, desorption to discharge and recharge.The lithium-ion capacitor that proposes recently use with the bigger carbonaceous material of the same specific area of common capacitor as positive pole, negative pole uses and the same carbonaceous material of lithium ion battery.Lithium-ion capacitor utilizes the absorption of lithium ion and electrolyte ion, desorption to discharge and recharge, as the novel capacitor of the energy density of having improved electric double layer capacitor and receive publicity.
These lithium ion batteries are in order to make the further high performance of electric double layer capacitor and lithium-ion capacitor, are that the exploitation of the high carbon electrode material of electrostatic capacitance and the power density of per unit area is indispensable to the carbon electrode material of high performance.Past, in order to obtain the carbon electrode material of such high performance, carried out various discussions, for the fillibility that improves per unit area or in order to improve the contact interface area with electrolyte, the little granular carbon material of particle diameter has been proposed.But, all having enough space fillibilities hardly, thereby, in order to obtain the more lithium ion battery of high performance, must further improve carbon electrode material.
Granular carbon electrode material of the present invention is characterised in that average grain diameter is below the 10 μ m, and the simple grain rate is more than 0.7, and is below 0.65 by the coefficient of alteration of the particle size distribution of said formula [1] expression.The sphericity of carbon electrode material particle is preferably more than 0.5.In addition, utilize the present invention, a kind of granular carbon electrode material mixture that the different granular carbon electrode material of the present invention more than 2 kinds of average grain diameter forms that mixes can be provided.
Below granular carbon electrode material of the present invention is elaborated.(term as relative 2 agglutinators is also referred to as predecessor to the particle of granular carbon electrode material of the present invention.) average grain diameter be below the 10 μ m.Through making average grain diameter is below the 10 μ m, and it is big that the external surface area of carbon particle becomes.Like this, lithium ion or the electrolyte ion intrusion frequency in carbon particle increases, and these ions also shorten in the inner diffusion length of granular carbon electrode material, so the turnover of this ion when discharging and recharging accelerates, the result can improve power density.In addition, of the back, through with littler carbon electrode material of suitable ratio combination average particle diameter and bigger carbon electrode material, can improve the packed density of carbon electrode material, like this, can increase the electrostatic capacitance of per unit area.To the not special restriction of the lower limit of average grain diameter, if too small, then when the non-thermofusible phenolic resins particle that the raw material of making as granular carbon electrode material of the present invention preferably uses, the Separation of Solid and Liquid difficulty that becomes sometimes.In addition, if average grain diameter is too small, then using this granular carbon electrode material preparation slip; It is coated with on collector body; Thereby when making the coating electrode, cause of the reduction of this slip sometimes, thereby the reduction of visible surface covered based on the flowability of dilatancy (dilatancy).Thereby from such viewpoint, the average grain diameter of granular carbon electrode material is preferably 0.5 μ m, more preferably more than the 1 μ m.
At this, the meaning of " average grain diameter " of granular carbon electrode material is identical with " average grain diameter " to granular phenol resin of above-mentioned definition.
In addition, granular carbon electrode material of the present invention has narrow particle size distribution, and particularly, the coefficient of alteration of particle size distribution that constitutes the particle (predecessor) of granular carbon electrode material of the present invention is below 0.65.The coefficient of alteration of particle size distribution and then be preferably below 0.6.At this, the meaning of " coefficient of alteration of particle size distribution " is identical with " coefficient of alteration of particle size distribution " to granular phenol resin of above-mentioned definition,, is the value of utilizing said formula [1] to calculate that is.
As stated; Through with littler carbon electrode material of suitable ratio combination average particle diameter and bigger carbon electrode material; Can improve the packed density of carbon electrode material, if but the particle size distribution of these granular carbon electrode materials wide (coefficient of alteration surpasses 0.65) then is difficult to obtain sufficiently high packed density; Thereby, be not enough to improve electrostatic capacitance.
In addition, the simple grain rate of granular carbon electrode material of the present invention is more than 0.7, to be preferably more than 0.8.If less than 0.7, there is agglutinator 2 times in the simple grain rate morely, then generate the gap of predecessor, packed density reduces.Thereby especially under the situation of mixing the different carbon electrode material raising packed density of average grain diameter; Be difficult in the gap of predecessor, fill the littler carbon electrode material of average grain diameter owing to become; So not only can not improve packed density, also have the trend of the flowability reduction of this slip when using electrolyte pulp carbon electrode material on the contrary.At this, the meaning of " the simple grain rate " of granular carbon electrode material is identical with " the simple grain rate " to granular phenol resin of above-mentioned definition.
Fig. 8 represent a preference of granular carbon electrode material of the present invention the scanning electron microscope photo (below be called the SEM photo.)。As shown in Figure 8, granular carbon electrode material of the present invention is the small granular phenol resin of particle diameter, and 2 agglutinators that the aggegation of this particle (predecessor) produces are few, and narrow particle size distribution is shown.Wherein, the average grain diameter of the granular carbon electrode material of Fig. 8 is 4 μ m, and the simple grain rate is 0.98, and the coefficient of alteration of particle size distribution is 0.51.
And then the shape of particle of granular carbon electrode material of the present invention is good more near spherical shape more.Particularly, sphericity is preferably more than 0.5, more preferably more than 0.7, is preferably more than 0.9 especially.Shape of particle is more near spherical shape, and promptly sphericity then can further improve the packed density of granular carbon electrode material more near 1.0, can also further improve the flowability of this slip when using electrolyte pulp carbon electrode material simultaneously.At this, the meaning of " spherical shape " is identical with " spherical shape " to granular phenol resin of above-mentioned definition.
Not special qualification of specific area to the BET method of utilizing nitrogen to adsorb of granular carbon electrode material of the present invention is measured under the situation of the negative material that is used as lithium ion battery or lithium-ion capacitor, is preferably 1～500m 2/ g, more preferably 1～200m 2/ g, and then be preferably 1～50m 2/ g.If specific area surpasses 500m 2/ g, the trend that then exists the ratio of the relative charging capacity of discharge capacity to reduce.In addition, be used as under the situation of electric double layer capacitor with electrode material, specific area is preferably 600～2300m 2/ g, more preferably 800～2000m 2/ g.At specific area less than 600m 2Under the situation of/g, the trend that exists electrolyte ion successfully in pore, not invade is if surpass 2300m 2/ g then becomes the big pore beyond the pore that utilizes in the absorption that is created on electrolyte ion, the desorption, thereby exists the density of electrode material to reduce the trend that can not guarantee enough electrostatic capacitances.
As the raw material of granular carbon electrode material of the present invention, get final product so long as can access carbon electrode material with described specific characteristic, not special restriction can not used known in the past raw material.As this raw material, thermosetting resins such as the phenolic resins of can giving an example out, melmac, carbamide resin, epoxy resin.Granular carbon electrode material of the present invention preferably obtains through the shot-like particle that burns till (carbonization) and/or these resins of activation.In above-mentioned resin, from the point of carbon residue rate, preferred phenolic resins, the above-mentioned non-thermofusible granular phenol resin of the present invention of preferred especially use.
Under with the situation of non-thermofusible granular phenol resin of the present invention as the raw material of granular carbon electrode material, it boils the dissolve with methanol degree preferably less than 30%, more preferably less than 20%.Basically the sphericity and the simple grain rate of granular carbon electrode material controlled in the raw material composition in the time of can utilizing the granular phenol resin that becomes raw material to make or the adjustment of reaction condition; But also can boil the dissolve with methanol degree less than 30% granular phenol resin, improve the sphericity and the simple grain rate of the granular carbon electrode material that obtains through use.
And then the free phenol content that becomes the non-thermofusible granular phenol resin of raw material is preferably below the 500ppm.This free phenol content is more preferably below the 300ppm, and then is preferably below the 200ppm.Through making free phenol content is below the 500ppm, can suppress or avoids following the generation of the fine crack that burns till or the reduction of carbon residue rate, in addition, can also obtain the distribute granular carbon electrode material of sharp-pointed (sharp) of pore diameter after the activation.In addition, because free phenol is harmful to human body or environment,, can provide human body or the safe manufacturing approach of environment through using such granular phenol resin.
At this, granular carbon electrode material of the present invention is being used as under electric double layer capacitor, lithium ion battery and the situation of lithium-ion capacitor with electrode material, also can mix and use the different granular carbon electrode material more than 2 kinds of average grain diameter.If the manufacturing approach of stating after utilizing of the present invention then can be controlled to the average grain diameter of granular carbon electrode material the value that needs, have average grain diameter that needs and the granular carbon electrode material that its particle size distribution is sharp-pointed, the simple grain rate is high so can provide.Wherein, the difference of the expression of " kind " in " more than 2 kinds " average grain diameter.Use the different granular carbon electrode material more than 2 kinds of average grain diameter through mixing, can between the bigger carbon electrode material of average grain diameter, get into the littler carbon electrode material of average grain diameter, so can improve the packed density of carbon electrode material.Under the situation of mixing the different granular carbon electrode material more than 2 kinds of average grain diameter; Its righttest blending ratio depends on the average grain diameter of these carbon electrode materials etc.; So cannot treat different things as the same; The average grain diameters of the preferred corresponding carbon electrode material that mixes etc., the electrostatic capacitance of suitably setting per unit area for becomes the highest.
Obtain under the situation of carbon electrode material mixture at the different granular carbon electrode material more than 2 kinds of mixing average grain diameter, at least a carbon electrode material composition must be carbon electrode material of the present invention.In order to obtain the effect that packed density and power density improve effectively, preferred all carbon electrode material compositions are carbon electrode material of the present invention.That is, the average grain diameter of the whole carbon electrode material compositions through making mixing is below the 10 μ m, can improve effectively as the whole power density of carbon electrode material mixture.In addition; If the particle size distribution of each carbon electrode material composition is sharp-pointed; The space that the particle that then average grain diameter is bigger constitutes becomes roughly certain size is shown; Become and to mix the Mixed Design of more small particle, so can improve easily as the whole fillibility of carbon electrode material mixture with the suitable size that can bury this space.On the other hand; Under the situation of the electrode material composition that mixes the particle diameter wider distribution; The space that the particle that average grain diameter is bigger constitutes becomes and distributes with all size, but is difficult to make the more fine particle of the particle size distribution with the space of burying such all size just.On the contrary, even can obtain having the electrode material composition of the particle size distribution of such complicacy, in order in meeting the space of each particle diameter, to accommodate all particles, essential special married operation, bad situation such as needs are long-time in the time of can mixing.In addition, from the viewpoint that fillibility improves, preferred all carbon electrode material compositions are near spherical shape (sphericity is more than 0.5).
Then, the manufacturing approach to granular carbon electrode material describes.Below shown in the manufacturing approach of granular carbon electrode material of the present invention can be well with acting on the method for making said granular carbon electrode material of the present invention.If utilize method of the present invention, then can utilize the adjustment of the concentration of colloid protective agent to control the average grain diameter of the granular carbon electrode material that obtains.In addition,, then can implement Mechanical Crushing to the phenolic resins that becomes intermediate raw material and carbon electrode material if utilize the present invention, and obtain that average grain diameter is small, narrow diameter distribution and the high carbon electrode material of simple grain rate.
Operation (a)～(d) shown in below the manufacturing approach of granular carbon electrode material of the present invention comprises.
(a) through the molar concentration in reactant liquor be more than the 2.0mol/L acidic catalyst and colloid protective agent in the presence of, in aqueous medium, aldehydes and phenols are reacted, the granular phenol resin that forms granular phenol resin form operation,
(b) heating contains the reactant liquor of said granular phenol resin, thereby the non-heat fusing operation of the granular phenol resin of formation non-thermofusible,
(c) from reactant liquor, separate the granular phenol resin of this non-thermofusible separation circuit,
(d) burn till the firing process of the granular phenol resin of this non-thermofusible.
Below each operation is elaborated, but for operation (a)～(c), because identical,, describe so omit a part with the manufacturing approach of described hot melt granular phenol resin.
Form the acidic catalyst in the operation as granular phenol resin, can preferably use highly acid catalyst such as hydrochloric acid, phosphoric acid, sulfuric acid, more preferably hydrochloric acid.This is because because hydrochloric acid is volatile acid, can utilize drying process easily to remove, so the oxidation reaction of residual acid composition brings dysgenic situation seldom for the surface chemistry or the intensity of granular phenol resin.
Granular phenol resin forms the use amount of the colloid protective agent in the operation with the solid constituent Mass Calculation, be preferably about the 0.04 weight % of use amount of phenols more than.Under the situation of use amount less than 0.04 weight % of colloid protective agent, deficiency is so that the average grain diameter of granular carbon electrode material is 10 μ m, for example must utilize other parameters such as phenols use amount or mixing speed to control granularity.In addition, to the not special restriction of the upper limit of the use amount of colloid protective agent, be preferably below the 3 weight % of use amount of phenols.Under situation more than 3 weight %, can not obtain average grain diameter and be the granular carbon electrode materials below the 10 μ m, and because the rising of the viscosity of reactant liquor, after exist separating rate to reduce in the separation circuit stated etc. trend.
Also can be after separation circuit, the operation of the granular phenol resin that washing separated is set.Concrete grammar as washing; For example can enumerate (i) adds cleaning solution in the phenolic resins filter cake that utilizes said lock out operation to separate method (for example inject cleaning solution in the phenolic resins filter cake on the filter that separates, utilize pressurization or decompression to remove cleaning solution etc.); (ii) in cleaning solution, disperse the phenolic resins filter cake separated, and then carry out the method for lock out operation.As cleaning solution, can make water well.Through using water washing, can remove the acid ingredient in the phenolic resins filter cake.
In addition,, perhaps replace the said washing operation that utilizes water, it is contacted with the aqueous solution that is alkalescence carry out neutralization reaction as the part of washing operation.Through carrying out neutralization reaction, can remove the acidic catalyst that is attached to the granular phenol resin surface effectively and become to grade.As the aqueous solution that is alkalescence that in neutralization reaction, uses, preferably use the weak alkaline aqueous solution of organic or inorganic.If use alkaline fortified aqueous, then the phenolic resins particle may variable color or dissolving.As weak alkaline aqueous solution, for example can use ammonia spirit well.Under the situation of using ammonia spirit, because the salt that generates is water-soluble, so can utilize washing to remove this salt.In addition, the salt residue of trace also can utilize heating sublimation to remove.
Typically, the coefficient of alteration of the particle size distribution of the non-thermofusible granular phenol resin that obtains as described above is below 0.65, and the simple grain rate is more than 0.7.In addition,, can utilize the adjustment of the use amount of colloid protective agent, for example become the value that needs in the scope below the 20 μ m about average grain diameter.In addition, also utilize the firing process and/or the activation procedure of next operation, the average grain diameter what (typically being about 3 one-tenth) have been dwindled particle is so consider this point, the average grain diameter of essential control non-thermofusible granular phenol resin.The characteristic of granular carbon electrode material (average grain diameter, particle size distribution, simple grain rate etc.) is by the characteristic decision as the non-thermofusible granular phenol resin of intermediate raw material.If utilize method of the present invention; Then can the Characteristics Control of non-thermofusible granular phenol resin be become suitable scope, so can obtain well having as electric double layer capacitor, lithium ion battery and lithium-ion capacitor granular carbon electrode material with the characteristic of electrode material ideal.In addition, if utilize said method, then can make the non-thermofusible granular phenol resin of free phenol content considerably less (below the 500ppm).The granular carbon electrode material that uses such non-thermofusible granular phenol resin to obtain has sharp-pointed pore diameter and distributes.
Then, firing process is described.Non-thermofusible granular phenol resin burn till (carbonization) under the non-oxidizing atmosphere of inert gases such as nitrogen, argon, helium, 500～2500 ℃, preferred 500～1200 ℃, more preferably carry out in 550～1000 ℃ the temperature range.After firing process, carry out under the situation of activation processing, firing temperature is become about 900 ℃ can advance activation effectively when following, so preferred.As the device that burns till, for example can use known in the past devices such as electric furnace, external-heat gas furnace.
After firing process, then carry out activation processing as required.The temperature of activation processing is 500～1100 ℃, preferred 800～1000 ℃ and then preferred 850～950 ℃.Be higher than in the temperature of activation processing under 1100 ℃ the situation, the reduction of the carbon residue rate that the oxidation of oxidation, the carbon skeleton on carbon electrode material surface causes etc. takes place sometimes.In addition, be lower than under 500 ℃ the situation, do not utilizing the pore of activation processing to form fully.
Activation processing can be used oxygen, carbon dioxide, steam or the mist more than 2 kinds wherein, or contains the atmosphere gas such as nitrogen, argon, helium of these gases, burning gases such as methane, propane, butane etc.Activation processing preferably becomes activation makes the weight slip of material with carbon element become 5～90%.In addition, be called as in formation under the situation of bigger pore of mesopore (mesopore), also can suitably add metals such as nickel, cobalt, iron or metallic compound and carry out activation processing.And then, also can add the medicine activation of medicines such as potassium hydroxide, zinc chloride.
Directly use non-thermofusible granular phenol resin through said operation (a)～(c) obtain to burn till and/or the situation of activation processing under; The phenolic resins particle waits in firing furnace to be waved in the wind; It is discharged in company with waste gas, and therefore the reduction of yield, the reduction of operability take place sometimes.Under these circumstances, also can be before the firing process with predecessor be a granulated into have appropriateness intensity and the particle of size.In granulation,, can use coal tar, pitch, creasote, liquid phenolic resin, liquid melamine resin, polyvinyl alcohol, starch, crystallinity cellulose powder, methylcellulose etc. as adhesive.They can use separately, also can make up and use more than 2 kinds.
Granulation can be through making at mixers such as using kneader after non-thermofusible granular phenol resin and adhesive mix equably; Use wet type extruding granulator, vertical comminutor, half dry type comminutor (semidry disc pellete), comminutor etc., form shot-like particle and carry out.Be shaped and at room temperature carry out usually, but under pitch becomes to grade more situation, also can under heating, implement.To the not special restriction of the shape of granulation thing, size, for example can become cylindric about diameter 0.5～5mm, long 1～10mm, spherical etc. about diameter 0.1～10mm.In addition; The raising of the operability during with mixing, shaping etc. is a purpose; For example also can add ethylene glycol, PEO, alkyl ether, polyoxyethylene fatty acid ester, gather surfactants such as ammonium carbonate salts; Curing agent such as liquid thermosetting resin, the plasticizer that pastes such as polyvinyl alcohol, extruding pelletization are used etc.The intensity of granulation thing for burn till and/or activation processing during can keep shape to a certain extent and can broken intensity after these processing finish.Fragmentation for example can be used ball mill, vibration mill, go round and round a millstone (rotor mill), hammer crusher, jet pulverizer pulverizer, disintegrating machines such as (jet mill).
< molecular-sieve carbon >
If utilize the present invention, then can be provided in nitrogen generator unit, especially transformation absorption (PressureSwing Adsorption is designated hereinafter simply as PSA.) molecular-sieve carbon that uses well in the formula nitrogen generator unit.
In recent years, as the technology of nitrogen in the separation of air and oxygen, developed transformation absorption (PSA method), by practicability.The PSA method is through sorbing materials such as filling molecular-sieve carbons in the adsorption tower more than 1 tower; Be repeated periodically in the regeneration that adds the selective absorption of depressing and the sorbing materials such as molecular-sieve carbon under decompression or normal pressure, the method for coming the special component in the separate raw materials gas.Think the gas separations of molecular-sieve carbon can result from adsorbed material with the molecular diameter that approaches the pore diameter that molecular-sieve carbon has with have poor than the adsorption rate of each adsorbed material in the specific combined of the adsorbed material of its little molecular diameter.
The PSA nitrogen generator unit that molecular-sieve carbon is used as the air separation of adsorbent is the normal temperature separate mode, because the use amount of nitrogen or the purity of its use are compared with the nitrogen generator unit of cryogenic separation mode; Favourable aspect cost, in industry, be widely used, and in order can more to use in the multipurpose; In addition; Also in order to obtain more cheap nitrogen, need PSA nitrogen generator unit, the high performance of molecular-sieve carbon especially, various molecular-sieve carbons have been proposed in recent years.
But,, still reckon without the width of average grain diameter or its particle size distribution of carbon initial size at present although there is the look-ahead technique of the certain limit of having mentioned the carbon initial size that constitutes particulate molecular sieve carbon.
This be because, though think different and different, summarize to get up according to its particle size distribution, the density of aggregate of carbon predecessor with particle size distribution of wide region uprises easily, the performance of such character pair molecular-sieve carbon is favourable.In addition, the reason that can also enumerate is, is difficult in industry, make molecular-sieve carbon with the particle size range that is controlled at several μ m unit with resin raw material, especially spherical resin raw material; And the spherical resin raw material that will have the particle size range that is controlled at several μ m unit is processed into the particulate molecular sieve carbon about preferred particle diameter 0.5～5mm as adsorbent; Deng.In addition, the reason that can also enumerate is, as raw material; Wait under the situation that reduces particle diameter at the big raw material of powder particle diameter; Owing to can not particle diameter be controlled at several μ units, perhaps, control particle size distribution even can utilize classification to wait; But can not raw material that count μ unit be classified into narrow particle size distribution, so in industry, be difficult to make the particle size distribution of particle diameter raw material of several μ units narrow.
Utilize the present invention, the granulated carbon particle that can provide that particle diameter is small and have narrow particle size range is compared with molecular-sieve carbon in the past, significantly the molecular-sieve carbon of high efficiency as predecessor.
Promptly; Molecular-sieve carbon of the present invention is to have a plurality of carbon predecessors three-dimensionally stack and the structure of zoariumization brokenly; The average grain diameter of this carbon predecessor is below the 10 μ m; And be below 0.65 by the coefficient of alteration of the particle size distribution of the carbon predecessor of following formula [3] expression, particle volume density is the molecular-sieve carbon of 0.7～1.2g/cc.
The coefficient of alteration of the particle size distribution of carbon predecessor=(standard deviation of carbon initial size)/(average grain diameter of carbon predecessor) [3]
Molecular-sieve carbon of the present invention is preferred: use oxygen; 25 ℃, 0.3MPa what add the per unit weight molecular-sieve carbon depressed when carrying out the absorption of single composition is 24～28mg/g from measuring the adsorbance of beginning after 60 seconds; And; Use nitrogen, 25 ℃, 0.3MPa what add the per unit weight molecular-sieve carbon depressed when carrying out single composition absorption is 0.5～5mg/g from measuring the adsorbance of beginning after 10 seconds.In addition, the carbon predecessor is preferably spherical.
Through will this molecular-sieve carbon of the present invention as adsorbent that for example nitrogen generator unit of the PSA mode of separating nitrogen is used from the admixture of gas of oxygen such as air and nitrogen; Can utilize the raising of the nitrogen recovery that the raising of nitrogen gas purity causes, realize the raising of the nitrogen generating capacity of per unit weight molecular-sieve carbon.
Below molecular-sieve carbon of the present invention is elaborated.Molecular-sieve carbon of the present invention typically uses adhesive ingredients etc. material powder is formed; Carrying out the molecular-sieve carbon that carbonization is fired into then, is to have a plurality of carbon predecessors granular carbonization shaping thing of stack and the internal structure that forms of zoariumization brokenly three-dimensionally.To the not special restriction of this coating of particles, for example can be column, spherical equigranular such as cylindric.Under the situation that is cylindrical particle, its diameter and length (highly) are preferably respectively about 0.5～3mm, and under the situation that is granular solid matter, its diameter is preferably about 0.5～3mm.Wherein, the carbon predecessor is meant the small carbon particle of the formation particulate molecular sieve carbon that carbonization obtains as granular phenol resin powder of material powder etc.
The adsorbent that molecular-sieve carbon of the present invention can be used as the nitrogen generator unit of the PSA mode of separating nitrogen from the admixture of gas of oxygen such as air and nitrogen; In addition, can also be in the middle use that separates of the various mists such as purifying of the separating of the separation of perfluorocarbon (perfluorocarbon), methane and carbon dioxide, hydrogen.
The average grain diameter of carbon predecessor is below the 10 μ m, and is below 0.65 by the coefficient of alteration of the particle size distribution of the carbon predecessor of above-mentioned formula [3] expression.The coefficient of alteration of the particle size distribution of carbon predecessor is preferably below 0.6.
Through the average grain diameter that makes the carbon predecessor is below the 10 μ m, can become the separation energy of the oxygen/nitrogen that keeps high and have the high oxygen adsorbance and the molecular-sieve carbon of adsorption rate simultaneously.Think this be because; Form in the operation at pores such as carbonizations; The generating capacity of the thermal decomposition gas of each predecessor tails off, so the fine pore number that forms on carbon predecessor surface increases and particle diameter is little, so adsorbed gas accelerates to the inner diffusion velocity of carbon predecessor.Therefore, for example under the situation of the adsorbent that is used as PSA formula nitrogen generator unit, can improve the nitrogen generating capacity of nitrogen recovery or per unit weight molecular-sieve carbon.To the not special restriction of the lower limit of average grain diameter,, then be preferably more than the 0.5 μ m if consider productivity ratio, the fail safe on the commercial production.In addition, as long as the shape of carbon predecessor does not limit especially, and when 500～1100 ℃ of following heating raws, in order to form the more pore of homogeneous, is preferably spherical for granular.In the present invention, " spherical " may not be spherical shape, and for example cross sectional shape also can be ellipticity etc.But; From form for the pore of homogeneous or commercial production on production stability and the raw material of shaping near the ball point that to be favourable point or the pore carbonization and other processes the thermal decomposition gas when forming further improve to the homogenieity of the diffusion of outside, the shape of carbon predecessor is also good more near spherical shape more.
At this; In the present invention; " average grain diameter of carbon predecessor " is in the observation of scanning electron microscope (below be called SEM) photo, to the molecular-sieve carbon surface and the plane of disruption, selects the visual field respectively randomly; When each visual field is at random selected to confirm as 100 spherical carbon predecessors, utilize the mean value of the particle diameter of these 200 carbon predecessors that the SEM photo measures.In addition, " standard deviation of carbon initial size " is the above-mentioned standard deviation that can confirm as the particle diameter of 200 spherical carbon predecessors.
Molecular-sieve carbon of the present invention is owing to the coefficient of alteration of the particle size distribution of being represented by above-mentioned formula [3] is below 0.65 and the narrow carbon predecessor formation of particle size distribution, so compare with molecular-sieve carbon in the past, the separating power of the mist of oxygen and nitrogen is outstanding.Think this be because, particle diameter narrow through the particle size distribution that makes the carbon predecessor, that reduce between each carbon predecessor is poor, the pore when carbonized stock etc. forms in the operation, the generating capacity of decomposition gas etc. becomes necessarily.Therefore, homogenized between each carbon predecessor at the inner pore that forms of carbon predecessor.Think also that in addition the degree of depth of the pore that the carbon predecessor is had by homogenization, roughly necessarily also is one of reason so the diffusion velocity of adsorbed gas becomes between each carbon predecessor between each carbon predecessor.
In addition, the particle volume density of molecular-sieve carbon of the present invention is 0.7～1.2g/cc, is preferably 0.8～1.15g/cc.Particle volume density can be calculated from the volume and weight of particulate molecular sieve carbon.The carbon containing ratio of molecular-sieve carbon is preferably more than the 80 weight %, more preferably more than the 85 weight %.
It is the function of adsorb oxygen optionally the unstrpped gas that constitutes of oxygen and nitrogen that molecular-sieve carbon of the present invention has from principal component.As its characterization of adsorption, use oxygen, 25 ℃, 0.3MPa (gauge pressure) add the per unit weight molecular-sieve carbon depressed when carrying out single composition absorption be preferably 24～28mg/g from measuring the adsorbance of beginning after 60 seconds.That is, in an optimal way of the present invention, molecular-sieve carbon of the present invention illustrates hyperoxia adsorbance (adsorption rate).In addition, use nitrogen, 25 ℃, 0.3MPa (gauge pressure) add the per unit weight molecular-sieve carbon depressed when carrying out single composition absorption be preferably 0.5～5mg/g from measuring the adsorbance of beginning after 10 seconds, 1.5～5mg/g more preferably.That is, in an optimal way of the present invention, molecular-sieve carbon of the present invention illustrates low nitrogen adsorption rate.If the nitrogen adsorbance in stage (for example between the several seconds) is many in the early stage, the trend that the separation accuracy that then exists oxygen/nitrogen to separate reduces, and through reducing from measuring the adsorbance of beginning after 10 seconds can suppress the reduction of such separation accuracy.Molecular-sieve carbon of the present invention and then preferred oxygen adsorbance after said 60 seconds are that 24～28mg/g and the nitrogen adsorbance after said 10 seconds are 0.5～5mg/g.
Molecular-sieve carbon of the present invention can carry out carbonization after the shaping raw material powder such as adhesive ingredients and burns till and obtain through using.As material powder; As long as the average grain diameter of the carbon predecessor of formation molecular-sieve carbon and the coefficient of alteration of particle size distribution can satisfy said scope; Not special restriction, but preferably use the described non-thermofusible granular phenol resin of the present invention of having controlled the coefficient of alteration of particle diameter and particle size distribution.
As material powder, under the situation of the granular phenol resin of use non-thermofusible, it boils the dissolve with methanol degree preferably less than 30%, more preferably less than 20%, and then preferably less than 10%.Boiling the dissolve with methanol degree also can be for more than 30%, but " non-thermofusible " in this case, is not shown sometimes.
In addition, as material powder, the also preferred granular phenol resin that uses hot melt.In this case, it boils the dissolve with methanol degree preferably less than 50%." boiling the dissolve with methanol degree " can become 1 index of the degree of the hot melt of understanding granular phenol resin.That is, exist " boiling the dissolve with methanol degree " low more, then the also low more trend of hot melt.If boiling the dissolve with methanol degree becomes more than 30%; Then under in use the effect of heating or pressurization, hot melt is shown, particle may be out of shape or fuse; If become more than 50% but boil the dissolve with methanol degree; Significant hot melt then is shown, particles Deformation, fusion during owing to carbonization, and the pore obturation that possibly not form pore fully in inside or form.Said " boiling the dissolve with methanol degree " is meant boils the dissolve with methanol degree by above-mentioned formula [2] expression.
At this, the definition of " non-thermofusible " as stated.In addition; " hot melt " is defined by about 5g granular phenol resin sample inserted between 2 thick corrosion resistant plates of 0.2mm; Utilize heat in advance to 100 ℃ forcing press with the total load punching press of 50kg in the time of 2 minutes, the granular phenol resin fusion, particularly; Under above-mentioned high-temperature pressurizing condition, because fusion and/or fusion and granular phenol resin forms dull and stereotyped character.Illustrate by the granular phenol resin of " hot melt " of definition in this wise and under for example about temperature more than 120 ℃ thermosetting is shown being higher than under 100 ℃ the temperature." thermosetting " is meant gelation in gel time (gel time) test at 180 ℃.
(term as relative 2 agglutinators is also referred to as predecessor to the particle of formation non-thermofusible or hot melt granular phenol resin.) average grain diameter be preferably below the 12 μ m.As raw material, be the granular phenol resin below the 12 μ m through using average grain diameter, can form average grain diameter is the carbon predecessor below the 10 μ m.At this, for the definition of " average grain diameter " of non-thermofusible and hot melt granular phenol resin, identical with the definition of " average grain diameter " of described non-thermofusible granular phenol resin.
The non-thermofusible or the hot melt granular phenol resin that use in the present invention have narrow particle size distribution, and particularly, formation is preferably below 0.65 by the coefficient of alteration of the particle size distribution of the particle (predecessor) of the granular phenol resin of above-mentioned formula [1] definition.The coefficient of alteration of particle size distribution is more preferably below 0.6.
Through making the coefficient of alteration by the particle size distribution of above-mentioned formula [1] expression is below 0.65, and the coefficient of alteration of the particle size distribution of carbon predecessor is become below 0.65, and the result can obtain the outstanding molecular-sieve carbon of separation energy of mist.Wherein, The coefficient of alteration of carbon predecessor is different with the condition determination of the coefficient of alteration of granular phenol resin; If but the coefficient of alteration that uses above-mentioned formula [1] is the granular phenol resin below 0.65, then can confirm to constitute coefficient of alteration that the carbon predecessor of the molecular-sieve carbon that obtains satisfies above-mentioned formula [3] below 0.65.
The simple grain rate of non-thermofusible or hot melt granular phenol resin is preferably more than 0.7, more preferably more than 0.8.The simple grain rate less than 0.7 situation under, the gas of the thermal decomposition when the utilizing carbonization treatment heterogeneity that becomes is utilized the heterogeneities that also become such as shape and distribution of the pore that thermal decomposition forms, result, the trend that exists the separating power of mist to reduce.The definition that " simple grain " reaches " simple grain rate " as stated.
The shape of particle of non-thermofusible or hot melt granular phenol resin is good more near spherical shape more.Particularly, sphericity is preferably more than 0.5, more preferably more than 0.7, is preferably more than 0.9 especially.Shape of particle more near spherical shape be sphericity more near 1.0, then can improve more to the density of the particulate molecular sieve carbon that the homogeneous mixture forms, carbonization obtains of adhesive ingredients etc.In addition, can also make the generation of thermal decomposition gas when utilizing carbonization treatment and the shape and the more homogeneous that distributes of the pore that forms, so can further improve the separation energy of mist.The definition of " sphericity " as stated.
And then the free phenol content of non-thermofusible or hot melt granular phenol resin is preferably below the 1000ppm.This free phenol content is more preferably below the 500ppm, and then is preferably below the 400ppm.Through making the content as the free phenol of harmful components is below the 1000ppm, the fail safe in the time of can improving granular phenol resin and handle.The definition of " free phenol content " as stated.
Then, the manufacturing approach to the granular phenol resin of the described raw material that is preferably used as molecular-sieve carbon of the present invention describes.For non-thermofusible granular phenol resin, can use described method of the present invention to make well.At this moment, the use amount of colloid protective agent is with the solid constituent Mass Calculation, is preferably more than about 0.05 weight % of use amount of said phenols.Under the situation of use amount less than about 0.05 weight % of colloid protective agent, deficiency for example must utilize other parameters such as phenols use amount or mixing speed to control granularity so that the average grain diameter of granular phenol resin is below the 12 μ m.To the not special restriction of the upper limit of the use amount of colloid protective agent, for example be below the 3 weight % of use amount of phenols.Under situation more than 3 weight %, exist because the viscosity of reactant liquor rises after the trend of separating rate reduction in the separation circuit stated etc.
The hot melt granular phenol resin can obtain through in the manufacturing approach of said non-thermofusible granular phenol resin of the present invention, omitting non-heat fusing operation.For the separating, washing operation, identical with non-thermofusible granular phenol resin.
Non-thermofusible that has been washed or hot melt granular phenol resin also can not make its drying and under moisture state, directly be used as the raw material of molecular-sieve carbon, but preferably make its drying.
Then, the manufacturing approach to molecular-sieve carbon of the present invention describes.Method of the present invention can be applicable to well makes said molecular-sieve carbon of the present invention.The manufacturing approach of molecular-sieve carbon of the present invention comprises following operation.
(i) to contain average grain diameter be below the 12 μ m and the coefficient of alteration of particle size distribution is the operation that the homogeneous mixture of granular phenol resin and adhesive ingredients below 0.65 forms the thing that obtains being shaped; And
(ii) under non-oxidizing atmosphere, heating should the shaping thing under the temperature of 500～1100 ℃ scopes, obtains the operation of the shaping thing of carbonization thus.
(i) forming process
In this operation; Be below the 12 μ m to average grain diameter and the coefficient of alteration of particle size distribution is after the granular phenol resin, adhesive ingredients below 0.65 and other uniform component ground of adding as required mix; Form, thereby obtain graininess shaping thing.For granular phenol resin, as stated, more preferably possess simple grain rate more than 0.7, sphericity more than 0.5 and the granular phenol resin below the free phenol content 1000ppm.
As adhesive ingredients, can enumerate polyvinyl alcohol, water-soluble or water-swellable cellulose derivative, coal tar oils etc.If enumerate concrete example water-soluble or the water-swellable cellulose derivative, then comprise methylcellulose, carboxymethyl cellulose, hydroxypropyl cellulose etc.In addition, as coal tar oils, can enumerate coal tar, coal tar asphalt, creasote and the mixture more than 2 kinds wherein.In addition, as other adhesive ingredients, also can add thermosetting resins such as phenolic resins or melmac.
Relative granular phenol resin 100 weight portions of the addition of adhesive ingredients are preferably about 1～50 weight portion, more preferably 1～30 weight portion.
In addition, adhesive ingredients also can use for example starch, its derivative or its modification body.These compositions of starch etc. can be well form material as pore, and to form pore relevant in thermal decomposition when under non-oxidizing atmosphere, carrying out carbonization.If enumerate the concrete example of starch etc., for example starch such as farina, cornstarch; Starch derivatives such as esterification starch, etherification starch, crosslinked starch; Modified starches such as enzyme modification dextrin etc.Relative granular phenol resin 100 weight portions of the addition of starch, its derivative or its modification body are preferably about 1～50 weight portion, more preferably 1～30 weight portion.
In addition, sieve in the scope of the characteristic of carbon, in order to improve operability, for example can add ethylene glycol, polyethylene oxide alkyl ethers, polyoxyethylene fatty acid ester on a small quantity, gather surfactants such as ammonium carbonate salts saboteur not; Curing agent such as liquid thermosetting resin; Crosslinking agents such as polyvinyl alcohol; The plasticizer that extruding pelletization is used; The cocoanut shell micropowder; The coal micropowder; Other synthetic resin etc.
When preparation homogeneous mixture, for example can use ribbon mixer, V-Mixer, cone-type mixer (cone mixer), kneader etc.In addition, as the homogeneous mixture is configured as granular method, can use prilling process such as extruding pelletization, rotation granulation, compression granulation.To the shape of graininess shaping thing, not special restriction for example can be column, spherical equigranular such as cylindric.Under the situation that is cylindrical particle, its diameter and length (highly) are preferably respectively about 0.5～3mm, and under the situation that is granular solid matter, its diameter is preferably about 0.5～3mm.
(ii) carbonation process
In this operation,, obtain the shaping thing of carbonization through the said graininess shaping thing of heating under non-oxidizing atmosphere, under the temperature of 500～1100 ℃ scope.Temperature during carbonization is preferably 650～850 ℃.Carburizing temperature less than 500 ℃ situation under; Do not have sufficient adsorption capacity, existence can only obtain lacking the trend of the carbide of selecting adsorptivity, is being higher than under 1100 ℃ the situation; The pore of the carbide that obtains shrinks, and has the trend that is difficult to obtain enough adsorption capacities.For example can be 1～24 hour heating time, is preferably 1～12 hour.As the gas that is used under non-oxidizing atmosphere, using, can enumerate nitrogen, argon etc.
As the heating furnace that is used for carbonization treatment, can use the formula of leaving standstill, flow-type, heating furnace such as rotary, but preferably use revolving rotary furnace (rotary kiln).
After said carbonization treatment,, also can under temperature below 500 ℃ or the temperature below 1100 ℃, implement heat treatment once more in order to adjust the characteristic of molecular-sieve carbon.In addition, the graininess shaping thing that also can utilize said carbonization treatment to obtain through pulverizing mixes with adhesive ingredients etc., granulation once more, and then implements heat treatment, adjusts the characteristic of molecular-sieve carbon.
Molecular-sieve carbon of the present invention can be used as the adsorbent of nitrogen generator unit well.As nitrogen generator unit; Can enumerate in being filled with the adsorption tower of molecular-sieve carbon of the present invention; For example supply with the unstrpped gas that principal component is oxygen and nitrogen, in adsorption tower, repeat the nitrogen generator unit of the PSA mode separation of nitrogen of high pressure absorption process and low pressure regeneration operation.The molecular-sieve carbon of the application of the invention is compared with nitrogen generator unit in the past, can utilize the raising of the nitrogen recovery that the raising of nitrogen gas purity causes, improves the nitrogen generating capacity of per unit weight molecular-sieve carbon.Below be that example is explained nitrogen generator unit of the present invention with PSA formula nitrogen generator unit.
Figure 14 is the summary ideograph of a preference of expression PSA formula nitrogen generator unit of the present invention.PSA formula nitrogen generator unit shown in Figure 14 comprises following structure, is filled with the 2 adsorption tower 101a and the 101b of molecular-sieve carbon of the present invention that is:; The unstrpped gas supply unit that constitutes by compressor 102 and air dryer 103 etc.; The goods groove 104 of the nitrogen that deposit separates; Be used to link the pipe arrangement of these inscapes; The electromagnetically operated valve that flows and its control system that are used for control gaseous; Flow-rate adjustment is taken into account the analysis meter of gas concentration etc.
Operation method to PSA formula nitrogen generator unit shown in Figure 14 describes.Wherein, following operation method is only represented an example, does not limit the present invention fully.At first, in the high pressure absorption process of adsorption tower 101a, the unstrpped gas of utilizing compressor 102 compression is by air dryer 103 dryings, via electromagnetically operated valve 105 and electromagnetically operated valve 106a, pipe arrangement 107a, supplies with to adsorption tower 101a then.At this, the principal component of the unstrpped gas of supply is oxygen and nitrogen (for example air), utilizes compressor 102 to be forced into preferred 3～10kgf/cm 2About G.
The molecular-sieve carbon that oxygen is adsorbed in the tower 101a optionally absorbs, temporarily be stored in the goods groove 104 by the nitrogen that concentrates through pipe arrangement 108a, electromagnetically operated valve 109a and pipe arrangement 110 after, be used as goods through pressure regulator 111, pipe arrangement 112 again and take out.Then, after adsorption time, close electromagnetically operated valve 106a and electromagnetically operated valve 109a through regulation.
In the low pressure regeneration operation of adsorption tower 101a; Open electromagnetically operated valve 113a; The unstrpped gas that is full of in the adsorption tower 101a under being in pressurized state is discharged into the atmosphere through pipe arrangement 114, and the interior pressure of adsorption tower 101a is reduced near the atmospheric pressure apace, makes molecular-sieve carbon regeneration.And then, open electromagnetically operated valve 115a and electromagnetically operated valve 116, the nitrogen in the goods groove 104 is circulated through pipe arrangement 117 to adsorption tower flow direction (with nitrogen removing direction rightabout), carry out the regeneration of adsorption tower 101a thus.If this step for regeneration finishes, then close electromagnetically operated valve 113a, electromagnetically operated valve 115a and electromagnetically operated valve 116, carry out pressure process as required, and then carry out the high pressure absorption process.Of the back, through repeating absorption process and step for regeneration, can successfully carry out the regeneration of the molecular-sieve carbon in the adsorption tower, can take out highly purified nitrogen simultaneously.Wherein, said operation method is that the situation of using 1 adsorption tower is illustrated, and under the situation of using 2 adsorption towers, uses 2 adsorption towers alternately to carry out the circulation of absorption process-step for regeneration.
In described operation method, also can add pressure process and reflow process, for example operate with the circulation of absorption process-pressure process-step for regeneration-pressure process-reflow process-absorption process and so on.Pressure process is meant and using under the situation of 2 above adsorption towers, and the adsorption tower of the adsorption tower of the high pressure absorption process that is through with and the low pressure regeneration operation that is through with carries out the operation of the pressure equalization of pressure in the adsorption tower.For example under for the situation of nitrogen generator unit of utilizing 2 adsorption towers; The situation on the top that only links 2 adsorption towers is called all pressures; The situation that only links the bottom is called down all pressures, is called up and down all pressures linking the situation that reaches the both sides between the bottom between the top.
Reflow process is meant that the part of nitrogen gets back in the adsorption tower from the goods groove, and this nitrogen is not discharged outside system and stayed in the adsorption tower, thereby makes the nitrogen that in absorption process, the takes out high concentration easy operation that becomes.
Below enumerate embodiment and illustrate in greater detail the present invention, but the present invention is not limited to these.
[preparation of non-thermofusible granular phenol resin]
< embodiment 1 >
Use 35 weight % hydrochloric acid and 36 weight % formalins; The preparation concentration of formaldehyde is that 10 weight % and concentration of hydrochloric acid are the mixed solution 2000g of 16 weight %; In this mixed solution, add 2 weight % aqueous solution 8g of sanlose then, stir into uniform solution.Then, the temperature of this uniform solution is adjusted to 20 ℃, adds 30 ℃ 95 weight % phenol 70g then while stirring.Wherein, the concentration of the phenols of relative response liquid total weight is 3.2 weight %, and the adding mol ratio of the phenol of phase PARA FORMALDEHYDE PRILLS(91,95) is 0.11, and the molar concentration of the hydrochloric acid in the reactant liquor is 4.7mol/L.When adding phenol and begin about 120 seconds, the reactant liquor gonorrhoeaization.After gonorrhoeaization, reduce mixing speed and proceed reaction, the result is after about 30 minutes after phenol adds, and reactant liquor is coloured to lightpink.At this moment, the temperature of reactant liquor reaches 30 ℃.After reactant liquor is painted, utilize external heat, reactant liquor is heated to 80 ℃, under this temperature, kept 30 minutes.Then, filter this reactant liquor, the filter cake with the water washing of 500g obtains makes in its 0.5 weight % ammonia spirit that is suspended in 500g then, under 40 ℃, carries out 1 hour neutralization reaction.After the neutralization reaction, use aspirator to attract to filter this suspension,, utilize 50 ℃ drying machine to make its dry 10 hours, obtain the lurid granular phenol resin 1A of 80g thus with the water washing of 500g.
< embodiment 2 >
Making the concentration of formaldehyde in the mixed liquor is that 18 weight %, concentration of hydrochloric acid are 18 weight %, in addition, likewise reacts with embodiment 1, obtains granular phenol resin 2A.Wherein, the concentration of the phenols of relative response liquid total weight is 3.2 weight %, and the adding mol ratio of the phenol of phase PARA FORMALDEHYDE PRILLS(91,95) is 0.06, and the molar concentration of the hydrochloric acid in the reactant liquor is 5.3mol/L.The gonorrhoeaization of reactant liquor is taking place after adding phenol to begin to count about 150 seconds, does not also have operational problems such as resin adhering on wall.The optical microscope photograph of the granular phenol resin that Fig. 2 representes to obtain in the present embodiment.
< embodiment 3 >
Making the concentration of formaldehyde in the mixed liquor is that 7 weight %, concentration of hydrochloric acid are 20 weight %, in addition, likewise reacts with embodiment 1, obtains granular phenol resin 3A.Wherein, the concentration of the phenols of relative response liquid total weight is 3.2 weight %, and the adding mol ratio of the phenol of phase PARA FORMALDEHYDE PRILLS(91,95) is 0.15, and the molar concentration of the hydrochloric acid in the reactant liquor is 5.9mol/L.The gonorrhoeaization of reactant liquor is taking place after adding phenol to begin about 30 seconds, does not also have operational problems such as resin adhering on wall.The optical microscope photograph of the granular phenol resin that Fig. 3 representes to obtain in the present embodiment.
< embodiment 4 >
Add 95 weight % phenol 52g, in addition, likewise react, obtain 62g granular phenol resin 4A with embodiment 1.Wherein, the concentration of the phenols of relative response liquid total weight is 2.4 weight %, and the adding mol ratio of the phenol of phase PARA FORMALDEHYDE PRILLS(91,95) is 0.08, and the molar concentration of the hydrochloric acid in the reactant liquor is 6.0mol/L.
< embodiment 5 >
Add 95 weight % phenol 105g, in addition, likewise react, obtain 115g granular phenol resin 5A with embodiment 1.Wherein, the concentration of the phenols of relative response liquid total weight is 4.7 weight %, and the adding mol ratio of the phenol of phase PARA FORMALDEHYDE PRILLS(91,95) is 0.16, and the molar concentration of the hydrochloric acid in the reactant liquor is 5.8mol/L.
< embodiment 6 >
Mix 36 weight % formalin 556g and 95 weight % phenol 70g and water 530g, preparation mixed solution 1156g, 2 weight % aqueous solution 8g of interpolation sanlose in this mixed solution stir into uniform solution then.Then, the temperature of this uniform solution is adjusted to 20 ℃, adds 30 ℃ 35 weight % hydrochloric acid 914g then while stirring.Wherein, the concentration of the phenols of relative response liquid total weight is 3.2 weight %, and the adding mol ratio of the phenol of phase PARA FORMALDEHYDE PRILLS(91,95) is 0.11, and the molar concentration of the hydrochloric acid in the reactant liquor is 4.7mol/L, and is identical with embodiment 1.When adding hydrochloric acid and begin about 20 seconds, the reactant liquor gonorrhoeaization.After gonorrhoeaization, still continue reaction, the result is after interpolation hydrochloric acid begins about 30 minutes, and reactant liquor is coloured to pink colour.Then, likewise carry out, heat, separate, wash and drying, obtain 78g granular phenol resin 6A thus with embodiment 1.
< embodiment 7 >
Add 95 weight % phenol 204g, in addition, likewise react, obtain 240g granular phenol resin 7A with embodiment 6.Wherein, the concentration of the phenols of relative response liquid total weight is 8.8 weight %, and the adding mol ratio of the phenol of phase PARA FORMALDEHYDE PRILLS(91,95) is 0.31, and the molar concentration of the hydrochloric acid in the reactant liquor is 4.4mol/L.
< embodiment 8 >
In the preparation of mixed liquor, use 36 weight % formalin 278g, 95 weight % phenol 204g and water 803g, in addition, likewise react, obtain 200g granular phenol resin 8A with embodiment 6.Wherein, the concentration of the phenols of relative response liquid total weight is 8.8 weight %, and the adding mol ratio of the phenol of phase PARA FORMALDEHYDE PRILLS(91,95) is 0.62, and the molar concentration of the hydrochloric acid in the reactant liquor is 4.4mol/L.
< embodiment 9 >
Replace 36 weight % formalins, use the paraformaldehyde aqueous solution of identical weight concentration, in addition, likewise react with embodiment 1.Process and the embodiment 1 of reaction obtain the granular phenol resin 9A of 77g much at one.
< embodiment 10 >
Making the concentration of hydrochloric acid in the mixed solution is 8 weight %, and after adding 95 weight % phenol, utilizes external heat; Reactant liquor is warming up to 50 ℃, after reactant liquor is painted, is heated to 80 ℃, in addition; Likewise react with embodiment 1, obtain granular phenol resin 10A.The concentration of the phenols of relative response liquid total weight is 3.2 weight %, and the adding mol ratio of the phenol of phase PARA FORMALDEHYDE PRILLS(91,95) is 0.11, and the molar concentration of the hydrochloric acid in the reactant liquor is 2.3mol/L.
< comparative example 1 >
The 2 weight % aqueous solution 8g that replace sanlose use 8g water, in addition, likewise react with embodiment 1, obtain 80g granular phenol resin 1C.The process of reaction except add phenol begin about 95 seconds after the reactant liquor generation gonorrhoea, identical with embodiment 1.Fig. 4 is illustrated in the optical microscope photograph of the granular phenol resin that obtains in this comparative example.For granular phenol resin 1C, as shown in Figure 4, can know the aggegation that more predecessor has taken place.The simple grain rate of granular phenol resin 1C is 0.60.
< comparative example 2 >
Making the concentration of hydrochloric acid among the mixed solution 2000g is 5 weight %, in addition, likewise reacts with embodiment 1.Do not see the gonorrhoea of reactant liquor, can not obtain granular phenol resin.Wherein, the molar concentration of the hydrochloric acid in the reactant liquor is 1.5mol/L.
< comparative example 3 >
In the preparation of mixed liquor, use 36 weight % formalin 140g, 95 weight % phenol 204g and water 940g, in addition, likewise react with embodiment 6.The concentration of the phenols of relative response liquid total weight is 8.8 weight %, and the adding mol ratio of the phenol of phase PARA FORMALDEHYDE PRILLS(91,95) is 1.23, and the molar concentration of the hydrochloric acid in the reactant liquor is 4.5mol/L.If resin is then adhered in the heating of beginning reactant liquor on reactor wall.When heating finishes, leach the powder that is in suspended state, washing, neutralization, drying obtain the granular phenol resin 3C of about 50g.Utilize the microscopic examination particle, there are a lot of atypic particles in the result, can not try to achieve sphericity, simple grain rate.
To granular phenol resin 1A～10A, 1C and 3C, measure the various characteristics shown in the table 1.To measure the result and be shown in table 1 with reaction condition.
Figure G2009101734092D00471
< embodiment 11 >
To carry out various changes as the sanlose phase Pyrogentisinic Acid's of colloid protective agent amount, in addition, likewise react, obtain granular phenol resin, measure the average grain diameter of each granular phenol resin then with embodiment 1.Fig. 5 is the curve chart of concentration (weight (ppm) of the colloid protective agent of relative response liquid total weight) with the relation of the average grain diameter of granular phenol resin of expression colloid protective agent.Wherein, if the measurement range 13 of colloid protective agent concentration～about 103ppm is converted into colloid protective agent use amount/phenol use amount than (weight %), then be equivalent to the scope of 0.04～0.32 weight %.As shown in Figure 5, can know and can control the average grain diameter of the granular phenol resin that obtains through the use amount of adjustment colloid protective agent.That is, can know and to reduce average grain diameter through the use amount that increases colloid protective agent.
< embodiment 12 >
Use 35 weight % hydrochloric acid and 36 weight % formalins; The preparation concentration of formaldehyde is that 8 weight % and concentration of hydrochloric acid are the mixed solution 10kg of 17 weight %; In this mixed solution, add 2 weight % aqueous solution 20g of sanlose then, stir into uniform solution.Then, the temperature of this uniform solution is adjusted to 20 ℃, adds 40 ℃ 95 weight % phenol 400g then while stirring.Wherein, the concentration of the phenols of relative response liquid total weight is 3.65 weight %, and the adding mol ratio of the phenol of phase PARA FORMALDEHYDE PRILLS(91,95) is 0.15, and the molar concentration of the hydrochloric acid in the reactant liquor is 5.0mol/L.When adding phenol and begin about 70 seconds, the reactant liquor gonorrhoeaization.After gonorrhoeaization, reduce mixing speed and still continue reaction, the result is after the phenol interpolation begins about 30 minutes, and reactant liquor is coloured to lightpink.At this moment, the temperature of reactant liquor reaches 30 ℃.After reactant liquor painted, utilize external heat, reactant liquor is heated to 80 ℃, under this temperature, kept 30 minutes.Then, filter this reactant liquor, the granular phenol resin filter cake with the water washing of 1kg obtains obtains the about 700g granular phenol resin 12A-a that wets thus.Utilize 50 ℃ drying machine to make its part dry with 10 hours, carry out fluorescent X-ray then and measure, the chlorinity of granular phenol resin is about 6500ppm as a result.In addition, the average grain diameter of granular phenol resin 12A-a is 3.5 μ m.
Then, said wet granular phenol resin 12A-a 500g is scattered among the ion exchange water 5L, is heated to 95 ℃ while stirring, under this temperature, kept 24 hours.Then, filter this dispersion liquid,, obtain granular phenol resin 12A-b (being equivalent to dry weight 320g) with the granular phenol resin on the ion-exchange water washing filter paper of 500g.Made the part of the granular phenol resin that obtains dry with 10 hours down at 105 ℃, carry out fluorescent X-ray then and measure, chlorinity is about 1100ppm as a result.
Then, wet granular phenol resin 12A-b (being equivalent to dry weight 300g) is scattered in the ethylene glycol of 900g, is heated to 180 ℃ while stirring, under this temperature, kept 3 hours.Then, be cooled to normal temperature after, filter this dispersion liquid, with the granular phenol resin on the ion-exchange water washing filter paper of 500g.In nitrogen current, the granular phenol resin that obtains 180 ℃ of following dryings 5 hours obtains 280g granular phenol resin 12A-c.The chlorinity of granular phenol resin 12A-c is 70ppm.
< embodiment 13 >
Carry out the washing that 2 times (2 times is the same terms with embodiment 12 all) makes spent glycol altogether, in addition, likewise carry out, obtain the granular phenol resin 13A of 280g with embodiment 12.The chlorinity of granular phenol resin 13A is 10ppm.Wherein, between the washing of the 1st time washing and the 2nd time, drying process is not set.
< embodiment 14 >
Use 35 weight % hydrochloric acid and 36 weight % formalins; The preparation concentration of formaldehyde is that 8 weight % and concentration of hydrochloric acid are the mixed solution 10kg of 18 weight %; In this mixed solution, add 2 weight % aqueous solution 30g of sanlose then, stir into uniform solution.Then, the temperature of this uniform solution is adjusted to 20 ℃, adds 40 ℃ 95 weight % phenol 400g then while stirring.Wherein, the concentration of the phenols of relative response liquid total weight is 3.64 weight %, and the adding mol ratio of the phenol of phase PARA FORMALDEHYDE PRILLS(91,95) is 0.15, and the molar concentration of the hydrochloric acid in the reactant liquor is 5.3mol/L.When the interpolation from phenol begins about 60 seconds, the reactant liquor gonorrhoeaization.After gonorrhoeaization, reduce mixing speed and still continue reaction, the result is after the phenol interpolation begins about 30 minutes, and reactant liquor is coloured to lightpink.At this moment, the temperature of reactant liquor reaches 30 ℃.After reactant liquor is painted, utilize external heat, reactant liquor is heated to 80 ℃, under this temperature, kept 30 minutes.Then, filter this reactant liquor, the granular phenol resin filter cake with the water washing of 1kg obtains obtains the about 700g granular phenol resin 14A-a that wets thus.Utilize 50 ℃ drying machine to make its part dry with 10 hours, carry out fluorescent X-ray then and measure, the chlorinity of granular phenol resin is about 6500ppm as a result.In addition, the average grain diameter of granular phenol resin 14A-a is 5.8 μ m.
Then, said wet granular phenol resin 14A-a 500g is scattered among the ion exchange water 5L, is heated to 95 ℃ while stirring, under this temperature, kept 24 hours.Then, filter this dispersion liquid,, obtain granular phenol resin 14A-b (being equivalent to dry weight 320g) with the granular phenol resin on the ion-exchange water washing filter paper of 500g.Made the part of the granular phenol resin that obtains dry with 10 hours down at 105 ℃, carry out fluorescent X-ray then and measure, chlorinity is 1700ppm as a result.
Then, wet granular phenol resin 14A-b (being equivalent to dry weight 300g) is scattered in the ethylene glycol of 900g, is heated to 180 ℃ while stirring, under this temperature, kept 3 hours.Then, be cooled to normal temperature after, filter this dispersion liquid, with the granular phenol resin on the ion-exchange water washing filter paper of 500g.In nitrogen current, the granular phenol resin that obtains 180 ℃ of following dryings 5 hours obtains 280g granular phenol resin 14A-c.The chlorinity of granular phenol resin 14A-c is 90ppm.
< embodiment 15 >
Carry out the washing that 2 times (2 times is the same terms with embodiment 14 all) makes spent glycol altogether, in addition, likewise carry out, obtain the granular phenol resin 15A of 280g with embodiment 14.The chlorinity of granular phenol resin 15A is 30ppm.Wherein, between the washing of the 1st time washing and the 2nd time, drying process is not set.
< embodiment 16 >
The granular phenol resin 12A-a 500g that will in embodiment 12, obtain is scattered among the 25 weight % ammonia spirit 1.5L (1350g), is heated to 37 ℃ while stirring, under this temperature, keeps 24 hours.Then, filter this dispersion liquid, with the granular phenol resin on the ion-exchange water washing filter paper of 500g.The granular phenol resin that obtains 105 ℃ of following dryings 10 hours obtains 320g granular phenol resin 16A.The chlorinity of granular phenol resin 16A is 300ppm.
< embodiment 17 >
Carry out the washing that 2 times (2 times is the same terms with embodiment 16 all) used 25 weight % ammonia spirits altogether, in addition, likewise carry out, obtain the granular phenol resin 17A of 320g with embodiment 16.The chlorinity of granular phenol resin 17A is 50ppm.Wherein, between the washing of the 1st time washing and the 2nd time, drying process is not set.
< embodiment 18 >
The wet granular phenol resin 12A-b (being equivalent to dry weight 300g) that will in embodiment 12, obtain is scattered among the 25 weight % ammonia spirit 900g, uses pressure cooker, stirs 2 hours down at 80 ℃.Then, filter this dispersion liquid, with the granular phenol resin on the ion-exchange water washing filter paper of 500g.The granular phenol resin that obtains 105 ℃ of following dryings 10 hours obtains 280g granular phenol resin 18A.The chlorinity of granular phenol resin 18A is below the detectable limit (10ppm).
< embodiment 19 >
The wet granular phenol resin 12A-a (being equivalent to dry weight 300g) that will in embodiment 12, obtain is scattered in the ethylene glycol of 900g, is heated to 180 ℃ while stirring, under this temperature, keeps 3 hours.Then, after being cooled to room temperature, filter this dispersion liquid, with the granular phenol resin on the ion-exchange water washing filter paper of 500g.In nitrogen current, the granular phenol resin that obtains 180 ℃ of following dryings 5 hours obtains 280g granular phenol resin 19A.The chlorinity of granular phenol resin 19A is 300ppm.
< embodiment 20 >
Carry out the washing that 2 times (2 times is the same terms with embodiment 19 all) makes spent glycol altogether, in addition, likewise carry out, obtain the granular phenol resin 20A of 280g with embodiment 19.The chlorinity of granular phenol resin 20A is 60ppm.In addition, between the washing of the 1st time washing and the 2nd time, drying process is not set.
< comparative example 4 >
Phenol 100 weight portions, 92 weight % paraformaldehyde, 39 weight portions, hexa 9 weight portions and Arabic gum 1 weight portion are dissolved in the water of 100 weight portions.Add Bellpearl R800 (liking water (strain) system) 7 weight portions and stir also lentamente and be warming up to 85 ℃ with 60 minutes simultaneously, and then keep 85 ℃ temperature and make its reaction 60 minutes simultaneously as nuclear matter.The reactant liquor that cooling obtains carries out Separation of Solid and Liquid, obtains the spherical resol that average grain diameter is about 500 μ m.These spherical resol 100 weight portions are scattered in the solution that contains 17 weight % hydrochloric acid and 9 weight % formaldehyde of 1000 weight portions, are warming up to 80 ℃, kept 1 hour.Utilize to filter reactant liquor is carried out Separation of Solid and Liquid, after the washing, drying is 5 hours under 85 ℃.The resin that obtains keeps spherical form and granularity constant, and non-thermofusible is shown in fact.Sphericity is 1.0, and the simple grain rate is 1.0, and average grain diameter is about 500 μ m, and boiling the dissolve with methanol degree is 6%, and chlorinity is 4500ppm.Average grain diameter directly reads from the particle size distribution of optical microphotograph mirror image.
Method according to record among the embodiment 13 makes spent glycol, and the non-thermofusible phenolic resins particle that this average grain diameter is about 500 μ m carries out carrying out washing treatment 2 times, obtains granular phenol resin 4C.The chlorinity of granular phenol resin 4C is 1200ppm.In addition, between the washing of the 1st time washing and the 2nd time, drying process is not set.
< reference implementation example 1 >
The granular phenol resin 14A-b 500g (chloride ion content 1700ppm) that will in said embodiment 14, obtain is scattered among the ion exchange water 5L, is heated to 95 ℃ while stirring, under this temperature, keeps 24 hours.Then, filter this dispersion liquid, with the granular phenol resin on the ion-exchange water washing filter paper of 500g.The granular phenol resin that obtains 105 ℃ of following dryings 10 hours obtains granular phenol resin 1S.The chlorinity of granular phenol resin 1S is 700ppm.
< reference implementation example 2 >
Granular phenol resin 1S is carried out and reference implementation example 1 identical operations, obtain granular phenol resin 2S.The chlorinity of granular phenol resin 2S is 600ppm.
< reference implementation example 3 >
Granular phenol resin 2S is carried out and reference implementation example 1 identical operations, obtain granular phenol resin 3S.The chlorinity of granular phenol resin 3S is 550ppm.
To granular phenol resin 12A～20A, 4C and 1S～3S, measure the various characteristics shown in the table 2.To measure the result and be shown in table 2 with reaction condition.Granular phenol resin 1C and 3C also are shown together.
Figure G2009101734092D00531
Can know from said embodiment 12～20, utilize the washing of ethylene glycol and/or the washing of ammonia spirit, can obtain the granular phenol resin below the chlorinity 100ppm effectively.Think that alcohols such as ethylene glycol has easily the chemical property to the diffusion inside of phenolic resins particle, can improve the diffusion velocity of chloride ion in phenolic resins, so can wash effectively.In addition, think that also the high-temperature area that the motility of preferably utilizing the phenolic resins molecule improves washs.Think use ammonia spirit situation too because ammonia spirit can improve the diffusion velocity of chloride ion in phenolic resins, so can wash effectively like this to the diffusion inside of phenolic resins particle.
On the other hand; If observe reference implementation example 1～3; Chlorinity 1700ppm) and the 2nd (granular phenol resin 1S: chlorinity 700ppm) during washing then visiblely utilizing hot water to carry out (granular phenol resin 14A-b: the 1st time; Chlorinity reduces owing to remove the chloride ion of phenolic resins particle surface, closes the inner chloride ion of phenolic resins but exist more on the contrary, and it is controlled to the diffusion translational speed of particle surface to be present in this inner chloride ion; The result is utilizing hot water to carry out the 3rd time and the 4th when washing, and clean result reduces significantly.Use under the situation of hot water, even carry out 4 washings, chlorinity can not become below the 500ppm yet, and is very inefficent.And then, shown in comparative example 4, utilizing the washing of alcohol even can know the bigger phenolic resins of average grain diameter, chlorinity is not reduced fully yet.
Fig. 6 is the scanning electron microscope photo (SEM photo, 500 times) of the granular phenol resin 12A-c that in embodiment 12, obtains.In addition, Fig. 7 is the SEM photo (3500 times) of the further amplification of granular phenol resin 12A-c.Can confirm from Fig. 6, Fig. 7 and table 2; Even utilize ethylene glycol washing and/or ammonia spirit washing; The surface state of average grain diameter, simple grain rate, sphericity and phenolic resins particle etc. almost do not change, and make the washing of spent glycol or ammonia spirit bring harmful effect can for the phenolic resins particle.
[preparation of compositions of thermosetting resin]
< embodiment 21 >
Heat to 70 ℃ of limits at mixing granular phenol resin 13A 6 weight portions that in said embodiment 13, obtain and epoxy resin (Dongdu system of changing into " Epotohto YD-128 ") 4 weight portions on the hot-rolling on the limit; Further add 2-ethyl-4-methylimidazole 0.2 weight portion then as curing agent; Mixing; Peel off mixing thing from hot-rolling, pulverize the cooling back, obtains the powder as compositions of thermosetting resin.This compositions of thermosetting resin illustrates good melt fluidity, and 150 ℃ of following gel times are 33 seconds, and 200 ℃ of following gel times are 18 seconds.
Then, this compositions of thermosetting resin is installed in the mould that is heated to 180 ℃, with 20kgf/cm 2Pressure kept 3 minutes, obtain solidfied material.The proportion of the solidfied material that obtains is 1.24, for light-duty.
< embodiment 22 >
Heat to 70 ℃ of limits at mixing granular phenol resin 13A 6 weight portions that in said embodiment 13, obtain and epoxy resin (Dongdu system of changing into " Epotohto YD-8125 ") 4 weight portions on the hot-rolling on the limit; Further add 2-ethyl-4-methylimidazole 0.2 weight portion then as curing agent; Mixing; Peel off mixing thing from hot-rolling, pulverize the cooling back, obtains the powder as compositions of thermosetting resin.This compositions of thermosetting resin illustrates good melt fluidity, and 150 ℃ of following gel times are 25 seconds, and 200 ℃ of following gel times are 14 seconds.
Then, this compositions of thermosetting resin is installed in the mould that is heated to 180 ℃, with 20kgf/cm 2Pressure kept 3 minutes, obtain solidfied material.The proportion of the solidfied material that obtains is 1.24, for light-duty.In addition, the chlorinity of the solidfied material that obtains is 70ppm, can be used as sealing material for semiconductor or adhesive for semiconductor well.
< embodiment 23 >
Mixing granular phenol resin 13A 15 weight portions that in said embodiment 13, obtain, epoxy resin (Dongdu system of changing into " Epotohto YD-8125 ") 60 weight portions and as phenol novolac resin (big Japanese ink chemical industry system TD-2093) 6 weight portions and dicyandiamide 4 weight portions of curing agent obtain the compositions of thermosetting resin of semi liquid state.
< embodiment 24 >
Mixing granular phenol resin 15A 60 weight portions that in said embodiment 15, obtain, epoxy resin (Dongdu system of changing into " Epotohto YD-8125 ") 40 weight portions and as 2-ethyl-4-methylimidazole 2 weight portions of curing agent obtain compositions of thermosetting resin I.On the other hand, replace granular phenol resin 15A, mixing fused silica (electrochemical industry system FB-301) 106 weight portions, as 2-ethyl-4-methylimidazole 2 weight portions of curing agent obtain compositions of thermosetting resin II.The volume ratio of the fused silica among the volume ratio of the granular phenol resin 15A among the compositions of thermosetting resin I and the compositions of thermosetting resin II is identical.Then, under 150 ℃ temperature conditions, compositions of thermosetting resin I and compositions of thermosetting resin II are heating and curing, obtain solidfied material (being called solidfied material Ia, IIa respectively).To solidfied material Ia and IIa, use ORIENTEC system curast meter VPS, measure 150 ℃ of torques (torque) of solidfied material.As a result, 150 of solidfied material Ia ℃ of torque values are 1.34 times of solidfied material IIa.Can confirm that from this some the obdurability during solidfied material hot of compositions of thermosetting resin of using non-thermofusible granular phenol resin of the present invention is improved.
[preparation of granular carbon electrode material]
< reference implementation example 4 >
At first, utilize the method for record among the embodiment 1, obtain 804g granular phenol resin 1A.Then; 680g in this granular phenol resin is divided into these 4 parts of granular phenol resin 1A-a (200g), granular phenol resin 1A-b (200g), granular phenol resin 1A-c (200g) and granular phenol resin 1A-d (80g); Condition shown in below utilizing; Burn till activation processing respectively, obtain carbon electrode material 1～4 respectively.
(1) carbon electrode material 1 (yield 94g): 1A-a puts into crucible with granular phenol resin, and this crucible is put into electric furnace.Use fully in the nitrogen replacement electric furnace, then flow into nitrogen then and heat up with 100 ℃/hour speed from room temperature simultaneously, in the moment heat treatment 3 hours that reaches 600 ℃.Then, heat up with 100 ℃/hour speed once more, with 850 ℃ following 5 hours, activation in the saturated nitrogen current that steam arranged.The weight slip of expression activation degree is 33%.
(2) carbon electrode material 2 (yield 60g): the temperature when making activation processing is 900 ℃, in addition, likewise carries out with granular phenol resin 1A-a, burns till, activation processing granular phenol resin 1A-b.The weight slip is 56%.
(3) carbon electrode material 3 (yield 35g): the temperature when making activation processing is 950 ℃, in addition, likewise carries out with granular phenol resin 1A-a, burns till, activation processing granular phenol resin 1A-c.The weight slip is 75%.
(4) carbon electrode material 4 (yield 44g): 1A-d puts into crucible with granular phenol resin, and this crucible is put into electric furnace.Use fully in the nitrogen replacement electric furnace, then flow into nitrogen then and heat up with 100 ℃/hour speed from room temperature simultaneously, in the moment heat treatment 3 hours that reaches 950 ℃.
< reference implementation example 5 >
The granular phenol resin 2A 200g that the method for utilizing among the embodiment 2 record is obtained; Utilize the identical condition of granular phenol resin 1A-a with reference implementation example 4; Burn till, activation processing, the weight slip when obtaining the 90g activation processing is 36% carbon electrode material 5.
< reference implementation example 6 >
The granular phenol resin 3A 200g that the method for utilizing among the embodiment 3 record is obtained; Utilize the identical condition of granular phenol resin 1A-a with reference implementation example 4; Burn till, activation processing, the weight slip when obtaining the 91g activation processing is 35% carbon electrode material 6.
< reference implementation example 7 >
The granular phenol resin 4A 200g that the method for utilizing among the embodiment 4 record is obtained; Utilize the identical condition of granular phenol resin 1A-a with reference implementation example 4; Burn till, activation processing, the weight slip when obtaining the 91g activation processing is 35% carbon electrode material 7.
< reference implementation example 8 >
The granular phenol resin 5A 200g that the method for utilizing among the embodiment 5 record is obtained; Utilize the identical condition of granular phenol resin 1A-a with reference implementation example 4; Burn till, activation processing, the weight slip when obtaining the 92g activation processing is 34% carbon electrode material 8.
< reference implementation example 9 >
The granular phenol resin 6A 200g that the method for utilizing among the embodiment 6 record is obtained; Utilize the identical condition of granular phenol resin 1A-a with reference implementation example 4; Burn till, activation processing, the weight slip when obtaining the 90g activation processing is 36% carbon electrode material 9.Fig. 9 representes the optical microscope photograph of the granular carbon electrode material of this reference implementation example.
< reference implementation example 10 >
The granular phenol resin 7A 200g that the method for utilizing among the embodiment 7 record is obtained; Utilize the identical condition of granular phenol resin 1A-a with reference implementation example 4; Burn till, activation processing, the weight slip when obtaining the 92g activation processing is 34% carbon electrode material 10.
< reference implementation example 11 >
The granular phenol resin 8A 200g that the method for utilizing among the embodiment 8 record is obtained; Utilize the identical condition of granular phenol resin 1A-a with reference implementation example 4; Burn till, activation processing, the weight slip when obtaining the 95g activation processing is 32% carbon electrode material 11.Figure 10 representes the optical microscope photograph of the granular carbon electrode material of this reference implementation example.
< reference implementation example 12 >
The granular phenol resin 9A 200g that the method for utilizing among the embodiment 9 record is obtained; Utilize the identical condition of granular phenol resin 1A-a with reference implementation example 4; Burn till, activation processing, the weight slip when obtaining the 90g activation processing is 36% carbon electrode material 12.
< reference implementation example 13 >
The granular phenol resin 10A 200g that the method for utilizing among the embodiment 10 record is obtained; Utilize the identical condition of granular phenol resin 1A-a with reference implementation example 4; Burn till, activation processing, the weight slip when obtaining the 91g activation processing is 35% carbon electrode material 13.
< with reference to comparative example 1 >
The granular phenol resin 1C 70g that the method for utilizing in the comparative example 1 record is obtained; Utilize the identical condition of granular phenol resin 1A-a with reference implementation example 4; Burn till, activation processing, the weight slip when obtaining the 35g activation processing is 30% carbon electrode material 14.Figure 11 is illustrated in this optical microscope photograph with reference to the granular carbon electrode material that obtains in the comparative example.
< with reference to comparative example 2 >
The granular phenol resin 3C 200g that the method for utilizing in the comparative example 3 record is obtained; Utilize the identical condition of granular phenol resin 1A-a with reference implementation example 4; Burn till, activation processing, the weight slip when obtaining the 88g activation processing is 30% carbon electrode material 15.
< with reference to comparative example 3 >
The cocoanut shell of drying is put into crucible, this crucible is put into electric furnace.Use fully in the nitrogen replacement electric furnace, then flow into nitrogen then and also heat up from the speed of room temperature simultaneously, burnt till in 3 hours in the moment heat treatment that reaches 600 ℃ with 100 ℃/hour.Then, then heat up with 100 ℃/hour speed, with 850 ℃ following 5 hours, activation in the saturated nitrogen current that steam arranged.Utilize power mill (dynamic mill) [MYD] (Mitsui Mining Co Ltd. BJ Offc's system), it is crushed to average grain diameter becomes 9 μ m, as granular carbon electrode material 16.
< with reference to comparative example 4 >
Utilize with the identical condition of granular phenol resin 1A-d of reference implementation example 4 and burn till the granular phenol resin 1C 70g that the method for utilizing comparative example 1 to put down in writing obtains, obtain 36g carbon electrode material 17.
To said granular carbon electrode material 1～17, measure the various characteristics shown in the table 3.To measure the result and be shown in table 3.Wherein, in the granular carbon electrode material 15 of the reference comparative example 2 in table 3, simple grain rate and sphericity become "-", show to have a lot of atypic particles, can not measure.
[table 3]
Figure G2009101734092D00591
< reference implementation example 14 >
Amount to as the phase Pyrogentisinic Acid of the sanlose of colloid protective agent is carried out various variations; In addition; Likewise carry out with reference implementation example 4, carry out the preparation of granular phenol resin and burn till, under 850 ℃, carry out 5 hours activation processing then; Obtain granular carbon electrode material, measure the average grain diameter of granular carbon electrode material.Figure 12 is the curve chart of concentration (weight (ppm) of the colloid protective agent of relative response liquid total weight) with the relation of the average grain diameter of granular carbon electrode material of expression colloid protective agent.Wherein, if the measurement range 13 of colloid protective agent concentration～about 103ppm is converted into colloid protective agent use amount/phenol use amount than (weight %), then be equivalent to the scope of 0.04～0.32 weight %.Shown in figure 12, can know and can control the average grain diameter of the granular carbon electrode material that obtains through the use amount of adjustment colloid protective agent.That is, can know and to reduce average grain diameter through the use amount that increases colloid protective agent.
[being suitable in electric double layer capacitor, lithium ion battery and lithium-ion capacitor of granular carbon electrode material]
< reference implementation example 15 >
According to the order shown in following, make the simple type electric double layer capacitor of structure shown in Figure 13.Figure 13 is the summary sectional view of the electric double layer capacitor of expression trial-production.At first; As collector body 602; Use the discoid platinum plate of thick 1mm, external diameter 18mm, on this collector body 602, press the discoid silicon rubber of sticking thick 0.5mm, internal diameter 3mm, external diameter 18mm, in the dark 0.5mm that in collector body 602 and distance piece 604, forms, the hole of internal diameter 3mm as distance piece 604; Fill the carbon electrode material 601 of the pulpous state of preparation in addition, with it as the polarity electrode.Make 2 such polarity electrodes.Then, the discoid polypropylene system dividing plate 603 of the thick 25 μ m of clamping, external diameter 18mm makes this 2 polarity electrode contrapositions between these 2 polarity electrodes.Then, press the sticking terminal board 605 that is used to take out the stainless steel of terminal from two side direction collector bodies 602.And then, apply the load of 10kg through upside from the terminal board 605 of the stainless steel that is used for fixing, make electric double layer capacitor.
Carry out with being described below, prepare the carbon electrode material 601 of said pulpous state.With the weight rate shown in the table 4; In container, add the granular carbon electrode material (carbon electrode material 13, average grain diameter 9 μ m) of reference implementation example 13 and the granular carbon electrode material (carbon electrode material 9, average grain diameter 1 μ m) of reference implementation example 9; Then; Add a certain amount of 30 weight % aqueous sulfuric acids, outgas as electrolyte.Then, in this mixed liquor, add 30 weight % aqueous sulfuric acids while stirring lentamente, the mixture in container stops to add when argillaceous is varied to pulpous state, obtains the pulpous state carbon electrode material.With the totally 7 kinds of pulpous state carbon electrode materials (slip 1～7) shown in such order preparation table 4.The employed electrolyte content of every 1g carbon electrode material (g) is called " electrolyte/electrode material ratio ", is shown in table 4.
Then, to diverse 7 kinds of electric double layer capacitors of the carbon electrode material 601 of pulpous state, measure the electrostatic capacitance (F/g) of per unit weight carbon electrode material respectively.Apply the voltage of 0.9V to two interpolars of electric double layer capacitor; Carry out 6 hours constant voltage charges; Make its constant-current discharge with 100 μ A then; Utilize voltage to reduce to the needed time of 0.45V, try to achieve the electrostatic capacitance (F) of electric double layer capacitor, calculate the electrostatic capacitance (F/g) of per unit weight carbon electrode material from this value and one group of (2) weight of polarity electrode from 0.54V.The result is shown in table 4.
In addition,, utilize following formula, try to achieve the coefficient of electrostatic capacity of per unit volume from the weight of the electrolyte of the weight of the electrostatic capacitance (F/g) of per unit weight carbon electrode material, the carbon electrode material that uses and interpolation.The result is shown in table 4.
The coefficient of electrostatic capacity of per unit volume=
(electrostatic capacitance of per unit weight carbon electrode material (F/g)) * (carbon electrode material weight)/(carbon electrode material weight+electrolyte weight)
Figure G2009101734092D00621
Can know through mixing to use and control the carbon electrode material of the present invention 9 and 13 that average grain diameter, particle size distribution and simple grain rate are made tightly; Compare with the situation of independent use; Can carry out slip with electrolyte still less regulates; So can in electric double layer capacitor, fill more carbon electrode material, thereby, the coefficient of electrostatic capacity of per unit volume can further be increased.Can know that especially the coefficient of electrostatic capacity of per unit volume becomes the highest under the situation of mixing carbon electrode material 9 and 13 with 15 pairs 85 (weight ratio) (slip 4).
In addition; Mensuration is with reference to the granular carbon electrode material (carbon electrode material 16 of comparative example 3; Average grain diameter 9 μ m) " electrolyte/electrode material ratio ", the result is 1.49, with the granular carbon electrode material (carbon electrode material 13 of reference implementation example 13; Average grain diameter 9 μ m) 1.37 (with reference to the slips 7 of table 4) are compared, and higher value is shown.This can infer it is that sphericity is low simultaneously because wide with reference to the particle size distribution of the granular carbon electrode material of comparative example 3, so that the gap of the carbon electrode material in the slip becomes is big, for slipization, needs the more electrolyte of volume.
< reference implementation example 16 >
Use the granular carbon electrode material (carbon electrode material 1 of reference implementation example 4; Average grain diameter 4 μ m), with reference to the granular carbon electrode material (carbon electrode material 14 of comparative example 1; Average grain diameter 15 μ m); They are utilized respectively and reference implementation example 15 order in opposite directions, make electric double layer capacitor, measure electrostatic capacitance.At this moment, the discharging current amount is become 1.0mA from 0.1mA, measure the electrostatic capacitance under each discharging current.The result is shown in table 5.
[table 5]
Figure G2009101734092D00631
* 1: the electrostatic capacitance of per unit weight carbon electrode material.
Can know that electrostatic capacitance greatly reduced when use increased with reference to the discharging current of the electric double layer capacitor of the granular carbon electrode material of comparative example 1, and use the reduction of electrostatic capacitance of electric double layer capacitor of granular carbon electrode material of reference implementation example 4 few.Think that this is because under the situation that is carbon electrode material 1, compare with carbon electrode material 14; The average grain diameter of electrode material is little, so 1) since the ratio that contacts on carbon electrode material and the electrolytical interface increase, so absorption, the desorption of the relative carbon electrode material of electrolyte ion that utilization discharges and recharges are successfully carried out; And 2) diffusion length owing to the inner ion of carbon electrode material shortens, thus utilize absorption, the desorption of the relative carbon electrode material of electrolyte ion that discharges and recharges successfully to carry out, promptly; Under the little situation of the average grain diameter of carbon electrode material; Even the increase discharging current, the desorption of electrolyte ion also can promptly be replied, and under the big situation of average grain diameter; The desorption of electrolyte ion can not promptly be replied, and electrostatic capacitance reduces along with the increase of discharging current.
< reference implementation example 17 >
Carry out the evaluation of the negative material of using as lithium ion battery or lithium-ion capacitor of granular carbon electrode material of the present invention with being described below.Be dissolved in the solution that N-methyl pyrrolidone 80 weight portions form through the granular carbon electrode material of hybrid reference embodiment 4 (carbon electrode material 4, average grain diameter 3 μ m) 100 weight portions fully with Kynoar powder 10 weight portions; It is become slip; This slip is coated Copper Foil (20 μ m are thick); Drying, punching press obtains negative pole.This negative pole is cut into 1.5cm * 2.0cm size, uses negative pole as evaluation.In-service evaluation is used negative pole, and as to the 1.5cm * 2.0cm size of electrode, the lithium metal of thick 200 μ m, the polyethylene system nonwoven fabrics as the thick 50 μ m of dividing plate is assembled into and estimates with battery (cell).As reference electrode, use lithium metal.As electrolyte, use with 1mol/L concentration LiPF 6Be dissolved in the solution that forms in the propylene carbonate.For relatively, use granular carbon electrode material (carbon electrode material 17, average grain diameter 15 μ m) with reference to comparative example 4, make identical evaluation and use battery.
Said each evaluation is discharged and recharged test with battery.Discharge and recharge for the first time on the basis of restriction current potential, charging, discharge are all with 0.2mA/cm 2Carry out.Potential range under the lithium benchmark is from 0V to 2V.Then, with 0.2mA/cm 2, the potential range from 0V to 0.5V is carried out the 2nd time～the 7th time discharge and recharge, and then, with 1.0mA/cm 2, the potential range from 0V to 0.5V is carried out the 8th time～the 15th time discharge and recharge.
With current density 0.2mA/cm 2The 7th time the discharge capacity of estimating with 1.0mA/cm 2(capability retention %), for the granular carbon electrode material 4 of reference implementation example 4, is 92% to the ratio of the 15th time the discharge capacity of estimating, and for for the granular carbon electrode material 17 of comparative example 4, is 69%.Can know that from this result the granular carbon electrode material of the application of the invention even improve current density, also can suppress the reduction of discharge capacity.
[preparation of molecular-sieve carbon]
< reference implementation example 18 >
Use 35 weight % hydrochloric acid and 36 weight % formalins; Preparation is as the mixed solution 2000g of concentration of formaldehyde 10 weight % and concentration of hydrochloric acid 18 weight %; In this mixed solution, add 2 weight % aqueous solution 8g of sanlose then, stirring becomes uniform solution.Then, the temperature with this uniform solution is adjusted to 20 ℃, limit stirring then, the 95 weight % phenol 70g that the limit adding is 30 ℃.Wherein, the concentration of phenols relative response liquid total weight is that the adding mol ratio of 3.2 weight %, phenol phase PARA FORMALDEHYDE PRILLS(91,95) is 0.11, and the molar concentration of the hydrochloric acid in the reactant liquor is 5.0mol/L.Began reactant liquor generation gonorrhoeaization about 120 seconds from adding phenol.After gonorrhoeaization, reduce mixing speed and still continue reaction, the result is after interpolation phenol begins about 30 minutes, and reactant liquor is coloured to lightpink.At this moment, the temperature of reactant liquor arrives 30 ℃.After reactant liquor is painted, utilize external heat, reactant liquor is heated to 80 ℃, under this temperature, kept 30 minutes.Then, filter this reactant liquor, the filter cake with the water washing of 500g obtains makes it be suspended in the 0.5 weight % ammonia spirit of 500g then, under 40 ℃, carries out 1 hour neutralization reaction.After the neutralization reaction, use aspirator to attract to filter this suspension,, utilize 50 ℃ drying machine to make its dry 10 hours, obtain the lurid granular phenol resin 21A of 80g thus with the water washing of 500g.
Then; Metering granular phenol resin 21A 100 weight portions, coal tar 23 weight portions, the melmac aqueous solution 5 weight portions (solid constituent conversion) of solid component concentration 80 weight %, polyvinyl alcohol water solution (use warm water; The polyvinyl alcohol of the degree of polymerization 1700, saponification degree 99% is dissolved into the aqueous solution of 20 weight %) 20 weight portions, cornstarch 24 weight portions, surfactant (Kao Corp's system, PELLEX NB-L) 9.3 weight portions and water 4 weight portions.
Wherein, mix 10 minutes compositions beyond the granular phenol resin 21A, add granular phenol resin 21A then, further mixed 20 minutes.Use two-way extruding granulator (only Paudal Co., Ltd. system, Pelletta-Double EXDF-100 type) to extrude this blend compositions, obtain the cylindrical pellet of diameter 1.3mm * length (height) 1～3mm.Under nitrogen current, with 350 ℃, the particle that heat treatment obtained in 4 hours; Then to the rotary furnace of effective dimensions 100mm φ * 1000mm; Supply with 100g/h, under the nitrogen current of 2L/min, carry out carbonization treatment with under 750 ℃ of 6 hours residence times, treatment temperature; Under nitrogen current, cool off then, obtain molecular-sieve carbon MSC-1.Figure 15 is the surperficial SEM photo of molecular-sieve carbon MSC-1 that obtains in the present embodiment.
< reference implementation example 19 >
The granular phenol resin 10A that use obtains in said embodiment 10 in addition, likewise carries out with reference implementation example 18, obtains molecular-sieve carbon MSC-2.
< reference implementation example 20 >
Be blended in the melmac aqueous solution 4 weight portions (solid constituent conversion) and water 40 weight portions of granular phenol resin 6A 100 weight portions that obtain among the said embodiment 6, coal tar 10 weight portions, solid component concentration 80 weight %; Use two-way extruding granulator (Fuji Paudal Co., Ltd. system then; Fine Ryuzer EXR-60 type) extrudes the blend compositions that obtains, be a granulated into cylindric.Then, use marmelizer (only Paudal Co., Ltd. system, QJ-230 type), granulation obtains the cylindrical pellet of diameter 1mm * length 2～3mm.Under nitrogen current, with 350 ℃, the particle that heat treatment obtained in 4 hours; The rotary furnace that adds effective dimensions 100mm φ * 1000mm then under nitrogen current, is warming up to 780 ℃; Under this temperature, kept 3 hours, under nitrogen current, cool off then, obtain molecular-sieve carbon MSC-3.
< reference implementation example 21 >
Mix 36 weight % formalin 556g, 95 weight % phenol 70g and water 530g, prepare mixed solution 1156g, in this mixed solution, add 2 weight % aqueous solution 8g of sanlose then, stirring becomes uniform solution.Then, the temperature with this uniform solution is adjusted to 20 ℃, limit stirring then, the 35 weight % hydrochloric acid 914g that the limit adding is 30 ℃.Wherein, the concentration of phenols relative response liquid total weight is that the adding mol ratio of 3.2 weight %, phenol phase PARA FORMALDEHYDE PRILLS(91,95) is 0.11, and the molar concentration of the hydrochloric acid in the reactant liquor is 4.7mol/L.Began reactant liquor generation gonorrhoeaization about 20 seconds from adding hydrochloric acid.After gonorrhoeaization, still continue reaction, the result is after interpolation hydrochloric acid begins about 30 minutes, and reactant liquor is coloured to pink colour.At this moment, the temperature of reactant liquor arrives 30 ℃.Then, filter this reactant liquor, the filter cake with the water washing of 500g obtains makes it be suspended in the 0.5 weight % ammonia spirit of 500g then, under 40 ℃, carries out 1 hour neutralization reaction.After the neutralization reaction, use aspirator to attract to filter this suspension,, utilize 50 ℃ drying machine to make its dry 10 hours, obtain the lurid granular phenol resin 5C of 75g thus with the water washing of 500g.
Then, use granular phenol resin 5C, in addition, likewise carry out, obtain molecular-sieve carbon MSC-4 with reference implementation example 20.
< with reference to comparative example 5 >
The melmac aqueous solution 8 weight portions of granular phenol resin 1C 100 weight portions that metering obtains in said comparative example 1, solid component concentration 80 weight % (solid constituent conversion), polyvinyl alcohol water solution (use warm water; The polyvinyl alcohol of the degree of polymerization 1700, saponification degree 99% is dissolved into the aqueous solution of 20 weight %) 20 weight portions, farina 2 weight portions and surfactant (Kao Corp's system, PELLEX NB-L) 0.7 weight portion.
Wherein, mix 5 minutes compositions beyond the granular phenol resin 1C, add granular phenol resin 1C then, further mixed 10 minutes.Use two-way extruding granulator (only Paudal Co., Ltd. system, Pelletta-Double EXDF-100 type) to extrude the blend compositions that obtains, obtain the cylindrical pellet of diameter 1.3mm * length (height) 1～3mm.Utilize the method identical, the particle that obtains is handled, obtain molecular-sieve carbon MSC-5 with reference implementation routine 18.
< with reference to comparative example 6 >
Use 35 weight % hydrochloric acid and 36 weight % formalins; The preparation concentration of formaldehyde is that 10 weight % and concentration of hydrochloric acid are the mixed solution 2000g of 16 weight %; In this mixed solution, add 2 weight % aqueous solution 8g of sanlose then, stir into uniform solution.Then, the temperature of this uniform solution is adjusted to 20 ℃, adds 30 ℃ 95 weight % phenol 70g then while stirring.Wherein, the concentration of the phenols of relative response liquid total weight is 3.2 weight %, and the adding mol ratio of the phenol of phase PARA FORMALDEHYDE PRILLS(91,95) is 0.11, and the molar concentration of the hydrochloric acid in the reactant liquor is 4.7mol/L.After the interpolation of phenol about 120 seconds the time, the reactant liquor gonorrhoeaization.After gonorrhoeaization, reduce mixing speed and still continue reaction, the result is after the phenol interpolation begins about 30 minutes, and reactant liquor is coloured to lightpink.At this moment, the temperature of reactant liquor reaches 30 ℃.Then, filter this reactant liquor, the filter cake with the water washing of 500g obtains makes in its 0.5 weight % ammonia spirit that is suspended in 500g then, under 40 ℃, carries out 1 hour neutralization reaction.After the neutralization reaction, use aspirator to attract to filter this suspension,, utilize 50 ℃ drying machine to make its dry 10 hours, obtain the lurid granular phenol resin 6C of 78g thus with the water washing of 500g.
Then, use granular phenol resin 6C, in addition, likewise carry out, obtain molecular-sieve carbon MSC-6 with reference implementation example 18.
To be summarized in table 6 as the granular phenol resin of raw material.
To said molecular-sieve carbon MSC-1～MSC-6, use characterization of adsorption determinator shown in Figure 16, utilize following method, carry out single composition adsorbance of oxygen and nitrogen and measure.In Figure 16, in sample room 312 (250ml), add the sample (molecular-sieve carbon) of 30g, shut off valve 303, electromagnetically operated valve 305 are opened valve 302, use vacuum pump 301, outgas 30 minutes, and shut off valve 302 then.Then; Under the state of closing electromagnetically operated valve 305, flow into mensuration gas (oxygen or nitrogen), control valve 308, valve 316, gas conditioner 309 to measuring cell 311 from gas bomb 310; Pressure in the measuring cell is adjusted to 1.5MPa (gauge pressure), shut off valve 308 and valve 316.And then, close electromagnetically operated valve 305, the interior pressure of measuring in the measuring cell 311 in the stipulated time changes, and tries to achieve and measures the adsorbance of gas under each time.The pressure of constant pressure valve 306 at this moment is adjusted to 0.3MPa (gauge pressure).Working pressure transducer 313,314 is measured the interior pressure of measuring cell 311 and sample room 312, and this measured value is used the identical show value of show value with the JISB7505 Bourdon tube pressure gauge of 1.6 grades of accuracy classes.
The equation of state PV=nRT of using gases calculates adsorbance Q (mg/g).At this, P is for measuring pressure (mensuration intraventricular pressure), and V is the spatial volume in the mensuration system, and n is the mensuration number of moles of gas in the mensuration system, and R is a gas constant, and T is for measuring temperature (25 ℃).Utilize the pressure P of the A-stage of measuring cell 0With the pressure P after the absorption tPressure differential, use following formula, calculate the molal quantity n at initial stage 0With the molal quantity n after the absorption tPoor Δ n.
N＝PV/RT
Δn＝(n 0-n t)＝(P 0-P t)V/RT
Δ n is the summation of molal quantity and the molal quantity of the gas that imports the sample room system of the mensuration gas of absorption, so use the molal quantity Δ n of mensuration gas of absorption that removes the molal quantity gained of the gas that imports the sample room system from Δ n 0, utilize following formula, try to achieve the adsorbance Q of every 1g molecular-sieve carbon.Q (mg/g)=1000 * Δ n 0(mol) * molecular weight (the g/mol)/molecular-sieve carbon weight (g) of absorbing molecules (mensuration gas)
The mensuration of utilizing said assay method to obtain is begun the oxygen adsorbance Q after 60 seconds O, 60sAnd from measuring the nitrogen adsorbance Q of beginning after 10 seconds N, 10sBe shown in table 7.
[table 7]
? Reference implementation example 18 Reference implementation example 19 Reference implementation example 20 Reference implementation example 21 With reference to comparative example 5 With reference to comparative example 6
Molecular-sieve carbon MSC-1 MSC-2 MSC-3 MSC-4 MSC-5 MSC-6
Oxygen adsorbance Q O，60s(mg/g) 25.8 24.7 27.8 24.3 22.8 20.5
Nitrogen adsorbance Q N，10s(mg/g) 4.4 2.0 3.3 3.0 2.7 2.0
[0411]In addition, adsorption tower 101a and 101b with said molecular-sieve carbon MSC-1～MSC-6 is filled in PSA formula nitrogen generator unit shown in Figure 14 estimate the nitrogen generating ability.The weight of the molecular-sieve carbon of filling is all identical.
At first, will utilize compressor 102 air compressed to deliver to adsorption tower 101a and 101b, and make the pressure of adsorption tower become gauge pressure 9.5kgf/cm 2G utilizes 4 operations of all pressure-absorption up and down-all pressure-regeneration up and down (purging (purge)) to implement the PSA operation.Under the control of sequencer (sequencer), carry out the switching of each operation.It is 2.5Nl/min that the taking-up flow (goods nitrogen amount) of goods nitrogen is unified into corresponding employed every 1kg molecular-sieve carbon, utilizes oxymeter to measure the oxygen concentration of the goods nitrogen that obtains, and estimates.In addition, the optimization adsorption time reaches and all presses the time.Table 8 illustrates the oxygen concentration (ppm) in the goods nitrogen.In addition, the average grain diameter of each molecular-sieve carbon, the coefficient of alteration and the particle volume density of particle size distribution also are shown in table 8 in the lump.Wherein, for molecular-sieve carbon MSC-6, fuse between the carbon predecessor, can not measure average grain diameter and coefficient of alteration.
[table 8]
? Reference implementation example 18 Reference implementation example 19 Reference implementation example 20 Reference implementation example 21 With reference to comparative example 5 With reference to comparative example 6
Molecular-sieve carbon MSC-1 MSC-2 MSC-3 MSC-4 MSC-5 MSC-6
Average grain diameter (μ m) 4.2 9.8 1.4 1.4 15 -
The coefficient of alteration of particle size distribution 0.2 0.6 0.1 0.1 0.7 -
Particle volume density (g/cc) 1.1 1.0 0.92 0.82 1.0 1.1
Oxygen concentration (ppm) 25 60 10 55 100 800
Can know the molecular-sieve carbon (MSC-1～MSC-4), can reduce the oxygen concentration in the goods nitrogen significantly of the application of the invention.At this; In PSA formula nitrogen generator unit, known usually under the situation of using same molecular sieve carbon, if increase the goods nitrogen amount; Then nitrogen purity reduces; If reduce the goods nitrogen amount, then nitrogen purity rise (for example list of references 1: " pressure swing adsorption is integrated " just sharp long industrial technology meeting of Chkawai, issue clear and in January, 61).Figure 17 be expression used yield (that is, and the separation energy of oxygen/nitrogen poor, yield is represented with yield=(nitrogen amount in goods nitrogen amount/base feed gas) in being filled with the nitrogen generator unit of molecular-sieve carbon.) the figure of relation of purity and goods nitrogen flow of goods nitrogen in the PSA formula nitrogen generator unit of different molecular-sieve carbon.Like this, illustrate in use under the situation of molecular-sieve carbon of high yield, can improve goods nitrogen purity with same nitrogen flow.That is, such relation shows: used can situation with the molecular-sieve carbon of the goods nitrogen of same goods nitrogen amount generation higher degree under, under the condition of same goods nitrogen purity, can further increase the goods nitrogen amount.
Thereby the molecular-sieve carbon of the application of the invention and was compared in the past, can make the goods nitrogen amount bigger, so can utilize the improvement of nitrogen recovery, came greatly to improve the nitrogen generating capacity of per unit weight molecular-sieve carbon.
In addition, the assay method of the various characteristics for granular phenol resin, granular carbon electrode material and molecular-sieve carbon and condition determination are described below.
(1) non-thermofusible and hot melt: about 5g granular phenol resin sample is inserted between 2 thick corrosion resistant plates of 0.2mm; Utilize and heat in advance to 100 ℃ forcing press, with the total load of 50kg, punching press 2 minutes; At this moment; Because fusion and/or fusion granular phenol resin take place form in the absence about being bonded to each other between flat board or distortion of phenolic resins particle or the phenolic resins particle, judge " non-thermofusible ".In addition, under this high-temperature pressurizing condition, because fusion and/or fusion, granular phenol resin forms under the dull and stereotyped situation, judges " hot melt ".
(2) boil the dissolve with methanol degree: the about 10g granular phenol resin of precision weighing sample; In the about 500mL of in fact anhydrous methyl alcohol; Heating under refluxing in 30 minutes, the glass filter with No.3 filters then, and then with the residue on the absolute methanol cleaning glass filter of about 100mL.Then, with the residue on the glass filter after the washing in 5 hours of 40 ℃ of dryings, this residue of precision weighing then.From dried residue weight and the granular phenol resin example weight that obtains,, calculate and boil the dissolve with methanol degree based on following formula.
Boil dissolve with methanol degree (weight %)=(granular phenol resin example weight and dried residue weight poor)/(granular phenol resin example weight) * 100
(3) average grain diameter: be to use carbon electrode material or granular phenol resin, the preparation aqueous dispersions, the cumulative frequency of utilizing the frequency distribution of laser diffraction formula granulometry machine (day machine dress (strain) system Microtrac X100) instrumentation is 50% value.
(4) simple grain rate: be meant and in water droplet, disperse carbon electrode material or granular phenol resin; Utilize light microscope to observe; In containing the visual field of selecting at random of 300 predecessors of having an appointment, this when the total number of counting predecessor and the number of simple grain is than the total number of simple grain number/predecessor.
(5) coefficient of alteration of particle size distribution: use carbon electrode material or granular phenol resin, the preparation aqueous dispersions from utilizing the frequency distribution of laser diffraction formula granulometry machine (day machine dress (strain) system MicrotracX100) instrumentation, utilizes following formula [1] to calculate.
The coefficient of alteration of particle size distribution=(d 84%-d 16%)/(2 * average grain diameter) [1]
At this, in above-mentioned formula [1], d 84%, d 16%It is respectively the particle diameter of expression cumulative frequency 84%, 16% in the frequency distribution that obtains.The earthquake coefficient is under the situation below 0.65, judges to become to have narrow particle size distribution.
(6) sphericity: be meant in observation by light microscope; Select to contain the visual field of 300 predecessors of having an appointment randomly; Select the minimum predecessor of 10 asperratios (being the ratio of minor axis/major diameter); To these 10 predecessors, the mean value of these 10 asperratios when measuring the asperratio in its projected area respectively.
(7) free phenol content: be defined as the value of utilizing the test be described below to calculate.That is, the about 10g of precision weighing granular phenol resin sample, in the methyl alcohol of 190mL, extraction is 30 minutes under refluxing, and filters with glass filter.Utilize the phenols concentration in the quantitative filtrating of liquid chromatogram, calculate the phenols weight in this filtrating.With the ratio of this phenols weight and example weight is that phenols weight/granular phenol resin example weight is as " free phenol content ".
(8) chlorinity: working sample (non-thermofusible phenolic resins particle) and mensuration are pressurizeed with binder powders; Become to measure and use particle; Use the system fluorescent x-ray analyzer ZSX100E of Co., Ltd. Neo-Confucianism then, utilize the EZ scan pattern to carry out x-ray fluorescence analysis.That utilizes the phenolic resin curing thing infers molecular formula (C 7H 6O 1) the Alpha-ray diffracted intensity measured value of standardization chlorine K, as chlorinity (wt/wt).
(9) specific area: the accurate about 0.1g carbon electrode material of weighing, in the dedicated slot (cell) of the full-automatic gas adsorbent equipment of the high accuracy of packing into then BELSORP-miniII (Japanese Bel Co., Ltd. system), utilize the B.E.T method that nitrogen adsorbs to try to achieve.
(10) average grain diameter of the carbon predecessor of formation molecular-sieve carbon: under the observation that utilizes the scanning electron microscope photo; To the molecular-sieve carbon surface and the plane of disruption; Select the visual field respectively randomly; When each visual field is at random selected to confirm as 100 spherical carbon predecessors, utilize the mean value of the particle diameter of these 200 carbon predecessors that the SEM photo measures.In addition, " standard deviation of carbon initial size " is the above-mentioned standard deviation that can confirm as the particle diameter of 200 spherical carbon predecessors.
(11) coefficient of alteration of the particle size distribution of the carbon predecessor of formation molecular-sieve carbon: utilize following formula to try to achieve.
The coefficient of alteration of the particle size distribution of carbon predecessor=(standard deviation of carbon initial size)/(average grain diameter of carbon predecessor)
Please be careful: this time disclosed execution mode and embodiment are illustration from all senses, are not restrictive execution mode and embodiment.Scope of the present invention is not described explanation and representing with claim, is included in and meaning that claim is impartial and the whole change in the scope.

Claims (8)

1. granular carbon electrode material, wherein,
Said granular carbon electrode material is the carbide of non-thermofusible phenolic resins,
The average grain diameter of said granular carbon electrode material is below the 10 μ m, and the simple grain rate is more than 0.7, and sphericity is more than 0.75, and the coefficient of alteration of the particle size distribution shown in the following formula [1] is below 0.65,
The coefficient of alteration of particle size distribution=(d 84%-d 16%)/(2 * average grain diameter) [1]
At this, d 84%, d 16%Be respectively the particle diameter of expression cumulative frequency 84%, 16% in the frequency distribution that utilizes the laser diffraction and scattering method to obtain,
Average grain diameter is meant that the assay method that utilize to use laser diffraction formula granulometry machine is cumulative frequency 50% value of the frequency distribution that obtains of laser diffraction and scattering method,
The simple grain rate is meant disperses granular carbon electrode material in water droplet; Carry out observation by light microscope; In the visual field of selecting at random that contains 300 predecessors of having an appointment, the total number of ratio simple grain number/predecessor when the total number of counting predecessor and the number of simple grain
Sphericity is meant in observation by light microscope; Select to contain the visual field of 300 predecessors of having an appointment randomly; The minimum predecessor of ratio that to select 10 asperratios be minor axis/major diameter; To these 10 predecessors, the mean value of these 10 asperratios when measuring the asperratio in its projected area respectively.
2. granular carbon electrode material mixture, it is that the different granular carbon electrode material more than 2 kinds of hybrid right requirement 1 described average grain diameter forms.
3. the manufacturing approach of a granular carbon electrode material, it is the method that is used to make the described granular carbon electrode material of claim 1, wherein,
Comprise:
(1) granular phenol resin forms operation, its through the molar concentration in reactant liquor be more than the 2.0mol/L acidic catalyst and colloid protective agent in the presence of, in aqueous medium, make aldehydes and phenols react the formation granular phenol resin;
(2) heating process, its heating contain the reactant liquor of said granular phenol resin and form the granular phenol resin of non-thermofusible;
(3) separation circuit, it separates the granular phenol resin of said non-thermofusible from reactant liquor;
(4) firing process, it burns till the granular phenol resin of said non-thermofusible.
4. the manufacturing approach of granular carbon electrode material according to claim 3, wherein,
Said acidic catalyst is a hydrochloric acid, and said aldehydes is formaldehyde, paraformaldehyde or their mixture.
5. the manufacturing approach of granular carbon electrode material according to claim 3, wherein,
The adding mol ratio of the said relatively aldehydes of said phenols is below 0.9.
6. the manufacturing approach of granular carbon electrode material according to claim 3, wherein,
Said colloid protective agent is the water-soluble polysaccharide analog derivative.
7. the manufacturing approach of granular carbon electrode material according to claim 3, wherein,
The free phenol content of the granular phenol resin of said non-thermofusible is below the 500ppm.
8. an electric double layer capacitor, lithium ion battery or lithium-ion capacitor, it has used described granular carbon electrode material of claim 1 or the described granular carbon electrode material mixture of claim 2.
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