CN103755849A - Carbon nanotube-polysilane-organic high-molecular composite material and preparation method thereof - Google Patents
Carbon nanotube-polysilane-organic high-molecular composite material and preparation method thereof Download PDFInfo
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- CN103755849A CN103755849A CN201410062162.8A CN201410062162A CN103755849A CN 103755849 A CN103755849 A CN 103755849A CN 201410062162 A CN201410062162 A CN 201410062162A CN 103755849 A CN103755849 A CN 103755849A
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Abstract
The invention discloses a carbon nanotube-polysilane-organic high-molecular composite material and a preparation method thereof, relates to a composite material and a preparation method thereof, and aims to solve the problems that when the conventional carbon nanotube/organic high-molecular composite material is prepared, the dispersity of a carbon nanotube is poor, and at present, the dispersity is increased mostly through a method of changing the structure of the carbon nanotube or using a conventional carbonaceous organic material to coat the carbon nanotube. The method comprises the following steps: 1, purifying the carbon nanotube; 2, preparing an alkali metal organic solvent suspension liquid; 3, polymerizing silane monomers to prepare polysilane; 4, purifying the polysilane; 5, compositing the carbon nanotube and the polysilane; 6, evaporating a solvent; 7, adopting an in-situ polymerization method to prepare the carbon nanotube-polysilane-organic polymer composite material. The method has the advantages as follows: the polysilane is added to enable the carbon nanotube to have good dispersity in organic polymers under the condition of ensuring the intact structure of the carbon nanotube, and the performance is greatly improved. The operation is simple and easy, and is easily controlled, and all processes are not mutually influenced.
Description
Technical field
What the present invention relates to is a kind of matrix material and preparation method thereof.
Background technology
Since carbon nanotube is found, due to its unique construction and character, and has been used as additive application in the preparation of various matrix materials, thereby has effectively changed the mechanics of polymkeric substance, optical, electrical character and thermostability.Yet, the surperficial relative inertness of carbon nanotube, be dissolved in hardly most of organic solvents, and the high surface energy that the winding causing due to its big L/D ratio and high-specific surface area cause, so normal, easily reunite, cause carbon nanotube at the non-constant of the degree of scatter in polymeric matrix, the performance of carbon nano-tube/polymer composite material can not get embodying well, has limited its range of application.
In order to improve the dispersiveness of carbon nanotube in macromolecular material, can adopt chemical modification and the large class methods of physically modified two.Chemical modification refers to through chemical reagent or pyroprocessing, and the closing structure of carbon nano tube surface is opened, and forms several active sites, as hydroxyl or carboxyl, thereby improves its consistency in matrix.The problem that this method exists is: the distinctive structure of carbon nanotube is broken, the sp in functionalization site
2hybrid structure is simultaneously destroyed, and its some performance (as electroconductibility) will be greatly affected; Physical modified method refers to that carbon nanotube is combined coating materials (as ionic surface active agent or organic polymer) is wrapped in to carbon nano tube surface by Van der Waals force, π-π interaction etc. with functional group.Compare with chemical modification, physically modified can the original chemical structure of destroying carbon nanometer tube self, can its good mechanics of complete reservation, the performance such as electricity.Therefore, if do not changing under the prerequisite of carbon nanotube structure, improve its dispersiveness in macromolecular material, will expand the range of application of carbon nanotube in matrix material, make the functional materials of various excellent performances.
But along with the develop rapidly of global economy, petroleum resources are day by day deficient, cause take the price of chemical products that carbon is chief component day by day to raise.In recent years, take the macromolecular material that silicon is main raw flourish.First, silicon is the abundantest element of reserves on the earth, and along with the continuous minimizing of petroleum resources, while originating finding resource that can petroleum replacing non-carbon functional materials abundant, silicon is first-selected naturally; Secondly the silicon of take can synthesize multiple conductive polymers as raw material, and their specific conductivity can change in the wider scope of isolator-semi-conductor-metallic state, and this is that other material is incomparable at present.In addition, these polymkeric substance have the features such as structure diversification, easy processing.
Therefore, if material is applied in existing chemical industry, functional materials production, substitute conventional organic reagent, will become the fine selection of low-carbon economy.The present invention is about to polysilane as carbon nanotube physically modified modifier, is wrapped in carbon nano tube surface, thereby improves the dispersiveness of carbon nanotube in macromolecular material.
Summary of the invention
The bad dispersibility of carbon nanotube when the object of the invention is existing carbon nanotube/organic polymer composite and preparing, and existing mostly by changing carbon nanotube structure or improving dispersed problem by the coated method of conventional carbonaceous organic material, and a kind of carbon nanotube-polysilane-organic polymer composite and preparation method thereof is provided.
A kind of carbon nanotube-polysilane-organic polymer composite of the present invention, to be made by carbon nanotube, organic solvent, dichlorosilane, trichlorosilane, basic metal, reaction terminating agent, blend organic solvent, organic polymer monomer and initiator, wherein, the quality of described dichlorosilane and the volume ratio of organic solvent are 1g:(60mL～125mL); Described dichlorosilane and alkali-metal mass ratio are (0.8～2): 1; Described dichlorosilane and the mass ratio of trichlorosilane are 1:(0～4); The quality of described dichlorosilane and the volume ratio of reaction terminating agent are 1g:(30mL～60mL); Described carbon nanotube and the mass ratio of dichlorosilane are 1:(1～10); The described carbon nanotube together mass volume ratio of mixed organic solvent is 1g:(15mL～240mL); Described organic polymer monomer and carbon nanotube mass ratio are (10～100): 1; The mass ratio of described initiator and organic polymer monomer is 1:(40～100).
The preparation method of a kind of carbon nanotube-polysilane-organic polymer composite of the present invention, carries out according to following steps:
One, Purification of Carbon Nanotubes: carbon nanotube is carried out to high-temperature calcination and acid treatment, obtain the carbon nanotube after purifying;
Two, prepare basic metal solvent suspension liquid: basic metal is added in organic solvent, form mixed solution, mixed solution is added in reaction unit, and low whipping speed is that 1000r/min～1500r/min, temperature are the 0.5h～1h that refluxes under 80 ℃～120 ℃ and nitrogen protection, then naturally cooling, obtains basic metal/organic solvent suspension;
Three, prepare silane monomer/organic solvent solution: dichlorosilane and trichlorosilane are dissolved in to organic solvent, mix and obtain silane monomer/organic solvent solution;
Four, polysilane is prepared in silane monomer polymerization: the silane monomer of step 3/organic solvent solution is imported in constant pressure funnel, then low whipping speed is 600r/min～1000r/min, temperature is 60 ℃～80 ℃, under the condition of nitrogen protection and lucifuge, by 1mL/min～1.5mL/min rate of addition, be added dropwise in step 2 gained basic metal/organic solvent suspension, after dropwising, control stirring velocity at 600r/min～1000r/min, temperature is at 80 ℃～120 ℃, under nitrogen protection and lucifuge condition, carry out back flow reaction, reaction times is 6h～8h, then be cooled to room temperature, carry out solid-liquid separation, obtain the mixture filtrate of polymkeric substance,
Five, purification polysilane: step 4 gained filtrate is used to Rotary Evaporators evaporating solvent, remaining liq is poured in beaker, added tetrahydrofuran (THF) to dissolve, then add reaction terminating agent to separate out polysilane, finally beaker lucifuge is stirred to 24h, solid-liquid separation, washing, the dry polysilane that obtains;
Six, carbon nanotube and polysilane are compound: the carbon nanotube after the purifying that step 1 is obtained is put into respectively blend organic solvent with the polysilane that step 5 obtains after grinding, and control temperature in 50 ℃, the ultrasonic concussion 4h of difference, then mix, after ultrasonic concussion 8h, obtain mixed solution;
Seven, evaporating solvent: by after the mixed solution evaporating solvent of step 6, vacuum-drying 24h, obtains carbon nano-tube/poly silane matrix material;
Eight, adopt situ aggregation method to prepare carbon nanotube-polysilane-organic polymer composite: to take the Powdered matrix material of carbon nano-tube/poly silane prepared by step 7, join in organic polymer monomer, reaction unit is placed in to ultrasonic thermostatic water bath, at bath temperature, be raised to after 75 ℃, add initiator, under ul-trasonic irradiation, carry out polyreaction, after question response 6h, liquid after prepolymerization is poured in mould, then mould is put into baking oven and in temperature be under the condition of 100 ℃, continue polymerization 8h, after cooling, obtain carbon nanotube-polysilane-organic polymer composite,
The mass volume ratio of the basic metal described in step 2 and organic solvent is 1g:(30mL～100mL);
Described in the quality of dichlorosilane described in step 3 and step 2, the volume ratio of organic solvent is 1g:(30mL～40mL); Described in dichlorosilane described in step 3 and step 2, alkali-metal mass ratio is (0.8～2): 1; Described in step 3, the mass ratio of dichlorosilane and trichlorosilane is 1:(0～4); Described in step 3, described in the quality of dichlorosilane and step 3, the volume ratio of organic solvent is 1g:(30mL～85mL); Described in the volume of tetrahydrofuran (THF) described in step 5 and step 3, dichlorosilane mass ratio is (5mL～20mL): 1g; Reaction terminating agent described in step 5 and tetrahydrofuran (THF) volume ratio are (5～12): 1; Described in step 6, carbon nanotube quality and polysilane mass ratio are 1:(1～4); Blend organic solvent volume described in step 6 and polysilane mass ratio are (15mL～60mL): 1g; Organic polymer monomer mass described in step 8 and carbon nano-tube/poly silane matrix material mass ratio are (5～20): 1; The mass ratio of the initiator described in step 8 and organic polymer monomer is 1:(40～100).
The present invention comprises following beneficial effect:
A kind of preparation method of carbon nanotube-polysilane-organic polymer composite of the present invention has plurality of advantages, guaranteeing under carbon nanotube structure fine status, adopt non-carbon surface modifier, add polysilane, make it under pi-pi accumulation effect, be coated on carbon nano tube surface, thereby improve the dispersiveness of carbon nanotube, and the performance of organic polymer material (organic polymer is polystyrene, polyethylene, polymethylmethacrylate) is increased dramatically, whole process operation is simple, easily control, and each process is independent of each other.
The present invention by pure polystyrene, Carbon Nanotubes/Polystyrene Nanocomposites, carbon nanotube-polysilane-poly styrene composite material by adding the carbon nanotube of different mass mark (wt%) to carry out specific conductivity test, test result shows, when in Carbon Nanotubes/Polystyrene Nanocomposites, content of carbon nanotubes is increased to 6% from 0, specific conductivity is from 4.187 * 10
-12s/cm is increased to 8.062 * 10
-10s/cm, has only increased by two orders of magnitude, and when in carbon nanotube-polysilane-poly styrene composite material, carbon nanotube is increased to 4% from 0, specific conductivity is from 4.187 * 10
-12s/cm is increased to 4.356 * 10
-9s/cm, has increased by three orders of magnitude, and when content is increased to 6%, specific conductivity has increased by six orders of magnitude, illustrates in the situation that there is no polysilane, and the dispersiveness of carbon nanotube is relatively poor, make matrix material conductivity can not be improved significantly.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of the carbon nanotube of the purifying that obtains of testing sequence one;
Fig. 2 is the branched polysilane infrared spectrum in test one;
Fig. 3 is the carbon nanotube/branched polysilane matrix material infrared spectrum in test one;
Fig. 4 is polystyrene surface figure;
Fig. 5 is carbon nano-tube/poly vinylbenzene exterior view;
Fig. 6 is carbon nanotube-polysilane-polystyrene surface figure.
Embodiment
Embodiment one: the preparation method of a kind of carbon nanotube-polysilane-organic polymer composite of present embodiment, carries out according to following steps:
One, Purification of Carbon Nanotubes: carbon nanotube is carried out to high-temperature calcination and acid treatment, obtain the carbon nanotube after purifying;
Two, prepare basic metal organic solvent suspension: basic metal is added in organic solvent, form mixed solution, mixed solution is added in reaction unit, and low whipping speed is that 1000r/min～1500r/min, temperature are the 0.5h～1h that refluxes under 80 ℃～120 ℃ and nitrogen protection, then naturally cooling, obtains basic metal/organic solvent suspension;
Three, prepare silane monomer/organic solvent solution: dichlorosilane and trichlorosilane are dissolved in to organic solvent, mix and obtain silane monomer/organic solvent solution;
Four, polysilane is prepared in silane monomer polymerization: the silane monomer of step 3/organic solvent solution is imported in constant pressure funnel, then low whipping speed is 600r/min～1000r/min, temperature is 60 ℃～80 ℃, under the condition of nitrogen protection and lucifuge, by 1mL/min～1.5mL/min rate of addition, be added dropwise in step 2 gained basic metal/organic solvent suspension, after dropwising, control stirring velocity at 600r/min～1000r/min, temperature is at 80 ℃～120 ℃, under nitrogen protection and lucifuge condition, carry out back flow reaction, reaction times is 6h～8h, then be cooled to room temperature, carry out solid-liquid separation, obtain the mixture filtrate of polymkeric substance,
Five, purification polysilane: step 4 gained filtrate is used to Rotary Evaporators evaporating solvent, remaining liq is poured in beaker, added tetrahydrofuran (THF) to dissolve, then add reaction terminating agent to separate out polysilane, finally beaker lucifuge is stirred to 24h, solid-liquid separation, washing, the dry polysilane that obtains;
Six, carbon nanotube and polysilane are compound: the carbon nanotube after the purifying that step 1 is obtained is put into respectively blend organic solvent with the polysilane that step 5 obtains after grinding, and control temperature in 50 ℃, the ultrasonic concussion 4h of difference, then mix, after ultrasonic concussion 8h, obtain mixed solution;
Seven, evaporating solvent: by after the mixed solution evaporating solvent of step 6, vacuum-drying 24h, obtains carbon nano-tube/poly silane matrix material;
Eight, adopt situ aggregation method to prepare carbon nanotube-polysilane-organic polymer composite: to take the Powdered matrix material of carbon nano-tube/poly silane prepared by step 7, join in organic polymer monomer, reaction unit is placed in to ultrasonic thermostatic water bath, at bath temperature, be raised to after 75 ℃, add initiator, under ul-trasonic irradiation, carry out polyreaction, after question response 6h, liquid after prepolymerization is poured in mould, then mould is put into baking oven and in temperature be under the condition of 100 ℃, continue polymerization 8h, after cooling, obtain carbon nanotube-polysilane-organic polymer composite,
The mass volume ratio of the basic metal described in step 2 and organic solvent is 1g:(30mL～100mL);
Described in the quality of dichlorosilane described in step 3 and step 2, the volume ratio of organic solvent is 1g:(30mL～40mL); Described in dichlorosilane described in step 3 and step 2, alkali-metal mass ratio is (0.8～2): 1; Described in step 3, the mass ratio of dichlorosilane and trichlorosilane is 1:(0～4); Described in step 3, described in the quality of dichlorosilane and step 3, the volume ratio of organic solvent is 1g:(30mL～85mL); Described in the volume of tetrahydrofuran (THF) described in step 5 and step 3, dichlorosilane mass ratio is (5mL～20mL): 1g; Reaction terminating agent described in step 5 and tetrahydrofuran (THF) volume ratio are (5～12): 1; Described in step 6, carbon nanotube quality and polysilane mass ratio are 1:(1～4); Blend organic solvent volume described in step 6 and polysilane mass ratio are (15mL～60mL): 1g; Organic polymer monomer mass described in step 8 and carbon nano-tube/poly silane matrix material mass ratio are (5～20): 1; The mass ratio of the initiator described in step 8 and organic polymer monomer is 1:(40～100).
A kind of preparation method of the carbon nanotube-polysilane-organic polymer composite of present embodiment has plurality of advantages, guaranteeing under carbon nanotube structure fine status, adopt non-carbon surface modifier, add polysilane, make it under pi-pi accumulation effect, be coated on carbon nano tube surface, thereby improve the dispersiveness of carbon nanotube, and the performance of organic polymer material is increased dramatically, whole process operation is simple, easily control, and each process is independent of each other.
Present embodiment by pure polystyrene, Carbon Nanotubes/Polystyrene Nanocomposites, carbon nanotube-polysilane-poly styrene composite material by adding the carbon nanotube of different mass mark (wt%) to carry out specific conductivity test, test result shows, when in Carbon Nanotubes/Polystyrene Nanocomposites, content of carbon nanotubes is increased to 6% from 0, specific conductivity is from 4.187 * 10
-12s/cm is increased to 8.062 * 10
-10s/cm, has only increased by two orders of magnitude, and when in carbon nanotube-polysilane-poly styrene composite material, carbon nanotube is increased to 4% from 0, specific conductivity is from 4.187 * 10
-12s/cm is increased to 4.356 * 10
-9s/cm, has increased by three orders of magnitude, and when content is increased to 6%, specific conductivity has increased by six orders of magnitude, illustrates in the situation that there is no polysilane, and the dispersiveness of carbon nanotube is relatively poor, make matrix material conductivity can not be improved significantly.
Embodiment two: present embodiment is different from embodiment one: described in step 1, carbon nanotube is carried out to high-temperature calcination and acid treatment, concrete operations are as follows: one, calcination processing: carbon nanotube is put into retort furnace, keeping temperature is 450 ℃～500 ℃, takes out after calcining about 30min; Two, HCl processes: the calcinate that step 1 is obtained is put into 5mol/LHCl solution again, be heated to 100～120 ℃ of backflow 6h～7h, then filter with sand core funnel, collect solid formation, deionized water rinsing dry for gained solid formation, obtains the carbon nanotube after purification process.Other is identical with embodiment one.
Embodiment three: present embodiment is different from embodiment one or two: described in step 2 is that low whipping speed is that 1000r/min～1500r/min, temperature are condensing reflux 0.5h～1h under 100 ℃～120 ℃ and nitrogen protection.Other is identical with embodiment one or two.
Embodiment four: present embodiment is different from one of embodiment one to three: described in step 2 and low whipping speed be that 1000r/min～1500r/min, temperature are condensing reflux 0.5h～1h under 110 ℃～120 ℃ and nitrogen protection.Other is identical with one of embodiment one to three.
Embodiment five: present embodiment is different from one of embodiment one to four: being added dropwise in step 2 gained basic metal/organic solvent suspension by 1.2mL/min～1.5mL/min rate of addition described in step 4.Other is identical with one of embodiment one to four.
Embodiment six: present embodiment is different from one of embodiment one to five: being added dropwise in step 2 gained basic metal/organic solvent suspension by 1.5mL/min rate of addition described in step 4.Other is identical with one of embodiment one to five.
Embodiment seven: present embodiment is different from one of embodiment one to six: the control stirring velocity described in step 4 is carried out back flow reaction at 600r/min～1000r/min, temperature under 100 ℃～120 ℃, nitrogen protection and lucifuge condition, and the reaction times is 6h～8h.Other is identical with one of embodiment one to six.
Embodiment eight: present embodiment is different from one of embodiment one to seven: the quality of the dichlorosilane described in step 3 and the volume ratio of organic solvent are 1g:(35～50) mL.Other is identical with one of embodiment one to seven.
Embodiment nine: present embodiment is different from one of embodiment one to eight: the dichlorosilane described in step 3 and alkali-metal mass ratio are (1～1.8): 1.Other is identical with one of embodiment one to eight.
Embodiment ten: present embodiment is different from one of embodiment one to nine: the dichlorosilane described in step 3 and alkali-metal mass ratio are (1.4～1.6): 1.Other is identical with one of embodiment one to nine.
Embodiment 11: present embodiment is different from one of embodiment one to ten: the dichlorosilane described in step 3 and the mass ratio of trichlorosilane are 1:(2～4).Other is identical with one of embodiment one to ten.
Embodiment 12: present embodiment is different from one of embodiment one to 11: the dichlorosilane described in step 3 and the mass ratio of trichlorosilane are 1:(2.5～3).Other is identical with one of embodiment one to 11.
Embodiment 13: present embodiment is different from one of embodiment one to 12: the quality of the dichlorosilane described in step 3 and the volume ratio of organic solvent are 1g:35mL.Other is identical with one of embodiment one to 12.
Embodiment 14: present embodiment is different from one of embodiment one to 13: the tetrahydrofuran (THF) volume described in step 5 and dichlorosilane mass ratio are (7mL～15mL): 1g.Other is identical with one of embodiment one to 13.
Embodiment 15: present embodiment is different from one of embodiment one to 14: reaction terminating agent described in step 5 and tetrahydrofuran (THF) volume ratio are (10～12): 1.Other is identical with one of embodiment one to 14.
Embodiment 16: present embodiment is different from one of embodiment one to 15: described in step 6, carbon nanotube and polysilane mass ratio are 1:(1～3).Other is identical with one of embodiment one to 15.
Embodiment 17: present embodiment is different from one of embodiment one to 16: described in step 6, carbon nanotube and polysilane mass ratio are 1:(1～2).Other is identical with one of embodiment one to 16.
Embodiment 18: present embodiment is different from one of embodiment one to 17: described in step 5, carbon nanotube and polysilane mass ratio are 1:(1～1.5).Other is identical with one of embodiment one to 17.
Embodiment 19: present embodiment is different from one of embodiment one to 18: described in step 6, carbon nanotube and polysilane mass ratio are 1:1.5.Other is identical with one of embodiment one to 18.
Embodiment 20: present embodiment is different from one of embodiment one to 19: described in step 6, organic solvent volume and polysilane mass ratio are (20mL～40mL): 1g.Other is identical with one of embodiment one to 19.
Embodiment 21: present embodiment is different from one of embodiment one to 20: described in step 6, organic solvent volume and silane mass ratio are 30mL:1g.Other is identical with one of embodiment one to 20.
Embodiment 22: present embodiment is different from one of embodiment one to 21: the organic polymer monomer mass described in step 8 and carbon nano-tube/poly silane matrix material mass ratio are (5～18): 1.Other is identical with one of embodiment one to 21.
Embodiment 23: present embodiment is different from one of embodiment one to 22: the organic polymer monomer mass described in step 8 and carbon nano-tube/poly silane matrix material mass ratio are (7～16): 1.Other is identical with one of embodiment one to 22.
Embodiment 24: present embodiment is different from one of embodiment one to 23: the organic polymer monomer mass described in step 8 and carbon nano-tube/poly silane matrix material mass ratio are (8～14): 1.Other is identical with one of embodiment one to 23.
Embodiment 25: present embodiment is different from one of embodiment one to 24: the organic polymer monomer mass described in step 8 and carbon nano-tube/poly silane matrix material mass ratio are (9～12): 1.Other is identical with one of embodiment one to 24.
Embodiment 26: present embodiment is different from one of embodiment one to 25: the organic polymer monomer mass described in step 8 and carbon nano-tube/poly silane matrix material mass ratio are 10:1.Other is identical with one of embodiment one to 25.
Embodiment 27: present embodiment is different from one of embodiment one to 26: the mass ratio of the initiator described in step 8 and organic polymer monomer is 1:(50～80).Other is identical with one of embodiment one to 26.
Embodiment 28: present embodiment is different from one of embodiment one to 27: the mass ratio of the initiator described in step 8 and organic polymer monomer is 1:(60～80).Other is identical with one of embodiment one to 27.
Embodiment 29: present embodiment is different from one of embodiment one to 28: the mass ratio of the initiator described in step 8 and organic polymer monomer is 1:70.Other is identical with one of embodiment one to 28.
Embodiment 30: present embodiment is different from one of embodiment one to 29: described organic solvent is toluene, dimethylbenzene, octane or suberane.Other is identical with one of embodiment one to 29.
Embodiment 31: present embodiment is different from one of embodiment one to 30: described basic metal is sodium Metal 99.5 or Na-K alloy.Other is identical with one of embodiment one to 30.
Embodiment 32: present embodiment is different from one of embodiment one to 31: described reaction terminating agent is anhydrous isopropyl alcohol or dehydrated alcohol.Other is identical with one of embodiment one to 31.
Embodiment 33: present embodiment is different from one of embodiment one to 32: described blend organic solvent is tetrahydrofuran (THF), toluene, DMF, acetone or dehydrated alcohol.Other is identical with one of embodiment one to 32.
Embodiment 34: present embodiment is different from one of embodiment one to 33: described initiator is Diisopropyl azodicarboxylate, benzoyl peroxide or methylethyl ketone peroxide.Other is identical with one of embodiment one to 33.
Embodiment 35: present embodiment is different from one of embodiment one to 34: described dichlorosilane is dichloromethyl phenylsilane, diphenyl dichlorosilane or methyl ethylene dichlorosilane; Described trichlorosilane is for being METHYL TRICHLORO SILANE, vinyl trichloro silane, phenyl-trichloro-silicane or nonyl trichlorosilane.Other is identical with one of embodiment one to 34.
Embodiment 36: present embodiment is different from one of embodiment one to 35: described carbon nanotube is Single Walled Carbon Nanotube or multi-walled carbon nano-tubes.Other is identical with one of embodiment one to 35.
Embodiment 37: present embodiment is different from one of embodiment one to 36: described polysilane is line style polysilane, branched polysilane or branched polysilanes.Other is identical with one of embodiment one to 36.
Embodiment 38: present embodiment is different from one of embodiment one to 37: described organic polymer monomer is vinylbenzene, ethene or methyl methacrylate.Other is identical with one of embodiment one to 37.
Embodiment 39: a kind of carbon nanotube-polysilane-organic polymer composite of present embodiment, to be made by carbon nanotube, organic solvent, dichlorosilane, trichlorosilane, basic metal, reaction terminating agent, blend organic solvent, organic polymer monomer and initiator, wherein, the quality of described dichlorosilane and the volume ratio of organic solvent are 1g:(60mL～125mL); Described dichlorosilane and alkali-metal mass ratio are (0.8～2): 1; Described dichlorosilane and the mass ratio of trichlorosilane are 1:(0～4); The quality of described dichlorosilane and the volume ratio of reaction terminating agent are 1g:(30mL～60mL); Described carbon nanotube and the mass ratio of dichlorosilane are 1:(1～10); The described carbon nanotube together mass volume ratio of mixed organic solvent is 1g:(15mL～240mL); Described organic polymer monomer and carbon nanotube mass ratio are (10～100): 1; The mass ratio of described initiator and organic polymer monomer is 1:(40～100).
Embodiment 40: present embodiment is different from embodiment 39: described carbon nanotube is Single Walled Carbon Nanotube or multi-walled carbon nano-tubes.Other is identical with embodiment 39.
Embodiment 41: present embodiment is different from embodiment 39 or 40: described polysilane is line style polysilane, branched polysilane or branched polysilanes.Other is identical with embodiment 39 or 40.
Embodiment 42: present embodiment is different from one of embodiment 39 to 41: the quality of described dichlorosilane and the volume ratio of organic solvent are 1g:(35～50) mL.Other is identical with one of embodiment 39 to 41.
Embodiment 43: present embodiment is different from one of embodiment 39 to 42: the quality of described dichlorosilane and the volume ratio of organic solvent are 1g:(40～45) mL.Other is identical with one of embodiment 39 to 42.
Embodiment 44: present embodiment is different from one of embodiment 39 to 43: described dichlorosilane and alkali-metal mass ratio are (1～1.8): 1.Other is identical with one of embodiment 39 to 43.
Embodiment 45: present embodiment is different from one of embodiment 39 to 44: described dichlorosilane and alkali-metal mass ratio are (1.4～1.6): 1.Other is identical with one of embodiment 39 to 44.
Embodiment 46: present embodiment is different from one of embodiment 39 to 45: described dichlorosilane and the mass ratio of trichlorosilane are 1:(2～4).Other is identical with one of embodiment 39 to 45.
Embodiment 47: present embodiment is different from one of embodiment 39 to 46: described dichlorosilane and the mass ratio of trichlorosilane are 1:(2.5～3).Other is identical with one of embodiment 39 to 46.
Embodiment 48: present embodiment is different from one of embodiment 39 to 47: the quality of described dichlorosilane and the volume ratio of reaction terminating agent are 1g:(40mL～50mL).Other is identical with one of embodiment 39 to 47.
Embodiment 49: present embodiment is different from one of embodiment 39 to 48: described carbon nanotube and the mass ratio of dichlorosilane are 1:(2～8).Other is identical with one of embodiment 39 to 48.
Embodiment 50: present embodiment is different from one of embodiment 39 to 49:: described carbon nanotube and the mass ratio of dichlorosilane are 1:(3～7).Other is identical with one of embodiment 39 to 49.
Embodiment 51: present embodiment is different from one of embodiment 39 to 50: described carbon nanotube and the mass ratio of dichlorosilane are 1:(4～6).Other is identical with one of embodiment 39 to 50.
Embodiment 52: present embodiment is different from one of embodiment 39 to 51:: described carbon nanotube and the mass ratio of dichlorosilane are 1:5.Other is identical with one of embodiment 39 to 51.
Embodiment 53: present embodiment is different from one of embodiment 39 to 52: the mass ratio of described initiator and organic polymer monomer is 1:(50～80).Other is identical with one of embodiment 39 to 52.
Embodiment 54: present embodiment is different from one of embodiment 39 to 53: the mass ratio of described initiator and organic polymer monomer is 1:(60～80).Other is identical with one of embodiment 39 to 53.
Embodiment 55: present embodiment is different from one of embodiment 39 to 54: the mass ratio of described initiator and organic polymer monomer is 1:70.Other is identical with one of embodiment 39 to 54.
Embodiment 56: present embodiment is different from one of embodiment 39 to 55: described organic solvent is toluene, dimethylbenzene, octane or suberane.Other is identical with one of embodiment 39 to 55.
Embodiment 57: present embodiment is different from one of embodiment 39 to 56: described basic metal is sodium Metal 99.5 or Na-K alloy.Other is identical with one of embodiment 39 to 56.
Embodiment 58: present embodiment is different from one of embodiment 39 to 57: described reaction terminating agent is anhydrous isopropyl alcohol or dehydrated alcohol.Other is identical with one of embodiment 39 to 57.
Embodiment 59: present embodiment is different from one of embodiment 39 to 58: described blend organic solvent is tetrahydrofuran (THF), toluene, DMF, acetone or dehydrated alcohol.Other is identical with one of embodiment 39 to 58.
Embodiment 60: present embodiment is different from one of embodiment 39 to 59: described initiator is Diisopropyl azodicarboxylate, benzoyl peroxide or methylethyl ketone peroxide.Other is identical with one of embodiment 39 to 59.
Embodiment 61: present embodiment is different from one of embodiment 39 to 60: described dichlorosilane is dichloromethyl phenylsilane, diphenyl dichlorosilane or methyl ethylene dichlorosilane; Described trichlorosilane is for being METHYL TRICHLORO SILANE, vinyl trichloro silane, phenyl-trichloro-silicane or nonyl trichlorosilane.Other is identical with one of embodiment 39 to 60.
Embodiment 62: present embodiment is different from one of embodiment 39 to 61: described organic polymer monomer is vinylbenzene, ethene or methyl methacrylate.Other is identical with one of embodiment 39 to 61.
Embodiment 63: present embodiment is different from one of embodiment 37 to 62: the preparation method of described polysilane is: the silane monomer of step 3/organic solvent solution is imported in constant pressure funnel, then low whipping speed is 600r/min～1000r/min, temperature is 60 ℃～80 ℃, under the condition of nitrogen protection and lucifuge, by 1mL/min～1.5mL/min rate of addition, be added dropwise in step 2 gained basic metal/organic solvent suspension, after dropwising, control stirring velocity at 600r/min～1000r/min, temperature is at 80 ℃～120 ℃, under nitrogen protection and lucifuge condition, carry out back flow reaction, reaction times is 6h～8h, then be cooled to room temperature, carry out solid-liquid separation, obtain the mixture filtrate of polymkeric substance.Other is identical with one of embodiment 37 to 62.
Content of the present invention is not limited only to the content of the respective embodiments described above, and the combination of one of them or several embodiments equally also can realize the object of invention.
Adopt following verification experimental verification effect of the present invention:
Test one:
The preparation method of a kind of carbon nanotube-polysilane-poly styrene composite material of this test, specifically completes according to the following steps:
One, Purification of Carbon Nanotubes is processed;
Two, prepare basic metal/organic solvent suspension: 0.6g sodium is added in 30mL toluene, form mixed solution, mixed solution is added in reaction unit, and low whipping speed is that 1200r/min, temperature are the 2h that refluxes under 120 ℃ and nitrogen protection, then naturally cool to room temperature, obtain basic metal/organic solvent suspension;
Three, prepare silane monomer/organic solvent solution: get 1.0541g phenyl-trichloro-silicane and 0.7051g dimethyldichlorosilane(DMCS) and be dissolved in the toluene of 40mL, after mixing, obtain chlorosilane/organic solvent solution;
Four, mix: low whipping speed is that 800r/min, oil bath temperature are the silane monomer/organic solvent solution that adds step 3 to prepare by the rate of addition of 1.2mL/min under 65 ℃, nitrogen protection and lucifuge condition, and low whipping speed is that 800r/min, oil bath temperature are to mix under 65 ℃ and nitrogen protection, obtain mixture;
Five, polymerization: mixture low whipping speed 800r/min, the oil bath temperature that step 4 obtains is to carry out back flow reaction under 85 ℃ and nitrogen protection and lucifuge condition, reaction times is 6h, then be cooled to room temperature, carry out solid-liquid separation, obtain the mixture filtrate of polymkeric substance;
Six, purification polysilane: step 5 gained filtrate is used to Rotary Evaporators evaporating solvent, after remaining a small amount of liquid, pour in beaker, add 10mL tetrahydrofuran (THF) to dissolve, add again 50mL Virahol to separate out polysilane, finally beaker lucifuge is stirred to 24h, solid-liquid separation, washing, the dry branched polysilane that obtains;
Seven, carbon nanotube and branched polysilane are compound: get the fine grinding of multi-walled carbon nano-tubes after 0.128g processes, put into 15mL tetrahydrofuran solution, get the branched polysilane that 0.523g step 6 makes and put into 30mL tetrahydrofuran solution, control temperature in 50 ℃, the ultrasonic concussion 4h of difference, then both solution are mixed, control temperature in 50 ℃, ultrasonic concussion 8h;
Eight, evaporating solvent: the turbid liquid evaporating solvent of mixing that step 7 is obtained, then, at the dry 24h of vacuum drying oven, obtains carbon nanotube/branched polysilane matrix material;
Nine, adopt situ aggregation method to prepare carbon nanotube-branched polysilane-poly styrene composite material: to get vinylbenzene 3.6g, add wherein 0.4g carbon nanotube/branched polysilane matrix material, reactor is placed in to ultrasonic thermostatic water bath, bath temperature rises to after 75 ℃, add initiator 0.08g Diisopropyl azodicarboxylate, under ul-trasonic irradiation, carry out polyreaction, after question response 6h, system becomes thick liquid, completes pre-polymerization process.The polystyrene reactant liquid that pre-polymerization is got togather is poured in mould, mould is put into baking oven and continue polymerization, and polymerization temperature is 100 ℃, and polymerization time is 6h, the cooling carbon nanotube-branched polysilane-poly styrene composite material that obtains.
Purifying carbon nano-tube concrete operations described in this testing sequence one are as follows: 1, calcination processing: carbon nanotube is put into retort furnace, and keeping temperature is 460 ℃, take out after calcining about 30min in air under static state; 2, HCl processes: the calcinate that step 1 obtains is put into 5mol/LHCl solution again, is heated to 120 ℃ of backflow 7h, then filters with sand core funnel, and then deionized water rinsing dry for products therefrom, obtains the carbon nanotube after purification process.
Adopt infrared spectrometer to obtaining purification of Multi-wall Carbon Nanotubes in this testing sequence one, carbon nanotube/branched polysilane matrix material of branched polysilane and this test preparation is analyzed, result as shown in Figure 1 to 4, Fig. 1 is the infrared spectrum of the multi-walled carbon nano-tubes of the purifying that obtains in this testing sequence one, figure bis-is infrared spectrograms of branched polysilane, Fig. 3 is the infrared spectrogram of carbon nanotube/branched polysilane matrix material matrix material of this test preparation, Fig. 4～Fig. 6 is polystyrene, test one makes the surperficial comparison diagram of Carbon Nanotubes/Polystyrene Nanocomposites and carbon nanotube-polysilane-poly styrene composite material, the multi-walled carbon nano-tubes obtaining in this testing sequence one is as shown in Figure 1 at 1560cm
-1there is a very strong absorption peak at place, and this is that C-C stretching vibration by multi-walled carbon nano-tubes agent structure causes, is the characteristic peak of multi-walled carbon nano-tubes, by Fig. 2 at 490cm
-1and 465cm
-1there is the vibration absorption peak of Si-Si key in place, at 697cm
-1, 732cm
-1, 800cm
-1, 837cm
-1and 997cm
-1there is the stretching vibration absorption peak of Si-C, 1089cm in place
-1there is Si-C in place
6h
5stretching vibration absorption peak, 1253cm
-1there is Si-CH in place
3symmetrical deformation vibration absorption peak, 1482cm
-1and 1427cm
-1place is phenyl ring skeletal vibration absorption peak, 2922cm
-1and 2852cm
-1place is CH
3stretching vibration absorption peak, 1629cm
-1c – H out-of-plane deformation vibration overtone, 3046cm
-1place is the hydrocarbon stretching vibration peak of phenyl ring, integral body, and polydimethyl-phenyl silane Infrared Characterization data and bibliographic reference value are very approaching, show that polymerization has occurred monomer, the characteristic peak of the carbon nanotube of the carbon nano-tube/poly silane matrix material of this test preparation is not obvious as shown in Figure 3, this is because the infrared vibration of carbon nanotube absorbs more than a little less than branched polysilane, so covered, and all there are some and moved in the charateristic avsorption band relevant with phenyl ring, think that this is that π-electron and the π-electron on polysilane of carbon nanotube side-wall exists pi-pi accumulation effect, this pi-pi accumulation effect makes features relevant absorption that variation occur just, the therefore compound success of carbon nano-tube/poly silane matrix material of known test preparation.Do not add as seen in Figure 5 the dispersiveness of carbon nanotube in the Carbon Nanotubes/Polystyrene Nanocomposites of polysilane bad, it is not very abundant making the performance that carbon nanotube embodies in polystyrene.As shown in Figure 6, add after polysilane, because the pi-pi accumulation effect between carbon nanotube and polysilane makes the dispersiveness of carbon nanotube, be improved, and make the performance that carbon nanotube embodies in polystyrene show more fully.
This test by pure polystyrene, Carbon Nanotubes/Polystyrene Nanocomposites, carbon nanotube-polysilane-poly styrene composite material by adding the carbon nanotube of different mass mark (wt%) to carry out specific conductivity test, test result is as shown in table 1, by table 1, can find out, when in Carbon Nanotubes/Polystyrene Nanocomposites, content of carbon nanotubes is increased to 6% from 0, specific conductivity is from 4.187 * 10
-12s/cm is increased to 8.062 * 10
-10s/cm, has only increased by two orders of magnitude, and when in carbon nanotube-polysilane-poly styrene composite material, carbon nanotube is increased to 4% from 0, specific conductivity is from 4.187 * 10
-12s/cm is increased to 4.356 * 10
-9s/cm, has increased by three orders of magnitude, and when content is increased to 6%, specific conductivity has increased by six orders of magnitude, illustrates in the situation that having polysilane, and the dispersiveness of carbon nanotube is relatively better, make matrix material conductivity be improved significantly.
Table 1 specific conductivity test test result
Test two:
The preparation method of a kind of carbon nanotube-polysilane-composite material of polymethyl methacrylate of this test, specifically completes according to the following steps:
One, Purification of Carbon Nanotubes is processed;
Two, prepare basic metal/organic solvent suspension: 0.6g sodium is added in 30mL toluene, and low whipping speed is that 1200r/min, temperature are condensing reflux 2h under 120 ℃ and nitrogen protection, then naturally cools to room temperature, obtain basic metal/organic solvent suspension;
Three, prepare chlorosilane/toluene solvant solution: methyl ethylene dichlorosilane 5.6428g is dissolved in and is had in 20mL toluene, and low whipping speed 800r/min, oil bath temperature are to mix under 65 ℃ and nitrogen protection, obtain mixture;
Four, polymerization: low whipping speed is that 800r/min, oil bath temperature are that the mixture that by the rate of addition of 1.25mL/min, step 3 obtained under 65 ℃, nitrogen protection and lucifuge condition joins in basic metal/organic solvent suspension that step 2 obtains, carry out back flow reaction, reaction times is 6h, then be cooled to room temperature, carry out solid-liquid separation, collect filtrate, obtain mixed with polymers liquid;
Five, purification polysilane: the mixed with polymers liquid that step 4 is obtained, use Rotary Evaporators evaporating solvent, after remaining a small amount of liquid, pour in beaker, add 10mL tetrahydrofuran (THF) to dissolve, add again 30mL dehydrated alcohol to separate out polysilane, finally beaker lucifuge is stirred to 24h, solid-liquid separation, washing, the dry line style polysilane that obtains;
Six, carbon nanotube and polysilane are compound: get the fine grinding of multi-walled carbon nano-tubes after 0.144g step 1 is processed, put into 15mL tetrahydrofuran solution, get the line style polysilane that 0.642g step 5 makes and put into 25mL tetrahydrofuran solution, control temperature in 50 ℃, the ultrasonic concussion 4h of difference, then both solution are mixed, control temperature in 50 ℃, ultrasonic concussion 8h;
Seven, evaporating solvent: the turbid liquid of mixing that step 6 is obtained, evaporating solvent, then, at the dry 24h of vacuum drying oven, obtains carbon nano-tube/poly silane matrix material;
Eight, adopt situ aggregation method to prepare carbon nanotube-polysilane-composite material of polymethyl methacrylate: to get 30ml methyl methacrylate, carbon nanotube-polysilane mixture 0.1876g of 0.09g benzoyl peroxide and step 7 mixes, move under room temperature with ultrasonic cleaning instrument concussion 15～30min, after being uniformly dispersed, system puts into reflux, while being under reflux conditions slowly heated to 80～83 ℃, when there is viscous liquid, stop heating, then under the condition of ultrasonic cleaning instrument concussion, be cooled to rapidly 50 ℃, liquid is poured in ready-made mould, then put in vacuum drying oven mould is whole, vacuum-drying 30min at 50 ℃, then in vacuum drying oven, be warming up to 80～83 ℃, and keep 24h to obtain carbon nanotube-polysilane-composite material of polymethyl methacrylate,
Purifying carbon nano-tube concrete operations described in this testing sequence one are as follows: 1, calcination processing: carbon nanotube is put into retort furnace, and keeping temperature is 460 ℃, take out after calcining about 30min in air under static state; 2, HCl processes: the calcinate that step 1 obtains is put into 5mol/L solution again, is heated to 120 ℃ of backflow 7h, then filters with sand core funnel, and then deionized water rinsing dry for products therefrom, obtains the carbon nanotube after purification process.
A kind of preparation method of the carbon nanotube-polysilane-organic polymer composite of this test has plurality of advantages, guaranteeing under carbon nanotube structure fine status, adopt non-carbon surface modifier, add polysilane, make it under pi-pi accumulation effect, be coated on carbon nano tube surface, thereby improve the dispersiveness of carbon nanotube, and the performance of polystyrene is increased dramatically, whole process operation is simple, easily control, and each process is independent of each other.
This test by pure polystyrene, Carbon Nanotubes/Polystyrene Nanocomposites, carbon nanotube-polysilane-poly styrene composite material by adding the carbon nanotube of different mass mark (wt%) to carry out specific conductivity test, test result shows, when in Carbon Nanotubes/Polystyrene Nanocomposites, content of carbon nanotubes is increased to 6% from 0, specific conductivity is from 4.187 * 10
-12s/cm is increased to 8.062 * 10
-10s/cm, has only increased by two orders of magnitude, and when in carbon nanotube-polysilane-poly styrene composite material, carbon nanotube is increased to 4% from 0, specific conductivity is from 4.187 * 10
-12s/cm is increased to 4.356 * 10
-9s/cm, has increased by three orders of magnitude, and when content is increased to 6%, specific conductivity has increased by six orders of magnitude, illustrates in the situation that there is no polysilane, and the dispersiveness of carbon nanotube is relatively poor, make matrix material conductivity can not be improved significantly.
Claims (10)
1. a carbon nanotube-polysilane-organic polymer composite, it is characterized in that it is to be made by carbon nanotube, organic solvent, dichlorosilane, trichlorosilane, basic metal, reaction terminating agent, blend organic solvent, organic polymer monomer and initiator, wherein, the quality of described dichlorosilane and the volume ratio of organic solvent are 1g:(60mL～125mL); Described dichlorosilane and alkali-metal mass ratio are (0.8～2): 1; Described dichlorosilane and the mass ratio of trichlorosilane are 1:(0～4); The quality of described dichlorosilane and the volume ratio of reaction terminating agent are 1g:(30mL～60mL); Described carbon nanotube and the mass ratio of dichlorosilane are 1:(1～10); The described carbon nanotube together mass volume ratio of mixed organic solvent is 1g:(15mL～240mL); Described organic polymer monomer and carbon nanotube mass ratio are (10～100): 1; The mass ratio of described initiator and organic polymer monomer is 1:(40～100).
2. the method for preparation a kind of carbon nanotube-polysilane-organic polymer composite claimed in claim 1, is characterized in that it carries out according to following steps:
One, Purification of Carbon Nanotubes: carbon nanotube is carried out to high-temperature calcination and acid treatment, obtain the carbon nanotube after purifying;
Two, prepare basic metal organic solvent suspension: basic metal is added in organic solvent, form mixed solution, mixed solution is added in reaction unit, and low whipping speed is that 1000r/min～1500r/min, temperature are the 0.5h～1h that refluxes under 80 ℃～120 ℃ and nitrogen protection, then naturally cooling, obtains basic metal/organic solvent suspension;
Three, prepare silane monomer/organic solvent solution: dichlorosilane and trichlorosilane are dissolved in to organic solvent, mix and obtain silane monomer/organic solvent solution;
Four, polysilane is prepared in silane monomer polymerization: the silane monomer of step 3/organic solvent solution is imported in constant pressure funnel, then low whipping speed is 600r/min～1000r/min, temperature is 60 ℃～80 ℃, under the condition of nitrogen protection and lucifuge, by 1mL/min～1.5mL/min rate of addition, be added dropwise in step 2 gained basic metal/organic solvent suspension, after dropwising, control stirring velocity at 600r/min～1000r/min, temperature is at 80 ℃～120 ℃, under nitrogen protection and lucifuge condition, carry out back flow reaction, reaction times is 6h～8h, then be cooled to room temperature, carry out solid-liquid separation, obtain the mixture filtrate of polymkeric substance,
Five, purification polysilane: step 4 gained filtrate is used to Rotary Evaporators evaporating solvent, remaining liq is poured in beaker, added tetrahydrofuran (THF) to dissolve, then add reaction terminating agent to separate out polysilane, finally beaker lucifuge is stirred to 24h, solid-liquid separation, washing, the dry polysilane that obtains;
Six, carbon nanotube and polysilane are compound: the carbon nanotube after the purifying that step 1 is obtained is put into respectively blend organic solvent with the polysilane that step 5 obtains after grinding, and control temperature in 50 ℃, the ultrasonic concussion 4h of difference, then mix, after ultrasonic concussion 8h, obtain mixed solution;
Seven, evaporating solvent: by after the mixed solution evaporating solvent of step 6, vacuum-drying 24h, obtains carbon nano-tube/poly silane matrix material;
Eight, adopt situ aggregation method to prepare carbon nanotube-polysilane-organic polymer composite: to take the Powdered matrix material of carbon nano-tube/poly silane prepared by step 7, join in organic polymer monomer, reaction unit is placed in to ultrasonic thermostatic water bath, at bath temperature, be raised to after 75 ℃, add initiator, under ul-trasonic irradiation, carry out polyreaction, after question response 6h, liquid after prepolymerization is poured in mould, then mould is put into baking oven and in temperature be under the condition of 100 ℃, continue polymerization 8h, after cooling, obtain carbon nanotube-polysilane-organic polymer composite,
The mass volume ratio of the basic metal described in step 2 and organic solvent is 1g:(30mL～100mL);
Described in the quality of dichlorosilane described in step 3 and step 2, the volume ratio of organic solvent is 1g:(30mL～40mL); Described in dichlorosilane described in step 3 and step 2, alkali-metal mass ratio is (0.8～2): 1; Described in step 3, the mass ratio of dichlorosilane and trichlorosilane is 1:(0～4); Described in step 3, described in the quality of dichlorosilane and step 3, the volume ratio of organic solvent is 1g:(30mL～85mL); Described in the volume of tetrahydrofuran (THF) described in step 5 and step 3, dichlorosilane mass ratio is (5mL～20mL): 1g; Reaction terminating agent described in step 5 and tetrahydrofuran (THF) volume ratio are (5～12): 1; Described in step 6, carbon nanotube quality and polysilane mass ratio are 1:(1～4); Blend organic solvent volume described in step 6 and polysilane mass ratio are (15mL～60mL): 1g; Organic polymer monomer mass described in step 8 and carbon nano-tube/poly silane matrix material mass ratio are (5～20): 1; The mass ratio of the initiator described in step 8 and organic polymer monomer is 1:(40～100).
3. the preparation method of a kind of carbon nanotube-polysilane-organic polymer composite according to claim 2, it is characterized in that, described in step 1, carbon nanotube is carried out to high-temperature calcination and acid treatment, concrete operations are as follows: one, calcination processing: carbon nanotube is put into retort furnace, keeping temperature is 450 ℃～500 ℃, takes out after calcining about 30min; Two, HCl processes: the calcinate that step 1 is obtained is put into 5mol/LHCl solution again, be heated to 100～120 ℃ of backflow 6h～7h, then filter with sand core funnel, collect solid formation, deionized water rinsing dry for gained solid formation, obtains the carbon nanotube after purification process.
4. the preparation method of a kind of carbon nanotube-polysilane-organic polymer composite according to claim 2, is characterized in that described in step 2 being that low whipping speed is that 1000r/min～1500r/min, temperature are the 0.5h～1h that refluxes under 100 ℃～120 ℃ and nitrogen protection.
5. the preparation method of a kind of carbon nanotube-polysilane-organic polymer composite according to claim 2, is characterized in that being added dropwise in step 2 gained basic metal/organic solvent suspension by 1.2mL/min～1.5mL/min rate of addition described in step 4.
6. the preparation method of a kind of carbon nanotube-polysilane-organic polymer composite according to claim 5, is characterized in that being added dropwise in step 2 gained basic metal/organic solvent suspension by 1.5mL/min rate of addition described in step 3.
7. the preparation method of a kind of carbon nanotube-polysilane-organic polymer composite according to claim 2; it is characterized in that the control stirring velocity described in step 4 carries out back flow reaction at 600r/min～1000r/min, temperature under 100 ℃～120 ℃, nitrogen protection and lucifuge condition, the reaction times is 6h～8h.
8. the preparation method of a kind of carbon nanotube-polysilane-organic polymer composite according to claim 2, is characterized in that dichlorosilane described in step 3 and the mass ratio of trichlorosilane are 1:(2～4).
9. the preparation method of a kind of carbon nanotube-polysilane-organic polymer composite according to claim 2, is characterized in that carbon nanotube and the polysilane mass ratio of the purifying described in step 6 is 1:(1～4).
10. the preparation method of a kind of carbon nanotube-polysilane-organic polymer composite according to claim 2, is characterized in that organic polymer monomer mass and the carbon nano-tube/poly silane matrix material mass ratio described in step 8 is (10～20): 1.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106245055A (en) * | 2016-09-22 | 2016-12-21 | 中国人民解放军国防科学技术大学 | A kind of electrochemical method for synthesizing of the liquid polysilane containing block structure |
| CN106832074A (en) * | 2017-03-10 | 2017-06-13 | 桂林电子科技大学 | A kind of preparation method of PMMA/CNTs composites |
| CN110408030A (en) * | 2019-08-13 | 2019-11-05 | 青岛科技大学 | The method that a kind of ring-opening polymerisation of cyclosiloxane original position prepares high-performance conductive silicon rubber |
| CN112538166A (en) * | 2020-12-11 | 2021-03-23 | 湖南前驱新材料有限公司 | Large-scale production method for ultrasonic-assisted synthesis of polymethylsilane |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1410455A (en) * | 2002-03-14 | 2003-04-16 | 四川大学 | Preparation method of polymer/carbon nano pipe composite emulsion and its in situ emulsion polymerization |
| CN1844176A (en) * | 2006-03-14 | 2006-10-11 | 同济大学 | Process for in-situ synthesis of amphiphilic polymer modified carbon nanotube |
| CN102786693A (en) * | 2012-08-31 | 2012-11-21 | 哈尔滨理工大学 | Polysilane/multi-walled carbon nanotube composite material and preparation method thereof |
| CN102796266A (en) * | 2012-09-13 | 2012-11-28 | 哈尔滨理工大学 | Multiwall carbon nanotube-polysilane composite material and preparation method thereof |
| CN103113593A (en) * | 2013-02-26 | 2013-05-22 | 哈尔滨理工大学 | Preparation method of hydroxylated multi-wall carbon nanotube-polysilane composite material |
-
2014
- 2014-02-24 CN CN201410062162.8A patent/CN103755849B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1410455A (en) * | 2002-03-14 | 2003-04-16 | 四川大学 | Preparation method of polymer/carbon nano pipe composite emulsion and its in situ emulsion polymerization |
| CN1844176A (en) * | 2006-03-14 | 2006-10-11 | 同济大学 | Process for in-situ synthesis of amphiphilic polymer modified carbon nanotube |
| CN102786693A (en) * | 2012-08-31 | 2012-11-21 | 哈尔滨理工大学 | Polysilane/multi-walled carbon nanotube composite material and preparation method thereof |
| CN102796266A (en) * | 2012-09-13 | 2012-11-28 | 哈尔滨理工大学 | Multiwall carbon nanotube-polysilane composite material and preparation method thereof |
| CN103113593A (en) * | 2013-02-26 | 2013-05-22 | 哈尔滨理工大学 | Preparation method of hydroxylated multi-wall carbon nanotube-polysilane composite material |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106245055A (en) * | 2016-09-22 | 2016-12-21 | 中国人民解放军国防科学技术大学 | A kind of electrochemical method for synthesizing of the liquid polysilane containing block structure |
| CN106245055B (en) * | 2016-09-22 | 2018-12-18 | 中国人民解放军国防科学技术大学 | A kind of electrochemical method for synthesizing of the liquid polysilane containing block structure |
| CN106832074A (en) * | 2017-03-10 | 2017-06-13 | 桂林电子科技大学 | A kind of preparation method of PMMA/CNTs composites |
| CN106832074B (en) * | 2017-03-10 | 2018-12-25 | 桂林电子科技大学 | A kind of preparation method of PMMA/CNTs composite material |
| CN110408030A (en) * | 2019-08-13 | 2019-11-05 | 青岛科技大学 | The method that a kind of ring-opening polymerisation of cyclosiloxane original position prepares high-performance conductive silicon rubber |
| CN112538166A (en) * | 2020-12-11 | 2021-03-23 | 湖南前驱新材料有限公司 | Large-scale production method for ultrasonic-assisted synthesis of polymethylsilane |
| CN112538166B (en) * | 2020-12-11 | 2022-05-06 | 湖南前驱新材料有限公司 | Large-scale production method for ultrasonic-assisted synthesis of polymethylsilane |
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