CN1827553A - Process for preparing polymer and graphite conductive nano composites - Google Patents
Process for preparing polymer and graphite conductive nano composites Download PDFInfo
- Publication number
- CN1827553A CN1827553A CN 200510040100 CN200510040100A CN1827553A CN 1827553 A CN1827553 A CN 1827553A CN 200510040100 CN200510040100 CN 200510040100 CN 200510040100 A CN200510040100 A CN 200510040100A CN 1827553 A CN1827553 A CN 1827553A
- Authority
- CN
- China
- Prior art keywords
- graphite
- polymer
- expanded graphite
- low molecule
- composite material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The present invention discloses a method for preparation of conducting composite material of polymer/graphite nanometer. The invention mixes the low molecular auxiliary agent such as plasticizer solution or emulsion with the expanded graphite, removes the solvent or disperse medium after the low molecular auxiliary agent solution or emulsion filters the expanded graphite, produces the composite expanded graphite of composite of the low molecular auxiliary agent and the expanded graphite, afterwards, mixes the composite expanded graphite with the polymer in the phase of fusion in order to prepare conducting composite material of polymer/graphite nanometer. The method of the invention is simple, without using special, expensive and poisonous solvent. The graphite of the conducting composite material disperses in the polymeric matrix in the form of layers of the nanometer graphite wafer, which is of low usage of graphite and excellent conductive property, and the obtained conducting composite material is of low coat and easy spread.
Description
One, technical field
The present invention relates to a kind of preparation method of polymer base conductive composite material, particularly relate to a kind of preparation method of polymer/graphite nanometer conducing composite material.
Two, background technology
Graphite is dispersed in the polymeric matrix, can prepares the polymer/graphite conducing composite material.If graphite disperses with nano level graphite wafer form in polymeric matrix, then the conduction of polymer/graphite conducing composite material exceedes that to ooze threshold values low, promptly under the low situation of graphite consumption, just can in the polymer/graphite conducing composite material, form the spatial conductive network, show excellent conductivity.
Making graphite be nano level graphite wafer form dispersive feasible method in polymeric matrix is to adopt expanded graphite and polymkeric substance to carry out compound.Concrete technological process is: at first with natural flake graphite through chemistry or electrochemical treatment, between the lamella of crystalline graphite, insert the intercalation thing and prepare expansible black lead; Then expansible black lead is placed under the high temperature and make its expansion make specific volume very big as 100～300mL/g even bigger expanded graphite; At last expanded graphite and polymkeric substance are carried out compoundly, be expected to prepare the polymer/graphite nanometer conducing composite material.
Because the specific volume of expanded graphite is very big, even slight stressed fluffy expanded graphite is subsided, therefore make expanded graphite disperse to be compound in the polymeric matrix with nano level graphite wafer form, bigger process implementing difficulty is arranged.The method for preparing the polymer/graphite nanometer conducing composite material mainly contains situ aggregation method, solution intercalation method and melting intercalation method at present.
Situ aggregation method be with the expanded graphite suspended dispersed in polymer monomer, polymer monomer is penetrated between the nano level graphite wafer lamella that expanded graphite expanded, carry out in-situ polymerization then, be dispersed in polymer/graphite nanometer conducing composite material in the polymeric matrix with nano level graphite wafer sheet form thereby prepare graphite.In the polymer/graphite nanometer conducing composite material that situ aggregation method prepares, graphite is dispersed in the polymeric matrix with nano level graphite wafer sheet form substantially, the conduction of matrix material exceedes that to ooze threshold values very low, can obtain the conducing composite material of conductivity excellence under the very low situation of graphite consumption.But the very flexible of situ aggregation method, and expanded graphite is introduced in the polymer monomer at polymerization stage, may bring disadvantageous effect to polymerization process and polymer product quality for the system that has, particularly for the polymkeric substance that has, situ aggregation method is unaccommodated, is that the polyethylene of gas phase polymerization process and polypropylene adopt relatively difficulty of situ aggregation method as industrial polymerization process.
The solution intercalation method is earlier polymer formulation to be become polymers soln, then with the expanded graphite suspended dispersed in polymers soln, treat to remove solvent again after polymers soln penetrates between the nano level graphite wafer lamella that expanded graphite expanded, prepare the polymer/graphite nanometer conducing composite material.The polymer/graphite nanometer conducing composite material that the solution intercalation method prepares, graphite still is dispersed in the polymeric matrix with nano level graphite wafer sheet form substantially, the conduction of matrix material exceedes that to ooze threshold values lower, can prepare the conducing composite material of conductivity excellence under the lower situation of graphite consumption.But the outstanding shortcoming of solution intercalation method is, the solvent difficulty of many polymkeric substance is looked for or is needed special solvent, the solubleness of polymkeric substance is generally less, solvent load is big, and dissolution process is very slow, and the viscosity of high polymeric solution is big, the time that penetrates into the nano level graphite wafer sheet interlayer that expanded graphite expanded is long, removing of the high boiling solvent that has is also very difficult, and therefore the technology cost of this method is very high, and industrial application is subjected to bigger limitation.
Melting intercalation method is that expanded graphite and polymer melt are carried out melting mixing, the effect that utilizes shearing force etc. is directly inserted the fused polymkeric substance between the nano level graphite wafer lamella that expanded graphite expanded, prepares the polymer/graphite nanometer conducing composite material.The method of melting intercalation method is very easy, the technology cost is low, but its fatal shortcoming is, fluffy expanded graphite is carrying out in the process of melt-mixing with polymkeric substance, expanded graphite subsides in a large number, the a large amount of bonding micron order wafers that become of the nano level graphite wafer that has expanded, the viscosity of adding polymer melt is very big, be difficult for penetrating between the nano level graphite wafer lamella that expanded graphite expanded, therefore it is less to be nano level dispersive graphite wafer in the polymer/graphite conducing composite material that melting intercalation method prepares, come down to graphite and be micron order dispersive conducing composite material, exceed and ooze threshold values height, poor electric conductivity.
Three, summary of the invention
The object of the present invention is to provide a kind of method for preparing the polymer/graphite nanometer conducing composite material simple and easy to do, with low cost.
The technical scheme that realizes the object of the invention is: a kind of preparation method of polymer/graphite nanometer conducing composite material, carry out following steps successively:
The first step at high temperature expands expansible black lead and to make expanded graphite;
Second step, expanded graphite is mixed with low molecule compounding agent solution or low molecule additive latex, after treating that low molecule compounding agent solution or low molecule additive latex penetrate between the nano level graphite wafer lamella that expanded graphite expanded, remove the solvent of low molecule compounding agent solution or the dispersion medium of low molecule additive latex, obtain expanded graphite and the low molecule auxiliary agent composite expanded graphite of compound mutually;
In the 3rd step,, make the polymer/graphite nanometer conducing composite material with composite expanded graphite and matrix polymer melting mixing.
Among the preparation method of polymer/graphite nanometer conducing composite material of the present invention, one or more in the softening agent that low molecule auxiliary agent can be a matrix polymer, tenderizer, lubricant, the oligopolymer.
Among the preparation method of polymer/graphite nanometer conducing composite material of the present invention, the mass ratio of low molecule auxiliary agent and expanded graphite should be greater than 0.1.
Among the preparation method of polymer/graphite nanometer conducing composite material of the present invention, matrix polymer can be a thermoplastic polymer, as polyvinyl chloride, polyethylene, polypropylene, polystyrene, polyester, polymeric amide, ABS, polycarbonate or derivatived cellulose.Also can be thermosetting polymer, as Resins, epoxy, resol, unsaturated polyester, natural rubber, cis-1,4-polybutadiene rubber, styrene-butadiene rubber(SBR), polyisoprene rubber, ethylene-propylene rubber(EPR), isoprene-isobutylene rubber or paracril.
Among the preparation method of polymer/graphite nanometer conducing composite material of the present invention, when the composite expanded graphite of preparation, can also in low molecule compounding agent solution or in the disperse phase of low molecule additive latex, dissolve in an amount of polymkeric substance, so that the also compound an amount of polymkeric substance compound low molecule auxiliary agent of expanded graphite the time.
Compared with prior art, the present invention has following remarkable advantage: (1) the present invention can need not to use special and the expensive deleterious solvent of valency, such as, for all selecting hypotoxicity, lower boiling ethanol and acetone for use the low molecule auxiliary agent (as softening agent) of great majority is the low molecule compounding agent solution of solvent preparation, is dispersion medium and be to use inexpensive nontoxic water during the low molecule additive latex of preparation; (2) all preparations easily of low molecule compounding agent solution of the present invention and low molecule additive latex, and the viscosity of low molecule compounding agent solution and low molecule additive latex is all very low, penetrate into easily between the nano level graphite wafer lamella that expanded graphite expanded, seepage velocity is fast, and the speed of dispersion medium that removes the solvent of low molecule compounding agent solution or low molecule additive latex is fast, and therefore composite expanded graphite prepares easily; (3) the polymer/graphite nanometer conducing composite material that makes of preparation method of the present invention exceedes that to ooze threshold values lower, the conductivity excellence; (4) preparation method of the present invention is easy flexibly, and the polymer/graphite nanometer conducing composite material cost for preparing is low, is easy to apply.
Four, description of drawings
Accompanying drawing is preparation method's schema of polymer/graphite nanometer conducing composite material of the present invention.
Five, embodiment
The present invention carries out following steps successively and prepares the polymer/graphite nanometer conducing composite material:
The first step at high temperature expands expansible black lead and to make expanded graphite;
Second step, expanded graphite is mixed with low molecule compounding agent solution or low molecule additive latex, after treating that low molecule compounding agent solution or low molecule additive latex penetrate between the nano level graphite wafer lamella that expanded graphite expanded, remove the solvent of low molecule compounding agent solution or the dispersion medium of low molecule additive latex, obtain expanded graphite and the low molecule auxiliary agent composite expanded graphite of compound mutually;
The 3rd step, composite expanded graphite and matrix polymer are carried out melting mixing, make the polymer/graphite nanometer conducing composite material.
When the present invention prepared composite expanded graphite, low molecule auxiliary agent can be the softening agent of matrix polymer, also can be other low molecule auxiliary agent, as tenderizer and lubricant.Low molecule auxiliary agent can also be oligopolymer (comprising prepolymer), can be the oligopolymer of matrix polymer, also can be the oligopolymer of non-matrix polymer.When the present invention prepares composite expanded graphite, preferably adopt with the good softening agent of matrix polymer consistency as low molecule auxiliary agent.When the present invention prepares composite expanded graphite, can adopt a kind of low molecule auxiliary agent, also can adopt multiple low molecule auxiliary agent.
When the present invention prepared composite expanded graphite, the mass ratio of low molecule auxiliary agent and expanded graphite should be greater than 0.1, more preferably greater than 0.5.If low molecule auxiliary dosage is low excessively, the low molecule auxiliary agent that inserts between the nano level graphite wafer lamella that expanded graphite has expanded is very few, be not enough to the nano level graphite wafer lamella that wetting effectively expanded graphite has expanded, so that be not enough to stop effectively a large amount of again bonding micron order wafers that become of the nano level graphite wafer that has expanded.
When the present invention prepares composite expanded graphite, preferably use the solution of low molecule auxiliary agent to mix, also can use the emulsion of hanging down the molecule auxiliary agent to mix with expanded graphite with expanded graphite.The consumption of low molecule compounding agent solution or low molecule additive latex should guarantee that low molecule compounding agent solution or low molecule additive latex can abundant wetting expanded graphites and penetrate into equably between the nano level graphite wafer lamella that expanded graphite expanded.The blended mode, can be with the expanded graphite suspended dispersed in low molecule compounding agent solution or low molecule additive latex, low molecule compounding agent solution or low molecule additive latex are with the expanded graphite submergence; Also can be that low molecule compounding agent solution or low molecule additive latex are sprayed on the expanded graphite surface, low then molecule compounding agent solution or low molecule additive latex enter between the nano level graphite wafer lamella that expanded graphite expanded by scattering and permeating.The low molecule compounding agent solution of last mode or low molecule additive latex large usage quantity, the low molecule compounding agent solution or the low molecule additive latex consumption of back one mode are less.
When the present invention prepares composite expanded graphite, can in low molecule compounding agent solution or low molecule additive latex, add coupling agent or tensio-active agent, change low molecule auxiliary agent to the wettability of expanded graphite and the surface property of the nano level graphite wafer lamella that changes expanded graphite, improve the nano level graphite wafer lamella of expanded graphite and combine, to improve the mechanical property of final polymer/graphite nanometer conducing composite material with interface between the matrix polymer.
When the present invention prepares composite expanded graphite, can also in low molecule compounding agent solution or in the disperse phase of low molecule additive latex, dissolve in an amount of polymkeric substance, so that the compound an amount of polymkeric substance compound low molecule auxiliary agent of expanded graphite the time.The compound polymkeric substance can be the matrix polymer of polymer/graphite nanometer conducing composite material, also can not be the matrix polymer of polymer/graphite nanometer conducing composite material.
The matrix polymer of polymer/graphite nanometer conducing composite material of the present invention can be a thermoplastic polymer, also can be thermosetting polymer.Thermoplastic polymer can be polyvinyl chloride, polyethylene, polypropylene, polystyrene, polyester, polymeric amide, ABS, polycarbonate or derivatived cellulose, also can be other thermoplastic polymer that can carry out the melting mixing operation.Thermosetting polymer can be Resins, epoxy, resol, unsaturated polyester, natural rubber, cis-1,4-polybutadiene rubber, styrene-butadiene rubber(SBR), polyisoprene rubber, ethylene-propylene rubber(EPR), isoprene-isobutylene rubber or paracril, also can be other thermosetting polymer.Matrix polymer can be a single polymers, also can be polymeric blends.
Embodiment 1
With allowance for expansion is that the commercially available expansible black lead of 250mL/g places 900 ℃ of High Temperature Furnaces Heating Apparatuss expanded, makes expanded graphite.In expanded graphite: dibutyl phthalate: the dehydrated alcohol mass ratio is 1: 2: 30 a ratio, earlier dibutyl phthalate and dehydrated alcohol are mixed to be mixed with solution, then with the expanded graphite suspended dispersed in the ethanol solution of dibutyl phthalate, and place 60 ℃ ultrasound bath supersound process 4h, place 80 ℃ of rotary drum dryer then, be under the situation of 50r/min dehydrated alcohol to be removed at the rotary drum rotating speed, obtain the composite expanded graphite of complex phthalic dibutyl phthalate.
In composite expanded graphite: polyvinyl chloride: calcium/zinc composite stabilizer mass ratio is 36: 62: 2 a ratio, composite expanded graphite, calcium/zinc composite stabilizer and polyvinyl chloride are carried out pre-mixing, adopt single screw extrusion machine to carry out melting mixing at 190 ℃ then and extrude and obtain polyvinyl chloride/graphite conductive nano composites, its volume conductance is 5.4 * 10
-5S/cm.
Embodiment 2
With allowance for expansion is that the commercially available expansible black lead of 300mL/g places 700 ℃ of High Temperature Furnaces Heating Apparatuss expanded, makes expanded graphite.In expanded graphite: dibutyl phthalate: the dehydrated alcohol mass ratio is 1: 0.5: 24 a ratio, earlier dibutyl phthalate and dehydrated alcohol are mixed to be mixed with solution, then with the expanded graphite suspended dispersed in the ethanol solution of dibutyl phthalate, and at 50 ℃ of following 4h that soak, dehydrated alcohol is removed in 50 ℃ of underpressure distillation then, obtains the composite expanded graphite of complex phthalic dibutyl phthalate.
In composite expanded graphite: polyvinyl chloride: calcium/zinc composite stabilizer: phthalic acid two (2-ethylhexyl) mass ratio is 10: 68: 2: 20 ratio, premix is even in kneader with composite expanded graphite, calcium/zinc composite stabilizer, polyvinyl chloride and phthalic acid two (2-ethylhexyl), adopt single screw extrusion machine to carry out melting mixing at 190 ℃ then and extrude and obtain polyvinyl chloride/graphite conductive nano composites, its volume conductance is 4.1 * 10
-9S/cm.
Embodiment 3
With allowance for expansion is that the commercially available expansible black lead of 200mL/g places 900 ℃ of High Temperature Furnaces Heating Apparatuss expanded, makes expanded graphite.In expanded graphite: dibutyl phthalate: the acetone mass ratio is 1: 0.2: 20 a ratio, earlier dibutyl phthalate and acetone are mixed to be mixed with solution, and the titanate coupling agent NDZ-201 of adding expanded graphite quality consumption 6%, then with the expanded graphite suspended dispersed in the acetone soln of dibutyl phthalate, and at 50 ℃ of following 4h that soak, acetone is removed in 50 ℃ of underpressure distillation then, obtains the composite expanded graphite of complex phthalic dibutyl phthalate.
In composite expanded graphite: polyvinyl chloride: calcium/zinc composite stabilizer: phthalic acid two (2-ethylhexyl) mass ratio is 13: 65: 2: 20 ratio, premix is even in kneader with composite expanded graphite, calcium/zinc composite stabilizer, polyvinyl chloride and phthalic acid two (2-ethylhexyl), adopt single screw extrusion machine to carry out melting mixing at 190 ℃ then and extrude and obtain polyvinyl chloride/graphite conductive nano composites, its volume conductance is 3.0 * 10
-7S/cm.
Embodiment 4
With allowance for expansion is that the commercially available expansible black lead of 300mL/g places 600 ℃ of High Temperature Furnaces Heating Apparatuss expanded, makes expanded graphite.In expanded graphite: dibutyl phthalate: phthalic acid two (2-ethylhexyl): the quality ratio is 1: 2: 2: 20 ratio, earlier dibutyl phthalate and phthalic acid two (2-ethylhexyl) are mixed, and be mixed with emulsion with emulsifying water, then with the expanded graphite suspended dispersed at dibutyl phthalate, in the emulsion of phthalic acid two (2-ethylhexyl), and at 60 ℃ of following 4h that soak, 60 ℃ of underpressure distillation remove and anhydrate then, obtain the composite expanded graphite of complex phthalic dibutyl phthalate and phthalic acid two (2-ethylhexyl).
In composite expanded graphite: polyvinyl chloride: calcium/zinc composite stabilizer mass ratio is 55: 43: 2 a ratio, composite expanded graphite, calcium/zinc composite stabilizer and polyvinyl chloride premix is even, adopting single screw extrusion machine to carry out melting mixing at 190 ℃ then extrudes, obtain polyvinyl chloride/graphite conductive nano composites, its volume conductance is 8.4 * 10
-6S/cm.
Embodiment 5
With allowance for expansion is that the commercially available expansible black lead of 250mL/g places 900 ℃ of High Temperature Furnaces Heating Apparatuss expanded, makes expanded graphite.In expanded graphite: diisodecyl adipate: solid paraffin: the ether mass ratio is 1: 2.8: 0.2: 6 ratio, earlier diisodecyl adipate, solid paraffin and ether are mixed to be mixed with solution, then the diethyl ether solution of solid paraffin, diisodecyl adipate is sprayed on the expanded graphite surface in the rotary drum dryer (the rotary drum rotating speed is 50r/min), and at 50 ℃ of following infiltration 4h, heat then ether is removed, obtain the composite expanded graphite of compound diisodecyl adipate and solid paraffin.
Adopt Haake system-40 plasticizing instrument, in composite expanded graphite: the polyethylene mass ratio is 44: 56 a ratio, composite expanded graphite and polyethylene are carried out melting mixing at 185 ℃ obtain the polyethylene/graphite conductive nano composites, its volume conductance is 9.1 * 10
-6S/cm.
Embodiment 6
With allowance for expansion is that the commercially available expansible black lead of 250mL/g places 900 ℃ of High Temperature Furnaces Heating Apparatuss expanded, makes expanded graphite.In expanded graphite: Octyl adipate: maleic anhydride inoculated polypropylene: the toluene mass ratio is 1: 1.5: 0.5: 30 ratio, earlier Octyl adipate and toluene are mixed to be mixed with solution, add maleic anhydride inoculated polypropylene then and be heated to 100 ℃ and make the maleic anhydride inoculated polypropylene dissolving, after treating that maleic anhydride inoculated polypropylene dissolves fully, with the expanded graphite suspended dispersed at maleic anhydride inoculated polypropylene, in the toluene solution of Octyl adipate, and at 90 ℃ of following 5h that soak, heat then toluene evaporates is removed, obtain the composite expanded graphite of compound maleic anhydride inoculated polypropylene and Octyl adipate.
Adopt Haake system-40 plasticizing instrument, in composite expanded graphite: polypropylene: the polyethylene mass ratio is 30: 50: 20 a ratio, composite expanded graphite and polypropylene, polyethylene are carried out melting mixing at 195 ℃ obtain polypropylene, polyethylene/graphite conductive nano composites, its volume conductance is 4.7 * 10
-7S/cm.
Embodiment 7
With allowance for expansion is that the commercially available expansible black lead of 250mL/g places 900 ℃ of High Temperature Furnaces Heating Apparatuss expanded, makes expanded graphite.In expanded graphite: neo-pentyl ethylene glycol bisthioglycolate benzoic ether: the dehydrated alcohol mass ratio is 1: 1: 18 a ratio, earlier neo-pentyl ethylene glycol bisthioglycolate benzoic ether and dehydrated alcohol are mixed to be mixed with solution, then with the expanded graphite suspended dispersed in the ethanol solution of neo-pentyl ethylene glycol bisthioglycolate benzoic ether, soak 4h down at 50 ℃, heat then dehydrated alcohol is removed, obtain the composite expanded graphite of compound neo-pentyl ethylene glycol bisthioglycolate benzoic ether.
In composite expanded graphite: the polyethylene terephthalate mass ratio is 20: 80 a ratio, composite expanded graphite and polyethylene terephthalate premix is even, adopt single screw extrusion machine to carry out melting mixing at 285 ℃ then and extrude and obtain polyethylene terephthalate/graphite conductive nano composites, its volume conductance is 7.3 * 10
-7S/cm.
Embodiment 8
With allowance for expansion is that the commercially available expansible black lead of 250mL/g places 900 ℃ of High Temperature Furnaces Heating Apparatuss expanded, makes expanded graphite.In expanded graphite: butyl benzyl phthalate: the acetone mass ratio is 1: 2: 18 a ratio, earlier butyl benzyl phthalate and acetone are mixed to be mixed with solution, then with the expanded graphite suspended dispersed in the acetone soln of butyl benzyl phthalate, and at 50 ℃ of following 4h that soak, heat then acetone is removed, obtain the composite expanded graphite of complex phthalic acid butyl benzyl.
In composite expanded graphite: resol prepolymer mass ratio is 30: 70 a ratio, composite expanded graphite and resol prepolymer powder elder generation premix is even, adopt single screw extrusion machine to carry out melting mixing then at 100 ℃, being heating and curing at last obtains resol/graphite conductive nano composites, and its volume conductance is 5.6 * 10
-7S/cm.
Embodiment 9
With allowance for expansion is that the commercially available expansible black lead of 250mL/g places 900 ℃ of High Temperature Furnaces Heating Apparatuss expanded, makes expanded graphite.In expanded graphite: Octyl adipate: the methanol quality ratio is 1: 2: 18 a ratio, earlier with Octyl adipate and methanol mixed evenly to be mixed with solution, then with the expanded graphite suspended dispersed in the methanol solution of Octyl adipate, and at 50 ℃ of following 4h that soak, water flush away methyl alcohol is also dried then, obtains the composite expanded graphite of compound Octyl adipate.
Adopt mill, composite expanded graphite, sulphur and benzothiazolyl mercaptan sneaked into make the styrene-butadiene rubber(SBR) rubber unvulcanizate in the styrene-butadiene rubber(SBR) rubber, the massfraction of wherein composite expanded graphite, sulphur and benzothiazolyl mercaptan is respectively 36%, 4% and 1%, then the styrene-butadiene rubber(SBR) rubber unvulcanizate is obtained styrene-butadiene rubber(SBR)/graphite conductive nano composites 165 ℃ of sulfurations, its volume conductance is 3.2 * 10
-5S/cm.
Embodiment 10
With allowance for expansion is that the commercially available expansible black lead of 250mL/g places 900 ℃ of High Temperature Furnaces Heating Apparatuss expanded, makes expanded graphite.In expanded graphite: Resorcinol type Resins, epoxy 680: dibutyl phthalate: the benzene mass ratio is 1: 0.5: 1: 18 ratio, earlier Resorcinol type Resins, epoxy 680, dibutyl phthalate and benzene are mixed to be mixed with solution, then with the expanded graphite suspended dispersed in the benzole soln of Resorcinol type Resins, epoxy 680, dibutyl phthalate, and at 50 ℃ of following 4h that soak, heat then benzene is removed, obtain the composite expanded graphite of complex phthalic dibutyl phthalate and Resorcinol type Resins, epoxy 680.
With the composite expanded graphite and the tricyanic acid three-glycidyl Resins, epoxy (ARRLLditePT810 of the Ciba-Geig company trade mark, white powder, 85～90 ℃ of fusing points), polyfunctional group acid anhydrides PAPA is even 100 ℃ of following melting mixing in 30: 28: 42 ratio of mass ratio, fully obtain Resins, epoxy/graphite conductive nano composites 150 ℃ of following curing at last, its volume conductance is 4.8 * 10
-5S/cm.
Comparative example 1
With allowance for expansion is that the commercially available expansible black lead of 250mL/g places 900 ℃ of High Temperature Furnaces Heating Apparatuss expanded, makes expanded graphite.In expanded graphite: dibutyl phthalate: polyvinyl chloride: calcium/zinc composite stabilizer mass ratio is 12: 24: 62: 2 ratio, expanded graphite, dibutyl phthalate, calcium/zinc composite stabilizer and polyvinyl chloride premix in kneader is even, adopt single screw extrusion machine to carry out melting mixing at 190 ℃ then and extrude and obtain polyvinyl chloride/graphite conductive nano composites, its volume conductance is 1.4 * 10
-7S/cm.
Comparative example 2
With allowance for expansion is that the commercially available expansible black lead of 250mL/g places 900 ℃ of High Temperature Furnaces Heating Apparatuss expanded, makes expanded graphite.Adopt Haake system-40 plasticizing instrument, in expanded graphite: diisodecyl adipate: solid paraffin: poly mass ratio is 11: 30.8: 2.2: 56 ratio, expanded graphite, diisodecyl adipate, solid paraffin and polyethylene are carried out melting mixing at 190 ℃ obtain the polyethylene/graphite conductive nano composites, its volume conductance is 2.1 * 10
-8S/cm.
Claims (7)
1, a kind of preparation method of polymer/graphite nanometer conducing composite material is characterized in that: carry out following steps successively:
The first step at high temperature expands expansible black lead and to make expanded graphite;
Second step, expanded graphite is mixed with low molecule compounding agent solution or low molecule additive latex, after treating that low molecule compounding agent solution or low molecule additive latex penetrate between the nano level graphite wafer lamella that expanded graphite expanded, remove the solvent of low molecule compounding agent solution or the dispersion medium of low molecule additive latex, obtain expanded graphite and the low molecule auxiliary agent composite expanded graphite of compound mutually;
In the 3rd step,, make the polymer/graphite nanometer conducing composite material with composite expanded graphite and matrix polymer melting mixing.
2, the preparation method of polymer/graphite nanometer conducing composite material according to claim 1 is characterized in that: low molecule auxiliary agent is one or more in softening agent, tenderizer, lubricant, the oligopolymer.
3, the preparation method of polymer/graphite nanometer conducing composite material according to claim 1 is characterized in that: the mass ratio of low molecule auxiliary agent and expanded graphite is greater than 0.1.
4, the preparation method of polymer/graphite nanometer conducing composite material according to claim 1 is characterized in that: matrix polymer is thermoplastic polymer or thermosetting polymer.
5, the preparation method of polymer/graphite nanometer conducing composite material according to claim 4 is characterized in that: thermoplastic polymer is polyvinyl chloride, polyethylene, polypropylene, polystyrene, polyester, polymeric amide, ABS, polycarbonate or derivatived cellulose.
6, the preparation method of polymer/graphite nanometer conducing composite material according to claim 4 is characterized in that: thermosetting polymer is Resins, epoxy, resol, unsaturated polyester, natural rubber, cis-1,4-polybutadiene rubber, styrene-butadiene rubber(SBR), polyisoprene rubber, ethylene-propylene rubber(EPR), isoprene-isobutylene rubber or paracril.
7, according to the preparation method of each described polymer/graphite nanometer conducing composite material of claim 1 to 6, it is characterized in that: when preparing composite expanded graphite, in low molecule compounding agent solution or in the disperse phase of low molecule additive latex, be dissolved with an amount of polymkeric substance, so that the compound an amount of polymkeric substance compound low molecule auxiliary agent of expanded graphite the time.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100401008A CN100430338C (en) | 2005-05-19 | 2005-05-19 | Process for preparing polymer and graphite conductive nano composites |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100401008A CN100430338C (en) | 2005-05-19 | 2005-05-19 | Process for preparing polymer and graphite conductive nano composites |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1827553A true CN1827553A (en) | 2006-09-06 |
| CN100430338C CN100430338C (en) | 2008-11-05 |
Family
ID=36946138
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100401008A Expired - Fee Related CN100430338C (en) | 2005-05-19 | 2005-05-19 | Process for preparing polymer and graphite conductive nano composites |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100430338C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103740092A (en) * | 2013-12-18 | 2014-04-23 | 江苏悦达新材料科技有限公司 | High-thermal conductivity graphene/nylon composite material and preparation method thereof |
| CN104033607A (en) * | 2013-11-14 | 2014-09-10 | 三峡大学 | Flake graphite composite sealing plate and manufacturing method |
| CN105585837A (en) * | 2016-03-14 | 2016-05-18 | 昆山聚威工程塑料有限公司 | Polyamide antistatic composite material |
| CN113185762A (en) * | 2021-05-07 | 2021-07-30 | 中国科学院深圳先进技术研究院 | Expanded graphite thermal interface material and preparation method thereof |
| CN113921844A (en) * | 2021-11-15 | 2022-01-11 | 成都先进金属材料产业技术研究院股份有限公司 | Styrene butadiene rubber-based bipolar plate for all-vanadium redox flow battery and preparation method thereof |
| CN116120682A (en) * | 2022-11-29 | 2023-05-16 | 佛山科学技术学院 | Preparation method and application of polyvinylidene fluoride/expanded graphite composite material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1262593C (en) * | 2004-05-13 | 2006-07-05 | 华侨大学 | High electricity conductive polymer composite material and its preparation method |
-
2005
- 2005-05-19 CN CNB2005100401008A patent/CN100430338C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104033607A (en) * | 2013-11-14 | 2014-09-10 | 三峡大学 | Flake graphite composite sealing plate and manufacturing method |
| CN104033607B (en) * | 2013-11-14 | 2016-01-06 | 三峡大学 | A kind of crystalline flake graphite compound seal plate and manufacture method |
| CN103740092A (en) * | 2013-12-18 | 2014-04-23 | 江苏悦达新材料科技有限公司 | High-thermal conductivity graphene/nylon composite material and preparation method thereof |
| CN103740092B (en) * | 2013-12-18 | 2016-01-20 | 江苏悦达新材料科技有限公司 | A kind of high thermal conductivity graphene/nylon composite material and preparation method thereof |
| CN105585837A (en) * | 2016-03-14 | 2016-05-18 | 昆山聚威工程塑料有限公司 | Polyamide antistatic composite material |
| CN113185762A (en) * | 2021-05-07 | 2021-07-30 | 中国科学院深圳先进技术研究院 | Expanded graphite thermal interface material and preparation method thereof |
| CN113921844A (en) * | 2021-11-15 | 2022-01-11 | 成都先进金属材料产业技术研究院股份有限公司 | Styrene butadiene rubber-based bipolar plate for all-vanadium redox flow battery and preparation method thereof |
| CN116120682A (en) * | 2022-11-29 | 2023-05-16 | 佛山科学技术学院 | Preparation method and application of polyvinylidene fluoride/expanded graphite composite material |
| CN116120682B (en) * | 2022-11-29 | 2024-01-30 | 佛山科学技术学院 | Preparation method and application of polyvinylidene fluoride/expanded graphite composite material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100430338C (en) | 2008-11-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100430338C (en) | Process for preparing polymer and graphite conductive nano composites | |
| CN105482417A (en) | Method for preparing graphene-containing polymer composite | |
| CN1858101A (en) | Inorganic nano particle modified high performance recovery plastic and its preparing process | |
| Liu et al. | Constructing a double-percolated conductive network in a carbon nanotube/polymer-based flexible semiconducting composite | |
| CN101275036B (en) | Preparation for polymer conductive nanometer compound material | |
| CN106543563B (en) | Thermoplastic high-voltage cable insulating material and preparation method thereof | |
| CN100412126C (en) | Composite material of similar fluid inorganic nano particle and polymer and preparation thereof | |
| CN102675893B (en) | Method for preparing polymer-based conducting composite material by melt blending | |
| CN100338118C (en) | Preparation method of biodegradable calcium phosphorus inorganic bioparticlel polymer composite material | |
| CN1974649A (en) | Method of utilizing waste unsaturated polyester button and handicraft in modifying plastic | |
| CN1305513A (en) | Modifier for improving behavior of bituminous mixtures used in road paving | |
| CN102336968A (en) | Modified polypropylene composite material and preparation method thereof | |
| CN107227031A (en) | Nano combined asphalt modifier and preparation method thereof | |
| CN103881403A (en) | Ultraviolet-rejected solid asphalt, preparation and application thereof | |
| CN1182199C (en) | Stable polymer-asphalt comosition | |
| JP2018111770A (en) | Gelatinous body, manufacturing method of gelatinous body, composite material and manufacturing method of composite material | |
| CN109384989B (en) | Dry-wet combined environment-friendly anti-rutting asphalt mixture | |
| CN1733833A (en) | SBS modified asphalt mother grain and its preparation method | |
| CN103087438A (en) | Impact-resistant polyvinyl chloride composition and preparation method thereof | |
| CN1167735C (en) | Composition composed of liquid rubber and clay | |
| CN104710692A (en) | Solubilizer for improving performance of natural rubber-ethylene propylene rubber co-blended rubber and preparation method thereof | |
| CN100349984C (en) | Danty composition modified asphalt and its preparing method | |
| CN114276641A (en) | In-situ compatibilization and chain extension based regenerated HIPS/PP alloy material and preparation method thereof | |
| CN1281678C (en) | Asphalt modified masterbatch and method for preparation | |
| CN1281677C (en) | Grafting type asphalt modified masterbatch and method for preparation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20081105 Termination date: 20100519 |