CN103755849B - A kind of preparation method of CNT-polysilane-organic polymer composite - Google Patents
A kind of preparation method of CNT-polysilane-organic polymer composite Download PDFInfo
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- CN103755849B CN103755849B CN201410062162.8A CN201410062162A CN103755849B CN 103755849 B CN103755849 B CN 103755849B CN 201410062162 A CN201410062162 A CN 201410062162A CN 103755849 B CN103755849 B CN 103755849B
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Abstract
The preparation method of a kind of CNT polysilane organic polymer composite, it refers to the preparation method of a kind of composite.The invention solves the problems that the bad dispersibility of CNT time prepared by existing CNT/organic polymer composite, and the problem that existing most method by change carbon nano tube structure or by conventional carbonaceous organic material cladding improves dispersibility.The inventive method is: one, Purification of Carbon Nanotubes；Two, alkali metal organic solvent suspension is prepared；Three, polysilane is prepared in silane monomer polymerization；Four, polysilane is purified；Five, CNT is combined with polysilane；Six, evaporation solvent；Seven, situ aggregation method is used to prepare CNT polysilane organic polymer composite.The inventive method, in the case of ensureing that carbon nano tube structure is intact, adds polysilane and makes it have good dispersibility in organic polymer so that it is performance is substantially improved, and operation is simple, be easily controlled, and each process is independent of each other.
Description
Technical field
The present invention relates to the preparation method of a kind of composite.
Background technology
Since CNT is found, due to its unique construction and character, and by as additive application in various multiple
The preparation of condensation material, thus effectively change the mechanics of polymer, optical, electrical character and heat stability.But, CNT
Surface relative inertness, be practically insoluble in most of organic solvent, and the winding that causes due to its big L/D ratio and Gao Bibiao
The high surface energy that area causes, so the most easily reuniting, causes CNT excessively poor in the degree of scatter in polymeric matrix,
The performance of carbon nano-tube/polymer composite material can not get embodying well, limits its range of application.
In order to improve CNT dispersibility in macromolecular material, chemical modification and the big class side of physical modification two can be used
Method.Chemical modification refers to, through chemical reagent or high-temperature process, make the closing structure of carbon nano tube surface open, form several
Active site, such as hydroxyl or carboxyl, thus improves its compatibility in the base.This method there is the problem that CNT is special
Some structures are broken, the sp in functionalization site2Hybrid structure is destroyed simultaneously, and its some performance (such as electric conductivity) will be subject to
To the biggest impact；Physical modified method refers to that CNT is tied by Van der Waals force, π-π interaction etc. mutually with functional group
Close and coating material (such as ionic surface active agent or organic polymer) is wrapped in carbon nano tube surface.With chemical modification phase
Ratio, physical modification will not the original chemical constitution of destroying carbon nanometer tube self, it is possible to complete retain its excellent mechanics, electricity
Etc. performance.Therefore, if on the premise of not changing carbon nano tube structure, improving its dispersibility in macromolecular material,
CNT range of application in the composite will be expanded, prepare the functional material of various excellent performances.
But being as developing rapidly of global economy, petroleum resources are the deficientest, causing with carbon is the chemical products mainly comprised
Price raises day by day.In recent years, the macromolecular material with silicon as main material is flourish.First, silicon is on the earth
The element that reserves are the abundantest, along with the continuous minimizing of petroleum resources, find can the resource of petroleum replacing and originate and enrich
Non-carbon functional material time, silicon is first-selected naturally；Secondly multiple conducting polymer can be synthesized with silicon for raw material, their electricity
Conductance can change in the scope that insulator-SEMICONDUCTOR-METAL state is wider, and this is that other material is incomparable at present.It addition,
These polymer have the feature such as structure diversification, easy processing.
Therefore, if material being applied in existing chemical industry, functional material production, substituting conventional organic reagent, will become
Fine selection for low-carbon economy.The present invention will polysilane as CNT physical modification dressing agent, be wrapped in carbon nanometer
Tube-surface, thus improve CNT dispersibility in macromolecular material.
Summary of the invention
It is an object of the invention to the bad dispersibility of CNT time prepared by existing CNT/organic polymer composite, and existing
There is most method by change carbon nano tube structure or by conventional carbonaceous organic material cladding to improve the problem of dispersibility, and carry
Supply the preparation method of a kind of CNT-polysilane-organic polymer composite.
A kind of CNT-polysilane-organic polymer composite of the present invention, be by CNT, organic solvent, two
Chlorosilane, trichlorosilane, alkali metal, reaction terminating agent, blended organic solvent, organic polymer monomer and initiator are made,
Wherein, the quality of described dichlorosilane and the volume ratio of organic solvent are 1g:(60mL～125mL)；Described dichloro silicon
Alkane and alkali-metal mass ratio are (0.8～2): 1；Described dichlorosilane is 1:(0～4 with the mass ratio of trichlorosilane)；Described
The quality of dichlorosilane and the volume ratio of reaction terminating agent are 1g:(30mL～60mL)；Described CNT and dichlorosilane
Mass ratio be 1:(1～10)；It is 1g that described CNT mixes the mass volume ratio of organic solvent together:
(15mL～240mL)；Described organic polymer monomer and carbon nanotube mass are than being (10～100): 1；Described initiator
It is 1:(40～100 with the mass ratio of organic polymer monomer).
The preparation method of a kind of CNT-polysilane-organic polymer composite of the present invention, is to enter according to following steps
Row:
One, Purification of Carbon Nanotubes: CNT is carried out high-temperature calcination and acid treatment, obtains CNT after purification；
Two, prepare alkali metal solvent suspension liquid: added by alkali metal in organic solvent, form mixed liquor, mixed liquor is added
In reaction unit, and low whipping speed be 1000r/min～1500r/min, temperature be that 80 DEG C～120 DEG C and nitrogen are protected next time
Stream 0.5h～1h, then natural cooling, obtain alkali metal/organic solvent suspension；
Three, prepare silane monomer/organic solvent solution: dichlorosilane and trichlorosilane are dissolved in organic solvent, mix and get final product
To silane monomer/organic solvent solution；
Four, polysilane is prepared in silane monomer polymerization: imported by the silane monomer of step 3/organic solvent solution in constant pressure funnel,
Then low whipping speed be 600r/min～1000r/min, temperature be 60 DEG C～80 DEG C, under conditions of nitrogen protection and lucifuge by
1mL/min～1.5mL/min rate of addition is added dropwise in step 2 gained alkali metal/organic solvent suspension, drips complete
After, control mixing speed and enter under the conditions of 80 DEG C～120 DEG C, nitrogen protection and lucifuge in 600r/min～1000r/min, temperature
Row back flow reaction, the response time is 6h～8h, is then cooled to room temperature, and carries out solid-liquid separation, i.e. obtains the mixing of polymer
Thing filtrate；
Five, polysilane is purified: step 4 gained filtrate is evaporated solvent with Rotary Evaporators, is poured into by remaining liq in beaker,
Add oxolane to dissolve, add reaction terminating agent and separate out polysilane, finally by beaker lucifuge stirring 24h, solid-liquid separation,
Wash, be dried to obtain polysilane；
Six, CNT is combined with polysilane: after the CNT after purification step one obtained grinds, obtain with step 5
To polysilane be respectively put in blended organic solvent, control temperature within 50 DEG C, respectively ultrasonic vibration 4h, then mix
Close, after ultrasonic vibration 8h, obtain mixed liquor；
Seven, evaporation solvent: after the mixed liquor of step 6 is evaporated solvent, is vacuum dried 24h, i.e. obtains carbon nano-tube/poly
Silane composite；
Eight, situ aggregation method is used to prepare CNT-polysilane-organic polymer composite: to weigh prepared by step 7
Carbon nano-tube/poly silane powder composite, joins in organic polymer monomer, reaction unit is placed in ultrasound wave permanent
In tepidarium, after bath temperature is raised to 75 DEG C, adds initiator, under ul-trasonic irradiation, carry out polyreaction, treat anti-
After answering 6h, the liquid after prepolymerization is poured in mould, then mould is put in baking oven in the condition that temperature is 100 DEG C
Under, continue polymerization 8h, after cooling, obtain CNT-polysilane-organic polymer composite；
Alkali metal described in step 2 is 1g:(30mL～100mL with the mass volume ratio of organic solvent)；
The quality of dichlorosilane described in step 3 is 1g:(30mL～40mL with the volume ratio of organic solvent described in step 2)；
Dichlorosilane described in step 3 is (0.8～2) with alkali-metal mass ratio described in step 2: 1；Dichlorosilane described in step 3 with
The mass ratio of trichlorosilane is 1:(0～4)；The volume of organic solvent described in the quality of dichlorosilane described in step 3 and step 3
Ratio is 1g:(30mL～85mL)；Oxolane volume described in step 5 with dichlorosilane mass ratio described in step 3 is
(5mL～20mL): 1g；Reaction terminating agent described in step 5 and oxolane volume ratio are (5～12): 1；Carbon described in step 6
Nanotube quality and polysilane mass ratio are 1:(1～4)；Blended organic solvent volume described in step 6 and polysilane mass ratio
For (15mL～60mL): 1g；Organic polymer monomer mass described in step 8 and carbon nano-tube/poly silane composite quality
Ratio be (5～20): 1；Initiator described in step 8 is 1:(40～100 with the mass ratio of organic polymer monomer).
The present invention comprises following beneficial effect:
A kind of preparation method of the CNT-polysilane-organic polymer composite of the present invention has plurality of advantages, is protecting
Under card carbon nano tube structure fine status, use non-carbon coating material, add polysilane so that it is under pi-pi accumulation effect
It is coated on carbon nano tube surface, thus improves the dispersibility of CNT, and make high-molecular organic material (organic polymer
For polystyrene, polyethylene, polymethyl methacrylate) performance be increased dramatically, whole process operation is simple,
Being easily controlled, each process is independent of each other.
Pure polystyrene, Carbon Nanotubes/Polystyrene Nanocomposites, CNT-polysilane-polystyrene are combined by the present invention
Material carries out electrical conductivity test by adding the CNT of different quality mark (wt%), and test result shows, when carbon is received
In mitron/poly styrene composite material content of carbon nanotubes from 0 increase to 6% time, electrical conductivity is from 4.187 × 10-12S/cm increases
It is added to 8.062 × 10-10S/cm, merely add two orders of magnitude, when carbon in CNT-polysilane-poly styrene composite material
Nanotube from 0 increase to 4% time, electrical conductivity is from 4.187 × 10-12S/cm increases to 4.356 × 10-9S/cm, adds three
The order of magnitude, when content increases to 6%, electrical conductivity adds six orders of magnitude, illustrates in the case of not having polysilane,
The dispersibility of CNT is relatively poor, make composite electric conductivity can not be improved significantly.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of the CNT of the purification that test procedure one obtains；
Fig. 2 is the branched polysilane infrared spectrum in test one；
Fig. 3 is the CNT/branched polysilane composite infrared spectrum in test one；
Fig. 4 is polystyrene surface figure；
Fig. 5 is carbon nano-tube/poly styrene exterior view；
Fig. 6 is CNT-polysilane-polystyrene surface figure.
Detailed description of the invention
Detailed description of the invention one: the preparation side of a kind of CNT-polysilane-organic polymer composite of present embodiment
Method, follows the steps below:
One, Purification of Carbon Nanotubes: CNT is carried out high-temperature calcination and acid treatment, obtains CNT after purification；
Two, prepare alkali metal organic solvent suspension: added by alkali metal in organic solvent, form mixed liquor, by mixed liquor
Add in reaction unit, and low whipping speed be 1000r/min～1500r/min, temperature be 80 DEG C～120 DEG C and nitrogen protection
Lower backflow 0.5h～1h, then natural cooling, obtain alkali metal/organic solvent suspension；
Three, prepare silane monomer/organic solvent solution: dichlorosilane and trichlorosilane are dissolved in organic solvent, mix and get final product
To silane monomer/organic solvent solution；
Four, polysilane is prepared in silane monomer polymerization: imported by the silane monomer of step 3/organic solvent solution in constant pressure funnel,
Then low whipping speed be 600r/min～1000r/min, temperature be 60 DEG C～80 DEG C, under conditions of nitrogen protection and lucifuge by
1mL/min～1.5mL/min rate of addition is added dropwise in step 2 gained alkali metal/organic solvent suspension, drips complete
After, control mixing speed and enter under the conditions of 80 DEG C～120 DEG C, nitrogen protection and lucifuge in 600r/min～1000r/min, temperature
Row back flow reaction, the response time is 6h～8h, is then cooled to room temperature, and carries out solid-liquid separation, i.e. obtains the mixing of polymer
Thing filtrate；
Five, polysilane is purified: step 4 gained filtrate is evaporated solvent with Rotary Evaporators, is poured into by remaining liq in beaker,
Add oxolane to dissolve, add reaction terminating agent and separate out polysilane, finally by beaker lucifuge stirring 24h, solid-liquid separation,
Wash, be dried to obtain polysilane；
Six, CNT is combined with polysilane: after the CNT after purification step one obtained grinds, obtain with step 5
To polysilane be respectively put in blended organic solvent, control temperature within 50 DEG C, respectively ultrasonic vibration 4h, then mix
Close, after ultrasonic vibration 8h, obtain mixed liquor；
Seven, evaporation solvent: after the mixed liquor of step 6 is evaporated solvent, is vacuum dried 24h, i.e. obtains carbon nano-tube/poly
Silane composite；
Eight, situ aggregation method is used to prepare CNT-polysilane-organic polymer composite: to weigh prepared by step 7
Carbon nano-tube/poly silane powder composite, joins in organic polymer monomer, reaction unit is placed in ultrasound wave permanent
In tepidarium, after bath temperature is raised to 75 DEG C, adds initiator, under ul-trasonic irradiation, carry out polyreaction, treat anti-
After answering 6h, the liquid after prepolymerization is poured in mould, then mould is put in baking oven in the condition that temperature is 100 DEG C
Under, continue polymerization 8h, after cooling, obtain CNT-polysilane-organic polymer composite；
Alkali metal described in step 2 is 1g:(30mL～100mL with the mass volume ratio of organic solvent)；
The quality of dichlorosilane described in step 3 is 1g:(30mL～40mL with the volume ratio of organic solvent described in step 2)；
Dichlorosilane described in step 3 is (0.8～2) with alkali-metal mass ratio described in step 2: 1；Dichlorosilane described in step 3 with
The mass ratio of trichlorosilane is 1:(0～4)；The volume of organic solvent described in the quality of dichlorosilane described in step 3 and step 3
Ratio is 1g:(30mL～85mL)；Oxolane volume described in step 5 with dichlorosilane mass ratio described in step 3 is
(5mL～20mL): 1g；Reaction terminating agent described in step 5 and oxolane volume ratio are (5～12): 1；Carbon described in step 6
Nanotube quality and polysilane mass ratio are 1:(1～4)；Blended organic solvent volume described in step 6 and polysilane mass ratio
For (15mL～60mL): 1g；Organic polymer monomer mass described in step 8 and carbon nano-tube/poly silane composite quality
Ratio be (5～20): 1；Initiator described in step 8 is 1:(40～100 with the mass ratio of organic polymer monomer).
A kind of preparation method of the CNT-polysilane-organic polymer composite of present embodiment has plurality of advantages,
Under ensureing carbon nano tube structure fine status, use non-carbon coating material, add polysilane so that it is make at pi-pi accumulation
It is coated on carbon nano tube surface under with, thus improves the dispersibility of CNT, and make the performance of high-molecular organic material obtain
To being substantially improved, whole process operation is simple, be easily controlled, and each process is independent of each other.
Present embodiment is by pure polystyrene, Carbon Nanotubes/Polystyrene Nanocomposites, CNT-polysilane-polystyrene
Composite carries out electrical conductivity test by adding the CNT of different quality mark (wt%), and test result shows, when
In Carbon Nanotubes/Polystyrene Nanocomposites content of carbon nanotubes from 0 increase to 6% time, electrical conductivity is from 4.187 × 10-12S/cm
Increase to 8.062 × 10-10S/cm, merely add two orders of magnitude, when in CNT-polysilane-poly styrene composite material
CNT from 0 increase to 4% time, electrical conductivity is from 4.187 × 10-12S/cm increases to 4.356 × 10-9S/cm, adds three
The individual order of magnitude, when content increases to 6%, electrical conductivity adds six orders of magnitude, illustrates in the case of not having polysilane,
The dispersibility of CNT is relatively poor, make composite electric conductivity can not be improved significantly.
Detailed description of the invention two: present embodiment is unlike detailed description of the invention one: described in step one by carbon nanometer
Pipe carries out high-temperature calcination and acid treatment, and concrete operations are as follows: one, calcination processing: put into by CNT in Muffle furnace, protects
Holding temperature is 450 DEG C～500 DEG C, takes out after calcining about 30min；Two, HCl process: calcining step one obtained is produced
Thing places in 5mol/L HCl solution, is heated to 100～120 DEG C of backflow 6h～7h, then filters with sand core funnel,
Collecting solid formation, gained solid formation deionized water rinsing is also dried, i.e. obtains the CNT after purification process.Other with
Detailed description of the invention one is identical.
Detailed description of the invention three: present embodiment is unlike detailed description of the invention one or two: described in step 2 be
Mixing speed is 1000r/min～1500r/min, temperature is 100 DEG C～120 DEG C and lower condensing reflux 0.5h～1h of nitrogen protection.
Other is identical with detailed description of the invention one or two.
Detailed description of the invention four: present embodiment is unlike one of detailed description of the invention one to three: described in step 2
And low whipping speed be 1000r/min～1500r/min, temperature be 110 DEG C～120 DEG C and the lower condensing reflux of nitrogen protection
0.5h～1h.Other is identical with one of detailed description of the invention one to three.
Detailed description of the invention five: present embodiment is unlike one of detailed description of the invention one to four: described in step 4
It is added dropwise in step 2 gained alkali metal/organic solvent suspension by 1.2mL/min～1.5mL/min rate of addition.Other
Identical with one of detailed description of the invention one to four.
Detailed description of the invention six: present embodiment is unlike one of detailed description of the invention one to five: described in step 4
It is added dropwise in step 2 gained alkali metal/organic solvent suspension by 1.5mL/min rate of addition.Other be embodied as
One of mode one to five is identical.
Detailed description of the invention seven: present embodiment is unlike one of detailed description of the invention one to six: described in step 4
Control mixing speed to carry out under the conditions of 100 DEG C～120 DEG C, nitrogen protection and lucifuge in 600r/min～1000r/min, temperature
Back flow reaction, the response time is 6h～8h.Other is identical with one of detailed description of the invention one to six.
Detailed description of the invention eight: present embodiment is unlike one of detailed description of the invention one to seven: described in step 3
The quality of dichlorosilane and the volume ratio of organic solvent are 1g:(35～50) mL.One of other and detailed description of the invention one to seven
Identical.
Detailed description of the invention nine: present embodiment is unlike one of detailed description of the invention one to eight: described in step 3
Dichlorosilane and alkali-metal mass ratio are (1～1.8): 1.Other is identical with one of detailed description of the invention one to eight.
Detailed description of the invention ten: present embodiment is unlike one of detailed description of the invention one to nine: described in step 3
Dichlorosilane and alkali-metal mass ratio are (1.4～1.6): 1.Other is identical with one of detailed description of the invention one to nine.
Detailed description of the invention 11: present embodiment is unlike one of detailed description of the invention one to ten: described in step 3
Dichlorosilane is 1:(2～4 with the mass ratio of trichlorosilane).Other is identical with one of detailed description of the invention one to ten.
Detailed description of the invention 12: present embodiment is unlike one of detailed description of the invention one to ten one: described in step 3
The mass ratio of dichlorosilane and trichlorosilane be 1:(2.5～3).Other is identical with one of detailed description of the invention one to ten one.
Detailed description of the invention 13: present embodiment is unlike one of detailed description of the invention one to ten two: described in step 3
The quality of dichlorosilane and the volume ratio of organic solvent be 1g:35mL.Other and one of detailed description of the invention one to ten two phase
With.
Detailed description of the invention 14: present embodiment is unlike one of detailed description of the invention one to ten three: institute in step 5
The oxolane volume stated and dichlorosilane mass ratio are (7mL～15mL): 1g.Other is with detailed description of the invention one to ten
One of three identical.
Detailed description of the invention 15: present embodiment is unlike one of detailed description of the invention one to ten four: institute in step 5
Stating reaction terminating agent with oxolane volume ratio is (10～12): 1.Other is identical with one of detailed description of the invention one to ten four.
Detailed description of the invention 16: present embodiment is unlike one of detailed description of the invention one to ten five: described in step 6
CNT and polysilane mass ratio are 1:(1～3).Other is identical with one of detailed description of the invention one to ten five.
Detailed description of the invention 17: present embodiment is unlike one of detailed description of the invention one to ten six: described in step 6
CNT and polysilane mass ratio are 1:(1～2).Other is identical with one of detailed description of the invention one to ten six.
Detailed description of the invention 18: present embodiment is unlike one of detailed description of the invention one to ten seven: described in step 5
CNT and polysilane mass ratio are 1:(1～1.5).Other is identical with one of detailed description of the invention one to ten seven.
Detailed description of the invention 19: present embodiment is unlike one of detailed description of the invention one to ten eight: described in step 6
CNT and polysilane mass ratio are 1:1.5.Other is identical with one of detailed description of the invention one to ten eight.
Detailed description of the invention 20: present embodiment is unlike one of detailed description of the invention one to ten nine: described in step 6
Organic solvent volume and polysilane mass ratio are (20mL～40mL): 1g.Other and one of detailed description of the invention one to ten nine phase
With.
Detailed description of the invention 21: present embodiment is unlike one of detailed description of the invention one to two ten: step 6 institute
Stating organic solvent volume with silane mass ratio is 30mL:1g.Other is identical with one of detailed description of the invention one to two ten.
Detailed description of the invention 22: unlike one of present embodiment and detailed description of the invention one to two 11: step 8
Described organic polymer monomer mass and carbon nano-tube/poly silane composite mass ratio are (5～18): 1.Other is with concrete
One of embodiment one to two 11 is identical.
Detailed description of the invention 23: unlike one of present embodiment and detailed description of the invention one to two 12: step 8
Described organic polymer monomer mass and carbon nano-tube/poly silane composite mass ratio are (7～16): 1.Other is with concrete
One of embodiment one to two 12 is identical.
Detailed description of the invention 24: unlike one of present embodiment and detailed description of the invention one to two 13: step 8
Described organic polymer monomer mass and carbon nano-tube/poly silane composite mass ratio are (8～14): 1.Other is with concrete
One of embodiment one to two 13 is identical.
Detailed description of the invention 25: unlike one of present embodiment and detailed description of the invention one to two 14: step 8
Described organic polymer monomer mass and carbon nano-tube/poly silane composite mass ratio are (9～12): 1.Other is with concrete
One of embodiment one to two 14 is identical.
Detailed description of the invention 26: unlike one of present embodiment and detailed description of the invention one to two 15: step 8
Described organic polymer monomer mass and carbon nano-tube/poly silane composite mass ratio are 10:1.Other is real with concrete
Execute one of mode one to two 15 identical.
Detailed description of the invention 27: unlike one of present embodiment and detailed description of the invention one to two 16: step 8
Described initiator is 1:(50～80 with the mass ratio of organic polymer monomer).Other is with detailed description of the invention one to two ten six
One of identical.
Detailed description of the invention 28: unlike one of present embodiment and detailed description of the invention one to two 17: step 8
Described initiator is 1:(60～80 with the mass ratio of organic polymer monomer).Other is with detailed description of the invention one to two ten seven
One of identical.
Detailed description of the invention 29: unlike one of present embodiment and detailed description of the invention one to two 18: step 8
Described initiator is 1:70 with the mass ratio of organic polymer monomer.Other is with detailed description of the invention one of one to two ten eight
Identical.
Detailed description of the invention 30: unlike one of present embodiment and detailed description of the invention one to two 19: described has
Machine solvent is toluene, dimethylbenzene, octane or cycloheptane.Other is one of one to two ten nine identical with detailed description of the invention.
Detailed description of the invention 31: present embodiment is unlike one of detailed description of the invention one to three ten: described alkali
Metal is metallic sodium or Na-K alloy.Other is identical with one of detailed description of the invention one to three ten.
Detailed description of the invention 32: unlike one of present embodiment and detailed description of the invention one to three 11: described
Reaction terminating agent is anhydrous isopropyl alcohol or dehydrated alcohol.Other is one of one to three ten one identical with detailed description of the invention.
Detailed description of the invention 33: unlike one of present embodiment and detailed description of the invention one to three 12: described
Blended organic solvent is oxolane, toluene, N,N-dimethylformamide, acetone or dehydrated alcohol.Other is real with concrete
Execute one of mode one to three 12 identical.
Detailed description of the invention 34: unlike one of present embodiment and detailed description of the invention one to three 13: described
Initiator is azodiisobutyronitrile, benzoyl peroxide or methyl ethyl ketone peroxide.Other is with detailed description of the invention one to three ten three
One of identical.
Detailed description of the invention 35: unlike one of present embodiment and detailed description of the invention one to three 14: described
Dichlorosilane is dichloromethyl phenylsilane, diphenyl dichlorosilane or methylvinyldichlorosilane；Described trichlorosilane
For for methyl trichlorosilane, vinyl trichlorosilane, phenyl trichlorosilane or nonyl trichlorosilane.Other and specific embodiment party
One of formula one to three 14 is identical.
Detailed description of the invention 36: unlike one of present embodiment and detailed description of the invention one to three 15: described
CNT is SWCN or multi-walled carbon nano-tubes.Other is one of one to three ten five identical with detailed description of the invention.
Detailed description of the invention 37: unlike one of present embodiment and detailed description of the invention one to three 16: described
Polysilane is line style polysilane, branched polysilane or branched polysilanes.Other is one of one to three ten six phase with detailed description of the invention
With.
Detailed description of the invention 38: unlike one of present embodiment and detailed description of the invention one to three 17: described
Organic polymer monomer is styrene, ethylene or methyl methacrylate.Other is with detailed description of the invention one of one to three ten seven
Identical.
Detailed description of the invention 39: a kind of CNT-polysilane-organic polymer composite of present embodiment, be
By CNT, organic solvent, dichlorosilane, trichlorosilane, alkali metal, reaction terminating agent, blended organic solvent, have
Machine high polymer monomer and initiator are made, and wherein, the quality of described dichlorosilane and the volume ratio of organic solvent are 1g:(60
ML～125mL)；Described dichlorosilane and alkali-metal mass ratio are (0.8～2): 1；Described dichlorosilane and trichlorine silicon
The mass ratio of alkane is 1:(0～4)；The quality of described dichlorosilane with the volume ratio of reaction terminating agent is
1g:(30mL～60mL)；Described CNT is 1:(1～10 with the mass ratio of dichlorosilane)；Described CNT is together
The mass volume ratio of mixed organic solvent is 1g:(15mL～240mL)；Described organic polymer monomer and CNT matter
Amount ratio is (10～100): 1；Described initiator is 1:(40～100 with the mass ratio of organic polymer monomer).
Detailed description of the invention 40: present embodiment is unlike detailed description of the invention 39: described CNT is
SWCN or multi-walled carbon nano-tubes.Other is identical with detailed description of the invention 39.
Detailed description of the invention 41: present embodiment is unlike detailed description of the invention 39 or 40: described is poly-
Silane is line style polysilane, branched polysilane or branched polysilanes.Other is identical with detailed description of the invention 39 or 40.
Detailed description of the invention 42: unlike one of present embodiment and detailed description of the invention 30 nine to four 11: institute
The quality of the dichlorosilane stated and the volume ratio of organic solvent are 1g:(35～50) mL.Other is with detailed description of the invention 39
Identical to one of 41.
Detailed description of the invention 43: unlike one of present embodiment and detailed description of the invention 30 nine to four 12: institute
The quality of the dichlorosilane stated and the volume ratio of organic solvent are 1g:(40～45) mL.Other is with detailed description of the invention 39
Identical to one of 42.
Detailed description of the invention 44: unlike one of present embodiment and detailed description of the invention 30 nine to four 13: institute
The dichlorosilane stated and alkali-metal mass ratio are (1～1.8): 1.Other with detailed description of the invention 30 nine to four ten three it
One is identical.
Detailed description of the invention 45: unlike one of present embodiment and detailed description of the invention 30 nine to four 14: institute
The dichlorosilane stated and alkali-metal mass ratio are (1.4～1.6): 1.Other with detailed description of the invention 30 nine to four ten four it
One is identical.
Detailed description of the invention 46: unlike one of present embodiment and detailed description of the invention 30 nine to four 15: institute
The dichlorosilane stated is 1:(2～4 with the mass ratio of trichlorosilane).Other with detailed description of the invention 30 nine to four ten five it
One is identical.
Detailed description of the invention 47: unlike one of present embodiment and detailed description of the invention 30 nine to four 16: institute
The dichlorosilane stated is 1:(2.5～3 with the mass ratio of trichlorosilane).Other with detailed description of the invention 30 nine to four ten six it
One is identical.
Detailed description of the invention 48: unlike one of present embodiment and detailed description of the invention 30 nine to four 17: institute
The quality of the dichlorosilane stated and the volume ratio of reaction terminating agent are 1g:(40mL～50mL).Other is with detailed description of the invention three
One of ten nine to four ten seven identical.
Detailed description of the invention 49: unlike one of present embodiment and detailed description of the invention 30 nine to four 18: institute
The CNT stated is 1:(2～8 with the mass ratio of dichlorosilane).Other is with detailed description of the invention one of 30 nine to four ten eight
Identical.
Detailed description of the invention 50: unlike one of present embodiment and detailed description of the invention 30 nine to four 19:: institute
The CNT stated is 1:(3～7 with the mass ratio of dichlorosilane).Other is with detailed description of the invention one of 30 nine to four ten nine
Identical.
Detailed description of the invention 51: present embodiment is unlike one of detailed description of the invention 30 nine to five ten: described
The mass ratio of CNT and dichlorosilane be 1:(4～6).Other is identical with one of detailed description of the invention 30 nine to five ten.
Detailed description of the invention 52: unlike one of present embodiment and detailed description of the invention 30 nine to five 11::
Described CNT is 1:5 with the mass ratio of dichlorosilane.Other is one of 30 nine to five ten one phases with detailed description of the invention
With.
Detailed description of the invention 53: unlike one of present embodiment and detailed description of the invention 30 nine to five 12: institute
The initiator stated is 1:(50～80 with the mass ratio of organic polymer monomer).Other is with detailed description of the invention 30 nine to five ten
One of two identical.
Detailed description of the invention 54: unlike one of present embodiment and detailed description of the invention 30 nine to five 13: institute
The initiator stated is 1:(60～80 with the mass ratio of organic polymer monomer).Other is with detailed description of the invention 30 nine to five ten
One of three identical.
Detailed description of the invention 55: unlike one of present embodiment and detailed description of the invention 30 nine to five 14: institute
The initiator stated is 1:70 with the mass ratio of organic polymer monomer.Other with detailed description of the invention 30 nine to five ten four it
One is identical.
Detailed description of the invention 56: unlike one of present embodiment and detailed description of the invention 30 nine to five 15: institute
The organic solvent stated is toluene, dimethylbenzene, octane or cycloheptane.Other is with detailed description of the invention one of 30 nine to five ten five
Identical.
Detailed description of the invention 57: unlike one of present embodiment and detailed description of the invention 30 nine to five 16: institute
The alkali metal stated is metallic sodium or Na-K alloy.Other is one of 30 nine to five ten six identical with detailed description of the invention.
Detailed description of the invention 58: unlike one of present embodiment and detailed description of the invention 30 nine to five 17: institute
The reaction terminating agent stated is anhydrous isopropyl alcohol or dehydrated alcohol.Other is one of 30 nine to five ten seven phases with detailed description of the invention
With.
Detailed description of the invention 59: unlike one of present embodiment and detailed description of the invention 30 nine to five 18: institute
The blended organic solvent stated is oxolane, toluene, N,N-dimethylformamide, acetone or dehydrated alcohol.Other with tool
One of body embodiment 30 nine to five 18 is identical.
Detailed description of the invention 60: unlike one of present embodiment and detailed description of the invention 30 nine to five 19: described
Initiator be azodiisobutyronitrile, benzoyl peroxide or methyl ethyl ketone peroxide.Other with detailed description of the invention 39 to
One of 59 identical.
Detailed description of the invention 61: present embodiment is unlike one of detailed description of the invention 30 nine to six ten: described
Dichlorosilane be dichloromethyl phenylsilane, diphenyl dichlorosilane or methylvinyldichlorosilane；Described trichlorine silicon
Alkane is methyl trichlorosilane, vinyl trichlorosilane, phenyl trichlorosilane or nonyl trichlorosilane.Other be embodied as
One of mode 30 nine to six ten is identical.
Detailed description of the invention 62: unlike one of present embodiment and detailed description of the invention 30 nine to six 11: institute
The organic polymer monomer stated is styrene, ethylene or methyl methacrylate.Other is with detailed description of the invention 30 nine to six
One of 11 identical.
Detailed description of the invention 63: unlike one of present embodiment and detailed description of the invention 30 seven to six 12: institute
The preparation method of the polysilane stated is: is imported in constant pressure funnel by the silane monomer of step 3/organic solvent solution, then exists
Mixing speed is 600r/min～1000r/min, temperature is 60 DEG C～80 DEG C, under conditions of nitrogen protection and lucifuge by
1mL/min～1.5mL/min rate of addition is added dropwise in step 2 gained alkali metal/organic solvent suspension, drips complete
After, control mixing speed and enter under the conditions of 80 DEG C～120 DEG C, nitrogen protection and lucifuge in 600r/min～1000r/min, temperature
Row back flow reaction, the response time is 6h～8h, is then cooled to room temperature, and carries out solid-liquid separation, i.e. obtains the mixing of polymer
Thing filtrate.Other is one of 30 seven to six ten two identical with detailed description of the invention.
Present invention is not limited only to the content of the respective embodiments described above, the combination of one of them or several detailed description of the invention with
Sample can also realize the purpose of invention.
Use following verification experimental verification effect of the present invention:
Test one:
The preparation method of a kind of CNT-polysilane-poly styrene composite material of this test, completes the most according to the following steps
:
One, Purification of Carbon Nanotubes is processed；
Two, alkali metal/organic solvent suspension is prepared: added by 0.6g sodium in 30mL toluene, form mixed liquor, will be mixed
Close liquid to add in reaction unit, and low whipping speed be 1200r/min, temperature be the 2h that refluxes under 120 DEG C and nitrogen protection,
Then naturally cool to room temperature, obtain alkali metal/organic solvent suspension；
Three, silane monomer/organic solvent solution is prepared: take 1.0541g phenyl trichlorosilane and 0.7051g dimethyl dichloro silicon
Alkane is dissolved in the toluene of 40mL, i.e. obtains chlorosilane/organic solvent solution after mixing；
Four, mixing: low whipping speed is 800r/min, oil bath temperature is 65 DEG C, under the conditions of nitrogen protection and lucifuge by
The rate of addition of 1.2mL/min adds silane monomer/organic solvent solution prepared by step 3, and low whipping speed is
800r/min, oil bath temperature are 65 DEG C and the lower mixing of nitrogen protection, i.e. obtain mixture；
Five, polymerization: mixture low whipping speed 800r/min, oil bath temperature that step 4 obtains are 85 DEG C and nitrogen protection
With carry out back flow reaction under the conditions of lucifuge, the response time is 6h, is then cooled to room temperature, and carries out solid-liquid separation, i.e. obtains
The mixture filtrate of polymer；
Six, purify polysilane: step 5 gained filtrate is evaporated solvent with Rotary Evaporators, after remaining a small amount of liquid, fall
Enter in beaker, add 10mL oxolane and dissolve, add 50mL isopropanol and separate out polysilane, finally by beaker lucifuge
Stirring 24h, solid-liquid separation, washs, is dried to obtain branched polysilane；
Seven, CNT is combined with branched polysilane: takes the fine grinding of multi-walled carbon nano-tubes after 0.128g processes, puts into
In 15mL tetrahydrofuran solution, the branched polysilane taking 0.523g step 6 prepared is put in 30mL tetrahydrofuran solution,
Control temperature within 50 DEG C, respectively ultrasonic vibration 4h, then will both solution mixing, control temperature within 50 DEG C,
Ultrasonic vibration 8h；
Eight, evaporation solvent: mixing turbid liquid evaporation solvent step 7 obtained, is then dried 24h at vacuum drying oven, i.e.
Obtain CNT/branched polysilane composite；
Nine, situ aggregation method is used to prepare CNT-branched polysilane-poly styrene composite material: to take styrene 3.6g,
It is added thereto to 0.4g CNT/branched polysilane composite, reactor is placed in ultrasonic thermostatic water bath, water-bath
After temperature rises to 75 DEG C, add initiator 0.08g azodiisobutyronitrile, under ul-trasonic irradiation, carry out polyreaction, treat
After reaction 6h, system becomes thick liquid, completes pre-polymerization process.The polystyrene reactant liquid that pre-polymerization is got togather pours mould into
In tool, being put into by mould and continue polymerization in baking oven, polymerization temperature is 100 DEG C, and polymerization time is 6h, and cooling obtains carbon nanometer
Pipe-branched polysilane-poly styrene composite material.
Purifying carbon nano-tube concrete operations described in this test procedure one are as follows: 1, calcination processing: put into by CNT
In Muffle furnace, keeping temperature is 460 DEG C, takes out after calcining about 30min in air under static state；2, at HCl
Reason: the calcined product that step one obtains places in 5mol/L HCl solution, is heated to 120 DEG C of backflow 7h, then uses
Sand core funnel filters, then products therefrom deionized water rinsing being dried, and i.e. obtains the CNT after purification process.
Use infrared spectrometer to this test procedure one obtains purification of Multi-wall Carbon Nanotubes, branched polysilane and this test preparation
CNT/branched polysilane composite be analyzed, as shown in Figure 1 to 4, Fig. 1 is this test procedure one to result
In the infrared spectrum of the multi-walled carbon nano-tubes of purification that obtains, figure two is the infrared spectrogram of branched polysilane, and Fig. 3 is this
The infrared spectrogram of CNT/branched polysilane composite material of test preparation, Fig. 4～Fig. 6 be polystyrene,
Test one prepares the surface pair of Carbon Nanotubes/Polystyrene Nanocomposites and CNT-polysilane-poly styrene composite material
Than figure；The multi-walled carbon nano-tubes obtained in this test procedure one as shown in Figure 1 is at 1560cm-1There is a suction the strongest at place
Receiving peak, this is to be caused by the C-C stretching vibration of multi-walled carbon nano-tubes agent structure, 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 bond in place, at 697cm-1、732cm-1、800cm-1、
837cm-1And 997cm-1There is the stretching vibration absworption peak of Si-C, 1089cm in place-1There is Si-C in place6H5Stretching vibration inhale
Receive peak, 1253cm-1There is Si-CH in place3Symmetrical deformation vibration absworption peak, 1482cm-1And 1427cm-1Place is phenyl ring bone
Frame vibration absorption peak, 2922cm-1And 2852cm-1Place is CH3Stretching vibration absworption peak, 1629cm-1It it is C H face
Outside sweep vibration overtone, 3046cm-1Place is the hydrocarbon stretching vibration peak of phenyl ring, from the point of view of entirety, poly dimethyl-phenyl silane
Infrared Characterization data and bibliographic reference value very close to, show that monomer there occurs polymerization；As shown in Figure 3 prepared by this test
The characteristic peak of the CNT of carbon nano-tube/poly silane composite is inconspicuous, this is because the infrared vibration of CNT is inhaled
Receiving weak more than branched polysilane, so being blanked, and the characteristic absorption peak relevant with phenyl ring all there occurs that some move,
Think that this is that the pi-electron on the pi-electron of carbon nanotube side-wall and polysilane exists pi-pi accumulation effect, the most this π-π heap
Long-pending effect makes relevant characteristic absorption there occurs change, it may thus be appreciated that the carbon nano-tube/poly silane composite of this test preparation
It is combined successfully.The most do not add CNT in the Carbon Nanotubes/Polystyrene Nanocomposites of polysilane
Poor dispersion so that the performance that CNT embodies in polystyrene is not the most abundant.It will be appreciated from fig. 6 that add poly-
After silane, owing to the pi-pi accumulation effect between CNT and polysilane makes the dispersibility of CNT be improved, and
And the performance making CNT be embodied in polystyrene obtains more abundant.
Pure polystyrene, Carbon Nanotubes/Polystyrene Nanocomposites, CNT-polysilane-polystyrene are combined by this test
Material carries out electrical conductivity test by adding the CNT of different quality mark (wt%), and test result is as shown in table 1,
By table 1 it can be seen that when in Carbon Nanotubes/Polystyrene Nanocomposites, content of carbon nanotubes increases to 6% from 0, electricity
Conductance is from 4.187 × 10-12S/cm increases to 8.062 × 10-10S/cm, merely add two orders of magnitude, when CNT-poly-silicon
In alkane-poly styrene composite material CNT from 0 increase to 4% time, electrical conductivity is from 4.187 × 10-12S/cm increases to
4.356×10-9S/cm, adds three orders of magnitude, and when content increases to 6%, electrical conductivity adds six orders of magnitude, says
Bright in the case of having polysilane, the dispersibility of CNT is relatively preferable, makes the electric conductivity of composite substantially be changed
Kind.
Table 1 electrical conductivity test test result
Test two:
The preparation method of a kind of CNT-polysilane-composite material of polymethyl methacrylate of this test is concrete by following
Step completes:
One, Purification of Carbon Nanotubes is processed；
Two, prepare alkali metal/organic solvent suspension: added in 30mL toluene by 0.6g sodium, and low whipping speed is
1200r/min, temperature are 120 DEG C and the lower condensing reflux 2h of nitrogen protection, then naturally cool to room temperature, obtain alkali metal/
Organic solvent suspension；
Three, chlorosilane/toluene solvant solution is prepared: be dissolved in by methylvinyldichlorosilane 5.6428g and have in 20mL toluene,
Low whipping speed 800r/min, oil bath temperature are 65 DEG C and the lower mixing of nitrogen protection, i.e. obtain mixture；
Four, polymerization: low whipping speed is 800r/min, oil bath temperature is 65 DEG C, under the conditions of nitrogen protection and lucifuge by
The mixture that step 3 is obtained by the rate of addition of 1.25mL/min joins alkali metal/organic solvent suspension that step 2 obtains
In liquid, carrying out back flow reaction, the response time is 6h, is then cooled to room temperature, and carries out solid-liquid separation, collects filtrate, i.e.
Obtain polymer mixed liquid；
Five, purify polysilane: polymer mixed liquid step 4 obtained, evaporate solvent with Rotary Evaporators, treat that residue is few
After quantity of fluid, pour in beaker, add 10mL oxolane and dissolve, add 30mL dehydrated alcohol and separate out polysilane,
Finally beaker lucifuge is stirred 24h, solid-liquid separation, washs, be dried to obtain line style polysilane；
Six, CNT is combined with polysilane: takes the fine grinding of multi-walled carbon nano-tubes after 0.144g step one processes, puts
Entering in 15mL tetrahydrofuran solution, the line style polysilane taking 0.642g step 5 prepared puts into 25mL tetrahydrofuran solution
In, control temperature within 50 DEG C, respectively ultrasonic vibration 4h, then will both solution mixing, control temperature 50 DEG C with
In, ultrasonic vibration 8h；
Seven, evaporation solvent: the turbid liquid of mixing step 6 obtained, evaporates solvent, is then dried 24h at vacuum drying oven,
I.e. obtain carbon nano-tube/poly silane composite；
Eight, situ aggregation method is used to prepare CNT-polysilane-composite material of polymethyl methacrylate: to take 30ml first
The CNT of base acrylic acid methyl ester., 0.09g benzoyl peroxide and step 7-polysilane complex 0.1876g mixing, moves
To room temperature, shake 15～30min with ultrasonic cleaning instrument, put into after being uniformly dispersed to system in reflux, at counterflow condition
Under when being slowly heated to 80～83 DEG C, during viscous liquid to appear, stop heating, then at the bar of ultrasonic cleaning instrument concussion
It is rapidly cooled to 50 DEG C under part, liquid is poured in the most ready-made mould, then put in vacuum drying oven by whole for mould,
At 50 DEG C, it is vacuum dried 30min, in vacuum drying oven, is then warming up to 80～83 DEG C, and keeps 24h i.e. to obtain CNT
-polysilane-composite material of polymethyl methacrylate；
Purifying carbon nano-tube concrete operations described in this test procedure one are as follows: 1, calcination processing: put into by CNT
In Muffle furnace, keeping temperature is 460 DEG C, takes out after calcining about 30min in air under static state；2, at HCl
Reason: the calcined product that step one obtains places in 5mol/L solution, is heated to 120 DEG C of backflow 7h, then uses core
Funnel filters, then products therefrom deionized water rinsing being dried, and i.e. obtains the CNT after purification process.
A kind of preparation method of the CNT-polysilane-organic polymer composite of this test has plurality of advantages, is protecting
Under card carbon nano tube structure fine status, use non-carbon coating material, add polysilane so that it is under pi-pi accumulation effect
It is coated on carbon nano tube surface, thus improves the dispersibility of CNT, and make the performance of polystyrene be increased dramatically,
Whole process operation is simple, be easily controlled, and each process is independent of each other.
Pure polystyrene, Carbon Nanotubes/Polystyrene Nanocomposites, CNT-polysilane-polystyrene are combined by this test
Material carries out electrical conductivity test by adding the CNT of different quality mark (wt%), and test result shows, when carbon is received
In mitron/poly styrene composite material content of carbon nanotubes from 0 increase to 6% time, electrical conductivity is from 4.187 × 10-12S/cm increases
It is added to 8.062 × 10-10S/cm, merely add two orders of magnitude, when carbon in CNT-polysilane-poly styrene composite material
Nanotube from 0 increase to 4% time, electrical conductivity is from 4.187 × 10-12S/cm increases to 4.356 × 10-9S/cm, adds three
The order of magnitude, when content increases to 6%, electrical conductivity adds six orders of magnitude, illustrates in the case of not having polysilane,
The dispersibility of CNT is relatively poor, make composite electric conductivity can not be improved significantly.
Claims (9)
1. the preparation method of CNT-polysilane-organic polymer composite, it is characterised in that it is according to following
Step is carried out:
One, Purification of Carbon Nanotubes: CNT is carried out high-temperature calcination and acid treatment, obtains CNT after purification；
Two, prepare alkali metal organic solvent suspension: added by alkali metal in organic solvent, form mixed liquor, by mixed liquor
Add in reaction unit, and low whipping speed be 1000r/min～1500r/min, temperature be under 80 DEG C～120 DEG C and nitrogen protection
Backflow 0.5h～1h, then natural cooling, obtain alkali metal/organic solvent suspension；
Three, silane monomer/organic solvent solution is prepared: dichlorosilane derivant and trichlorosilane derivatives are dissolved in organic solvent,
Mixing i.e. obtains silane monomer/organic solvent solution；
Described dichlorosilane derivant is dichloromethyl phenylsilane, diphenyl dichlorosilane or methylvinyldichlorosilane；
Described trichlorosilane derivatives is methyl trichlorosilane, vinyl trichlorosilane, phenyl trichlorosilane or nonyl trichlorine
Silane；
Four, polysilane is prepared in silane monomer polymerization: imported by the silane monomer of step 3/organic solvent solution in constant pressure funnel,
Then low whipping speed be 600r/min～1000r/min, temperature be 60 DEG C～80 DEG C, under conditions of nitrogen protection and lucifuge by
1mL/min～1.5mL/min rate of addition is added dropwise in step 2 gained alkali metal/organic solvent suspension, after dropping,
Control mixing speed to carry out back under the conditions of 80 DEG C～120 DEG C, nitrogen protection and lucifuge in 600r/min～1000r/min, temperature
Stream reaction, the response time is 6h～8h, is then cooled to room temperature, and carries out solid-liquid separation, i.e. obtains the mixture filter of polymer
Liquid；
Five, polysilane is purified: step 4 gained filtrate is evaporated solvent with Rotary Evaporators, is poured into by remaining liq in beaker,
Add oxolane to dissolve, add reaction terminating agent and separate out polysilane, finally by beaker lucifuge stirring 24h, solid-liquid separation,
Wash, be dried to obtain polysilane；
Six, CNT is combined with polysilane: after the CNT after purification step one obtained grinds, obtain with step 5
To polysilane be respectively put in blended organic solvent, control temperature within 50 DEG C, respectively ultrasonic vibration 4h, then mix,
After ultrasonic vibration 8h, obtain mixed liquor；
Seven, evaporation solvent: after the mixed liquor of step 6 is evaporated solvent, is vacuum dried 24h, i.e. obtains carbon nano-tube/poly silicon
Alkane composite；
Eight, situ aggregation method is used to prepare CNT-polysilane-organic polymer composite: to weigh carbon prepared by step 7
Nanotube/polysilane powder composite, joins in organic polymer monomer, reaction unit is placed in ultrasonic constant-temperature water
In bath, after bath temperature is raised to 75 DEG C, adds initiator, under ul-trasonic irradiation, carry out polyreaction, question response 6h
After, the liquid after prepolymerization is poured in mould, then mould is put in baking oven under conditions of temperature is 100 DEG C, continue
Continuous polymerization 8h, after cooling, obtains CNT-polysilane-organic polymer composite；Described organic polymer monomer
For styrene, ethylene or methyl methacrylate；
Alkali metal described in step 2 is 1g:(30mL～100mL with the mass volume ratio of organic solvent)；
The quality of dichlorosilane derivant described in step 3 with the volume ratio of organic solvent described in step 2 is
1g:(30mL～40mL)；Dichlorosilane derivant described in step 3 is (0.8～2) with alkali-metal mass ratio described in step 2: 1；
Dichlorosilane derivant described in step 3 is 1:(0～4 with the mass ratio of trichlorosilane derivatives)；Described in step 3, dichlorosilane spreads out
Biological quality is 1g:(30mL～85mL with the volume ratio of organic solvent described in step 3)；Oxolane body described in step 5
Long-pending is (5mL～20mL): 1g with dichlorosilane derivant mass ratio described in step 3；Reaction terminating agent described in step 5 and four
Hydrogen furan volume ratio is (5～12): 1；Carbon nanotube mass described in step 6 and polysilane mass ratio are 1:(1～4)；Step 6 institute
The blended organic solvent volume stated and polysilane mass ratio are (15mL～60mL): 1g；Organic polymer monomer described in step 8
Quality and carbon nano-tube/poly silane composite mass ratio are (5～20): 1；Initiator described in step 8 and organic polymer
The mass ratio of monomer is 1:(40～100).
The preparation method of a kind of CNT-polysilane-organic polymer composite the most according to claim 1, its
Being characterised by, described in step one, CNT is carried out high-temperature calcination and acid treatment, concrete operations are as follows: one, at calcining
Reason: put into by CNT in Muffle furnace, keeping temperature is 450 DEG C～500 DEG C, takes out after calcining about 30min；Two, HCl
Process: calcined product step one obtained places in 5mol/L HCl solution, is heated to 100～120 DEG C of backflows
6h～7h, then filter with sand core funnel, collect solid formation, gained solid formation deionized water rinsing is also dried, i.e. obtains pure
CNT after change process.
The preparation method of a kind of CNT-polysilane-organic polymer composite the most according to claim 1, its
The temperature being characterised by step 2 is 100 DEG C～120 DEG C.
The preparation method of a kind of CNT-polysilane-organic polymer composite the most according to claim 1, its
It is characterised by being imported in constant pressure funnel by the silane monomer of step 3/organic solvent solution described in step 4, then presses
1.2mL/min～1.5mL/min rate of addition is added dropwise in step 2 gained alkali metal/organic solvent suspension.
The preparation method of a kind of CNT-polysilane-organic polymer composite the most according to claim 4, its
It is characterised by being imported in constant pressure funnel by the silane monomer of step 3/organic solvent solution described in step 4, then presses
1.5mL/min rate of addition is added dropwise in step 2 gained alkali metal/organic solvent suspension.
The preparation method of a kind of CNT-polysilane-organic polymer composite the most according to claim 1, its
After being characterised by the dropping described in step 4, control mixing speed and exist in 600r/min～1000r/min, temperature
Carrying out back flow reaction under the conditions of 100 DEG C～120 DEG C, nitrogen protection and lucifuge, the response time is 6h～8h.
The preparation method of a kind of CNT-polysilane-organic polymer composite the most according to claim 1, its
It is characterised by that dichlorosilane derivant described in step 3 is 1:(2～4 with the mass ratio of trichlorosilane derivatives).
The preparation method of a kind of CNT-polysilane-organic polymer composite the most according to claim 1, its
It is characterised by that the CNT of the purification described in step 6 and polysilane mass ratio are 1:(1～3).
The preparation method of a kind of CNT-polysilane-organic polymer composite the most according to claim 1, its
It is characterised by that the organic polymer monomer mass described in step 8 with carbon nano-tube/poly silane composite mass ratio is
(10～20): 1.
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| 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 |
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