CN101864015B - Method for preparing polyacrylonitrile/carbon nano tube composite material by taking ionic liquid as solvent - Google Patents
Method for preparing polyacrylonitrile/carbon nano tube composite material by taking ionic liquid as solvent Download PDFInfo
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Abstract
The invention relates to a method for preparing a polyacrylonitrile/carbon nano tube composite material by taking ionic liquid as a solvent. The method comprises the following steps of: dispersing carbon nano tubes to the ionic liquid; adding monomers and an initiator into the ionic liquid for polymerizing to obtain stock solution of the polyacrylonitrile/carbon nano tube composite material; and obtaining the polyacrylonitrile/carbon nano tube composite material by washing and drying the obtained stock solution. The polyacrylonitrile/carbon nano tube composite material is prepared into a polyacrylonitrile/carbon nano tube composite membrane by adopting a coating method or is prepared into polyacrylonitrile/carbon nano tube composite fibers by adopting a wet spinning process or a dry-jet wet spinning process. The adopted solvent ionic liquid can make the carbon nano tubes disperse uniformly, and has no volatility and environmental-friendliness. In the preparation method, an in-site polymerization method is adopted, so the preparation method is simple and convenient to operate. The composite material can be used in the fields such as the enhancement, the conductivity, the anti-static property, the electromagnetic shielding and the like of a material.
Description
Technical field
The invention belongs to the preparation field of matrix material, particularly relating to a kind of is the method that solvent prepares polyacrylonitrile/carbon nano tube compound material with the ionic liquid.
Background technology
Polyacrylonitrile/carbon nano tube compound material is one of emerging in recent years matrix material.Because having significantly than polyacrylonitrile, the adding of carbon nanotube, the mechanical property of polyacrylonitrile/carbon nano tube compound material, electric property, thermal characteristics aspect improve.This matrix material all has wide practical use in fields such as space flight, weaving, automobiles.
The preparation method of polyacrylonitrile/carbon nano tube compound material adopts solution blended process and situ aggregation method usually, and solution blended process is simple, but carbon nanotube is difficult to reach homodisperse in full-bodied polymers soln.Situ aggregation method is a kind of effective way for preparing nano composite material, and it can effectively improve the bonding strength and the dispersion effect of filler in matrix of Nano filling and polymer interface.The preparation method is simple, is convenient to operation.
In the preparation process of polyacrylonitrile/carbon nano tube compound material, the solvent that adopts has Sodium Thiocyanate 99 (NaSCN) aqueous solution, dimethyl sulfoxide (DMSO) (DMSO), dimethyl formamide (DMF) etc. usually.At first need in the preparation process carbon nanotube is carried out covalent modification or non-covalent modification, carbon nanotube is dispersed in the solvent, and then prepares matrix material by solution blending or situ aggregation method.Preparation process is loaded down with trivial details, and efficient is low.Application number is 200410067019.4 patent disclosure by adopting situ aggregation method to prepare the method for polyacrylonitrile/carbon nano tube compound material fiber, but carbon nanotube just reaches homodisperse through the purification process of strong acid, after surfactant modified in polymeric matrix.
Application number has been 200810034458.3 patent disclosure by carbon nanotube and polyacrylonitrile spinning solution blend, and prepares the method for PAN-based carbon fiber by wet-spinning.But carbon nanotube is easily reunited in full-bodied polyacrylonitrile solution, and this can reduce the spinning property of spinning solution, and the reunion of carbon nanotube causes the defective that is unfavorable for oxidation.Application number a kind of method that rapidly and efficiently prepares acrylonitrile polymer that has been 200510111530.4 patent disclosure, the ionic liquid that adopts is accelerated polymerization rate greatly, and transformation efficiency improves.Transformation efficiency reaches more than 70%.The viscosity-average molecular weight of prepared acrylonitrile copolymer can reach 3 * 10
4～8 * 10
4, but only related to the preparation method of polyacrylonitrile in this document, do not relate to the preparation method of matrix material.
Read that to yet there are no in the document with the ionic liquid be the report that solvent prepares polyacrylonitrile/carbon nano tube compound material.The present invention utilize viscosity of il big, with carbon nanotube characteristics than strong interaction are arranged, adopt situ aggregation method to prepare polyacrylonitrile/carbon nano tube compound material, overcome carbon nanotube bad dispersibility and loaded down with trivial details, the inefficient shortcoming of preparation technology in the above-mentioned solution blended process.
Summary of the invention
It is the method that solvent prepares polyacrylonitrile/carbon nano tube compound material with the ionic liquid that technical problem to be solved by this invention provides a kind of, the ionic liquid that is adopted promptly can be used as the dispersion agent of carbon nanotube as solvent again, and carbon nanotube not surface modification just can reach homodisperse.And monomeric polymerization rate is fast in the ionic liquid, the transformation efficiency height.The preparation method of matrix material adopts situ aggregation method, can effectively improve the dispersion effect of carbon nanotube in the polyacrylonitrile matrix, and method is simple, is convenient to operation.
Method of the present invention comprises and is prepared as follows step:
(1) carbon nanotube is dispersed in the suspension that obtains carbon nanotube and ionic liquid formation in the alkyl imidazole ionic liquid;
(2) monomer, initiator are joined successively in the suspension of carbon nanotube and ionic liquid formation, mix; Polymerization 2～5h under 50～70 ℃ of temperature condition of normal pressure, monomer conversion is 70～85%, obtains polyacrylonitrile/carbon nano tube compound material stoste; Described monomer comprises first monomer at least, and described first monomer is a vinyl cyanide;
The mass concentration of monomer in ionic liquid is 10～35%, and the monomeric relatively mass percent of initiator is 0.5～1.5%, and the monomeric relatively mass percent of carbon nanotube is 0.1～10%;
(3) polyacrylonitrile/carbon nano tube compound material stoste is through washing, be drying to obtain polyacrylonitrile/carbon nano tube compound material; Wherein, the viscosity-average molecular weight of the polyacrylonitrile in the polyacrylonitrile/carbon nano tube compound material of gained is 3 * 10
4～2 * 10
5, the mass percent of carbon nanotube is 0.12～12.50%, the radially cohesive size of carbon nanotube is 3～52nm;
Perhaps the matrix material stoste of step (2) gained adopts filming technology to prepare polyacrylonitrile/carbon nano-tube compound film; The breaking tenacity of the polyacrylonitrile/carbon nano-tube compound film of gained is 90～120MPa, and specific conductivity is 10
-8～10
-2S/cm, the radially cohesive size of carbon nanotube is 2～60nm;
Perhaps the matrix material stoste of step (2) gained adopts solvent spinning to prepare polyacrylonitrile/carbon nano tube composite fibre; The filament number of the polyacrylonitrile/carbon nano tube composite fibre of gained is 1.0～3.3dtex, and breaking tenacity is 3～6.5cN/dtex, and specific conductivity is 10
-8～10
-2S/cm; The orientation degree of carbon nanotube＞70%, the radially cohesive size of carbon nanotube is 10～150nm;
Described alkyl imidazole ionic liquid is made up of positively charged ion and negatively charged ion, and wherein positively charged ion is the alkyl imidazole ion, and its structural formula is as follows:
Wherein, R
1, R
2Can be identical, also can be different, they are respectively that H or carbonatoms are 1～8 alkyl;
The preferred Cl of negatively charged ion
-, Br
-In a kind of.
The purity of described carbon nanotube 〉=90%; Described carbon nanotube is Single Walled Carbon Nanotube and/or multi-walled carbon nano-tubes; Wherein, the diameter 0.75～3nm of described Single Walled Carbon Nanotube, length 1～5 μ m; Described multi-walled carbon nano-tubes diameter 20～30nm, length 0.5～5 μ m.
At room temperature the settling time is more than 5 days to described carbon nanotube.
Described monomer also comprises second monomer except that comprising first monomer, described second monomer be acrylamide, methyl acrylate, methyl methacrylate, methacrylonitrile,, a kind of in the vinyl acetate, isopropene cyanide.
The massfraction of the relative total monomer of described first monomer is that the massfraction of 80～99%, the second relative total monomer of monomer is 1～20%.
Described monomer is except that comprising first monomer, also comprise second monomer and the 3rd monomer, what described the 3rd monomer was methylene-succinic acid, sodium allylsulfonate, methylpropene sodium sulfonate, methacrylic benzene sulfonic acid sodium salt, right-vinylbenzenesulfonic acid sodium, vinyl pyridine, dimethylaminoethyl acrylate methyl in amino ethyl ester, the 2-methyl-5-vinylpyridine is a kind of.
The massfraction of the relative total monomer of described first monomer is that the massfraction of 80～98%, the second relative total monomer of monomer is that the massfraction of the 1～17%, the 3rd relative total monomer of monomer is 1%～3%.
Described initiator is a kind of in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide, dilauroyl peroxide, di-isopropyl peroxydicarbonate, di-cyclohexylperoxy dicarbonate, the peroxy dicarbonate two (2-ethylhexyl).
Beneficial effect
(1) ionic liquid of the present invention can make even carbon nanotube disperse.
(2) ionic liquid physical efficiency of the present invention is accelerated the speed of polyreaction greatly, the molecular weight height of polymerisate.
(3) the present invention can effectively strengthen the dispersion effect of carbon nanotube in the polyacrylonitrile matrix, and the preparation method is simple because of adopting situ aggregation method, is convenient to operation.
(4) adding of carbon nanotube increases substantially the mechanical property and the conductivity of matrix material.
Embodiment
Embodiment 1
(1) be that 0.75nm, length are that 1 μ m, purity are 90%, to account for monomer mass percentage ratio be that 0.1% Single Walled Carbon Nanotube is added in ionic liquid 1-butyl-3-Methylimidazole muriate with diameter, utilize ultrasonic dispersing to obtain the suspension of carbon nanotube and ionic liquid formation, the settling time of carbon nanotube is 16 days under the room temperature.
(2) vinyl cyanide, Diisopropyl azodicarboxylate are joined successively in the suspension of carbon nanotube and ionic liquid formation, mix; The mass concentration of vinyl cyanide in 1-butyl-3-Methylimidazole muriate is 20%, and the mass percent of the relative vinyl cyanide of Diisopropyl azodicarboxylate is 0.5%.Be warming up to 55 ℃ under the normal pressure, reacted 3 hours, monomer conversion is 71%, obtains polyacrylonitrile/carbon nano tube compound material stoste, and the viscosity-average molecular weight of the polyacrylonitrile of gained is 3.0 * 10
4
(3) polyacrylonitrile/carbon nano tube compound material stoste is 0.14% polyacrylonitrile/carbon nano tube compound material through washing, being drying to obtain content of carbon nanotubes, and the radially cohesive size of carbon nanotube is 3nm.
Embodiment 2
(1) be that 20nm, length are that 0.5 μ m, purity are 93%, to account for monomer mass percentage ratio be that 0.7% multi-walled carbon nano-tubes is added in ionic liquid 1-allyl group-3-Methylimidazole bromide with diameter, utilize ultrasonic dispersing to obtain the suspension of carbon nanotube and ionic liquid formation, the settling time of carbon nanotube is 15 days under the room temperature.
(2) vinyl cyanide, acrylamide, 2,2'-Azobis(2,4-dimethylvaleronitrile) are joined successively in the suspension of carbon nanotube and ionic liquid formation, mix; The mass concentration of total monomer in 1-allyl group-3-Methylimidazole bromide is 15%, the mass percent of the relative total monomer of vinyl cyanide is 80%, the mass percent of the relative total monomer of acrylamide is 20%, and the mass percent of the relative total monomer of 2,2'-Azobis(2,4-dimethylvaleronitrile) is 0.7%.Be warming up to 60 ℃ under the normal pressure, reacted 3.5 hours, monomer conversion is 74%, obtains polyacrylonitrile/carbon nano tube compound material stoste, and the viscosity-average molecular weight of the polyacrylonitrile of gained is 4.7 * 10
4
(3) polyacrylonitrile/carbon nano tube compound material stoste is 0.94% polyacrylonitrile/carbon nano tube compound material through washing, being drying to obtain content of carbon nanotubes, and the radially cohesive size of carbon nanotube is 40nm.
Embodiment 3
(1) be that 0.8nm, length are that 2 μ m, purity are 96%, to account for monomer mass percentage ratio be that 1% Single Walled Carbon Nanotube and diameter are that 23nm, length are that 2 μ m, purity are 95%, to account for monomer mass percentage ratio be that 1% multi-walled carbon nano-tubes is added in ionic liquid 1-butyl-3-Methylimidazole bromide with diameter, utilize ultrasonic dispersing to obtain the suspension of carbon nanotube and ionic liquid formation, the settling time of carbon nanotube is 13 days under the room temperature.
(2) vinyl cyanide, methyl acrylate, methylene-succinic acid, dibenzoyl peroxide are joined successively in the suspension of carbon nanotube and ionic liquid formation, mix; The mass concentration of total monomer in 1-butyl-3-Methylimidazole bromide is 25%, the mass percent of the relative total monomer of vinyl cyanide is 80%, the mass percent of the relative total monomer of methyl acrylate is 17%, the mass percent of the relative total monomer of methylene-succinic acid is 3%, and the mass percent of the relative total monomer of dibenzoyl peroxide is 1.2%.Be warming up to 70 ℃ under the normal pressure, reacted 2.5 hours, monomer conversion is 78%, obtains polyacrylonitrile/carbon nano tube compound material stoste, and the viscosity-average molecular weight of the polyacrylonitrile of gained is 6.0 * 10
4
(3) polyacrylonitrile/carbon nano tube compound material stoste is 2.50% polyacrylonitrile/carbon nano tube compound material through washing, being drying to obtain content of carbon nanotubes, and the radially cohesive size of carbon nanotube is 46.8nm.
Embodiment 4
(1) be that 26nm, length are that 1 μ m, purity are 97%, to account for monomer mass percentage ratio be that 3% multi-walled carbon nano-tubes is added in ionic liquid 1-allyl group-3-Methylimidazole muriate with diameter, utilize ultrasonic dispersing to obtain the suspension of carbon nanotube and ionic liquid formation, the settling time of carbon nanotube is 15 days under the room temperature.
(2) vinyl cyanide, methyl methacrylate, methacrylic benzene sulfonic acid sodium salt, dilauroyl peroxide are joined successively in the suspension of carbon nanotube and ionic liquid formation, mix; The mass concentration of total monomer in 1-allyl group-3-Methylimidazole muriate is 17%, the mass percent of the relative total monomer of vinyl cyanide is 85%, the mass percent of the relative total monomer of methyl methacrylate is 12%, the mass percent of the relative total monomer of methacrylic benzene sulfonic acid sodium salt is 3%, and the mass percent of the relative total monomer of dilauroyl peroxide is 0.8%.Be warming up to 67 ℃ under the normal pressure, reacted 4 hours, monomer conversion is 74%, obtains polyacrylonitrile/carbon nano tube compound material stoste, and the viscosity-average molecular weight of the polyacrylonitrile of gained is 5.3 * 10
4
(3) polyacrylonitrile/carbon nano tube compound material stoste is 3.90% polyacrylonitrile/carbon nano tube compound material through washing, being drying to obtain content of carbon nanotubes, and the radially cohesive size of carbon nanotube is 52nm.
Embodiment 5
(1) be that 1nm, length are that 1 μ m, purity are 95%, to account for monomer mass percentage ratio be that 3% Single Walled Carbon Nanotube is added in ionic liquid 1-methyl-3-butyl imidazole bromination thing with diameter, utilize ultrasonic dispersing to obtain the suspension of carbon nanotube and ionic liquid formation, the settling time of carbon nanotube is 12 days under the room temperature.
(2) vinyl cyanide, methyl methacrylate, dibenzoyl peroxide are joined successively in the suspension of carbon nanotube and ionic liquid formation, mix; The mass concentration of total monomer in 1-methyl-3-butyl imidazole bromination thing is 22%, the mass percent of the relative total monomer of vinyl cyanide is 88%, the mass percent of the relative total monomer of methyl methacrylate is 12%, and the mass percent of the relative total monomer of dilauroyl peroxide is 1.3%.Be warming up to 70 ℃ under the normal pressure, reacted 3.5 hours, monomer conversion is 80%, obtains polyacrylonitrile/carbon nano tube compound material stoste, and the viscosity-average molecular weight of the polyacrylonitrile of gained is 7.3 * 10
4
(3) polyacrylonitrile/carbon nano tube compound material stoste content that adopts coating method to prepare carbon nanotube is 3.61% polyacrylonitrile/carbon nano-tube compound film.The breaking tenacity of the polyacrylonitrile/carbon nano-tube compound film of gained is 90MPa, and specific conductivity is 7.9 * 10
-5S/cm, the radially cohesive size of carbon nanotube is 2nm.
Embodiment 6
(1) be that 25nm, length are that 4 μ m, purity are 98%, to account for monomer mass percentage ratio be that 6% multi-walled carbon nano-tubes is added in ionic liquid 1-ethyl-3-Methylimidazole bromide with diameter, utilize ultrasonic dispersing to obtain the suspension of carbon nanotube and ionic liquid formation, the settling time of carbon nanotube is 10 days under the room temperature.
(2) vinyl cyanide, vinyl acetate, sodium allylsulfonate, di-isopropyl peroxydicarbonate are joined successively in the suspension of carbon nanotube and ionic liquid formation, mix; The mass concentration of total monomer in 1-ethyl-3-Methylimidazole bromide is 35%, the mass percent of the relative total monomer of vinyl cyanide is 85%, the mass percent of the relative total monomer of vinyl acetate is 13%, the mass percent of the relative total monomer of sodium allylsulfonate is 2%, and the mass percent of the relative total monomer of di-isopropyl peroxydicarbonate is 1.5%.Be warming up to 68 ℃ under the normal pressure, reacted 5 hours, monomer conversion is 85%, obtains polyacrylonitrile/carbon nano tube compound material stoste, and the viscosity-average molecular weight of the polyacrylonitrile of gained is 1.0 * 10
5
(3) polyacrylonitrile/carbon nano tube compound material stoste content that adopts coating method to prepare carbon nanotube is 6.59% polyacrylonitrile/carbon nano-tube compound film.The breaking tenacity of the polyacrylonitrile/carbon nano-tube compound film of gained is 104MPa, and specific conductivity is 6.3 * 10
-4S/cm, the radially cohesive size of carbon nanotube is 50nm.
Embodiment 7
(1) be that 4nm, length are that 4 μ m, purity are 92%, to account for monomer mass percentage ratio be that 7% Single Walled Carbon Nanotube is added in ionic liquid 1-methyl-3-butyl imidazole muriate with diameter, utilize ultrasonic dispersing to obtain the suspension of carbon nanotube and ionic liquid formation, the settling time of carbon nanotube is 9 days under the room temperature.
(2) vinyl cyanide, methacrylonitrile, methylpropene sodium sulfonate, dibenzoyl peroxide are joined successively in the suspension of carbon nanotube and ionic liquid formation, mix; The mass concentration of total monomer in 1-methyl-3-butyl imidazole muriate is 27%, the mass percent of the relative total monomer of vinyl cyanide is 89%, the mass percent of the relative total monomer of methacrylonitrile is 10%, and the mass percent of the relative total monomer of methylpropene sodium sulfonate is 1%.The mass percent of the relative total monomer of dibenzoyl peroxide is 1.0%.Be warming up to 70 ℃ under the normal pressure, reacted 2 hours, monomer conversion is 78%, obtains polyacrylonitrile/carbon nano tube compound material stoste, and the viscosity-average molecular weight of the polyacrylonitrile of gained is 8.6 * 10
4
(3) polyacrylonitrile/carbon nano tube compound material stoste content that adopts coating method to prepare carbon nanotube is 8.24% polyacrylonitrile/carbon nano-tube compound film.The breaking tenacity of the polyacrylonitrile/carbon nano-tube compound film of gained is 120MPa, and specific conductivity is 8.1 * 10
-4S/cm, the radially cohesive size of carbon nanotube is 12nm.
Embodiment 8
(1) be that 3nm, length are that 3 μ m, purity are 97%, to account for monomer mass percentage ratio be that 2% Single Walled Carbon Nanotube and diameter are that 27nm, length are that 3 μ m, purity are 92%, to account for monomer mass percentage ratio be that 2% multi-walled carbon nano-tubes is added in ionic liquid 1-ethyl-3-Methylimidazole muriate with diameter, utilize ultrasonic dispersing to obtain the suspension of carbon nanotube and ionic liquid formation, the settling time of carbon nanotube is 11 days under the room temperature.
(2) vinyl cyanide, Diisopropyl azodicarboxylate are joined successively in the suspension of carbon nanotube and ionic liquid formation, mix; The mass concentration of vinyl cyanide in 1-ethyl-3-Methylimidazole muriate is 30%, the mass percent of the relative vinyl cyanide of Diisopropyl azodicarboxylate is 1.1%, be warming up to 65 ℃ under the normal pressure, reacted 2.5 hours, monomer conversion is 73%, obtain polyacrylonitrile/carbon nano tube compound material stoste, the viscosity-average molecular weight of the polyacrylonitrile of gained is 6.0 * 10
4
(3) polyacrylonitrile/carbon nano tube compound material stoste content that adopts coating method to prepare carbon nanotube is 5.19% polyacrylonitrile/carbon nano-tube compound film.The breaking tenacity of the polyacrylonitrile/carbon nano-tube compound film of gained is 96MPa, and specific conductivity is 4.0 * 10
-4S/cm, the radially cohesive size of carbon nanotube is 60nm.
Embodiment 9
(1) be that 30nm, length are that 5 μ m, purity are 90%, to account for monomer mass percentage ratio be that 8% multi-walled carbon nano-tubes is added in ionic liquid 1-butyl-3-Methylimidazole bromide with diameter, utilize ultrasonic dispersing to obtain the suspension of carbon nanotube and ionic liquid formation, the settling time of carbon nanotube is 7 days under the room temperature.
(2) vinyl cyanide, methacrylonitrile, dibenzoyl peroxide are joined successively in the suspension of carbon nanotube and ionic liquid formation, mix; The mass concentration of total monomer in 1-butyl-3-Methylimidazole bromide is 18%, the mass percent of the relative total monomer of vinyl cyanide is 99%, the mass percent of the relative total monomer of methacrylonitrile is 1%, and the mass percent of the relative total monomer of dibenzoyl peroxide is 1.4%.Be warming up to 70 ℃ under the normal pressure, reacted 5 hours, monomer conversion is 83%, obtains polyacrylonitrile/carbon nano tube compound material stoste, and the viscosity-average molecular weight of the polyacrylonitrile of gained is 2 * 10
5
(3) polyacrylonitrile/carbon nano tube compound material stoste is through taking off list, and deaeration is filtered, and the content that adopts the dry-jet wet-spinning moulding process to prepare carbon nanotube is 8.79% polyacrylonitrile/carbon nano tube compound material fiber.The filament number of composite fiber is 3.3dtex, and the breaking tenacity of composite fiber is 4.9cN/dtex, and specific conductivity is 3.3 * 10
-3S/cm.The orientation degree of carbon nanotube is 76%, and the radially cohesive size of carbon nanotube is 150nm.
Embodiment 10
(1) be that 28nm, length are that 4 μ m, purity are 99%, to account for monomer mass percentage ratio be that 6% multi-walled carbon nano-tubes and diameter are that 2nm, length are that 4 μ m, purity are 93%, to account for monomer mass percentage ratio be that 4% Single Walled Carbon Nanotube is added in ionic liquid 1-hexyl-3-Methylimidazole muriate with diameter, utilize ultrasonic dispersing to obtain the suspension of carbon nanotube and ionic liquid formation, the settling time of carbon nanotube is 6 days under the room temperature.
(2) vinyl cyanide, methyl acrylate, di-isopropyl peroxydicarbonate are joined successively in the suspension of carbon nanotube and ionic liquid formation, mix; The mass concentration of total monomer in 1-hexyl-3-Methylimidazole muriate is 22%, the mass percent of the relative total monomer of vinyl cyanide is 85%, the mass percent of the relative total monomer of methyl acrylate is 15%, and the mass percent of the relative total monomer of di-isopropyl peroxydicarbonate is 1.0%.Be warming up to 60 ℃ under the normal pressure, reacted 3.5 hours, monomer conversion is 76%, obtains polyacrylonitrile/carbon nano tube compound material stoste, and the viscosity-average molecular weight of the polyacrylonitrile of gained is 6.9 * 10
4
(3) polyacrylonitrile/carbon nano tube compound material stoste is through taking off list, and deaeration is filtered, and the content that adopts the wet spinning moulding process to prepare carbon nanotube is 11.63% polyacrylonitrile/carbon nano tube compound material fiber.The filament number of composite fiber is 1.9dtex, and the breaking tenacity of composite fiber is 5.3cN/dtex, and specific conductivity is 1.2 * 10
-2S/cm.The carbon nanotube orientation degree is 80%, and the radially cohesive size of carbon nanotube is 120nm.
Embodiment 11
(1) be that 24nm, length are that 3 μ m, purity are 96%, to account for monomer mass percentage ratio be that 7% multi-walled carbon nano-tubes is added in ionic liquid 1-hexyl-3-Methylimidazole bromide with diameter, utilize ultrasonic dispersing to obtain the suspension of carbon nanotube and ionic liquid formation, the settling time of carbon nanotube is 5 days under the room temperature.
(2) vinyl cyanide, vinyl acetate, dimethylaminoethyl acrylate methyl are joined in the suspension of carbon nanotube and ionic liquid formation successively for amino ethyl ester, 2,2'-Azobis(2,4-dimethylvaleronitrile), mix; The mass concentration of total monomer in 1-hexyl-3-Methylimidazole bromide is 24%, the mass percent of the relative total monomer of vinyl cyanide is 83%, the mass percent of the relative total monomer of vinyl acetate is 15%, dimethylaminoethyl acrylate methyl is 2% for the mass percent of the relative total monomer of amino ethyl ester, and the mass percent of the relative total monomer of 2,2'-Azobis(2,4-dimethylvaleronitrile) is 0.6%.Be warming up to 69 ℃ under the normal pressure, reacted 3 hours, monomer conversion is 81%, obtains polyacrylonitrile/carbon nano tube compound material stoste, and the viscosity-average molecular weight of the polyacrylonitrile of gained is 1.3 * 10
5
(3) polyacrylonitrile/carbon nano tube compound material stoste is through taking off list, and deaeration is filtered, and the content that adopts the wet spinning moulding process to prepare carbon nanotube is 7.95% polyacrylonitrile/carbon nano tube compound material fiber.The filament number of composite fiber is 2.4dtex, and the breaking tenacity of composite fiber is 6.5cN/dtex, and specific conductivity is 8.0 * 10
-4S/cm.The orientation degree of carbon nanotube is 78%, and the radially cohesive size of carbon nanotube is 48nm.
Embodiment 12
(1) be that 2.5nm, length are that 5 μ m, purity are 94%, to account for monomer mass percentage ratio be that 5% single wall carbon nanometer is added in ionic liquid 1-methyl-3-propyl imidazole bromide with diameter, utilize ultrasonic dispersing to obtain the suspension of carbon nanotube and ionic liquid formation, the settling time of carbon nanotube is 9 days under the room temperature.
(2) vinyl cyanide, acrylamide, vinyl pyridine, Diisopropyl azodicarboxylate are joined successively in the suspension of carbon nanotube and ionic liquid formation, mix; The mass concentration of total monomer in 1-methyl-3-propyl imidazole bromide is 27%, the mass percent of the relative total monomer of vinyl cyanide is 98%, the mass percent of the relative total monomer of acrylamide is 1%, the mass percent of the relative total monomer of vinyl pyridine is 1%, and the mass percent of the relative total monomer of Diisopropyl azodicarboxylate is 1.4%.Be warming up to 63 ℃ under the normal pressure, reacted 2 hours, monomer conversion is 73%, obtains polyacrylonitrile/carbon nano tube compound material stoste, and the viscosity-average molecular weight of the polyacrylonitrile of gained is 5.9 * 10
4
(3) polyacrylonitrile/carbon nano tube compound material stoste is through taking off list, and deaeration is filtered, and the content that adopts the dry-jet wet-spinning moulding process to prepare carbon nanotube is 6.41% polyacrylonitrile/carbon nano tube compound material fiber.The filament number of composite fiber is 1.0dtex, and the breaking tenacity of composite fiber is 4.4cN/dtex, and specific conductivity is 5.1 * 10
-4S/cm.The orientation degree of carbon nanotube is 81%, and the radially cohesive size of carbon nanotube is 10nm.
Claims (8)
1. one kind is the method that solvent prepares polyacrylonitrile/carbon nano tube compound material with the ionic liquid, and its feature preparation process is:
(1) carbon nanotube is dispersed in the suspension that obtains carbon nanotube and ionic liquid formation in the alkyl imidazole ionic liquid;
(2) monomer, initiator are joined successively in the suspension of carbon nanotube and ionic liquid formation, mix; Polymerization 2～5h under 50～70 ℃ of temperature condition of normal pressure, monomer conversion is 70～85%, obtains polyacrylonitrile/carbon nano tube compound material stoste; Described monomer comprises first monomer at least, and described first monomer is a vinyl cyanide;
The mass concentration of monomer in ionic liquid is 10～35%, and the monomeric relatively mass percent of initiator is 0.5～1.5%, and the monomeric relatively mass percent of carbon nanotube is 0.1～10%;
(3) polyacrylonitrile/carbon nano tube compound material stoste is through washing, be drying to obtain polyacrylonitrile/carbon nano tube compound material; Wherein, the viscosity-average molecular weight of the polyacrylonitrile in the polyacrylonitrile/carbon nano tube compound material of gained is 3 * 10
4～2 * 10
5, the mass percent of carbon nanotube is 0.12～12.50%; The radially cohesive size of described carbon nanotube is 3～52nm;
Perhaps the matrix material stoste of step (2) gained adopts filming technology to prepare polyacrylonitrile/carbon nano-tube compound film; The breaking tenacity of the polyacrylonitrile/carbon nano-tube compound film of gained is 90～120MPa, and specific conductivity is 10
-8～10
-2S/cm, the radially cohesive size of carbon nanotube is 2～60nm;
Perhaps the matrix material stoste of step (2) gained adopts solvent spinning to prepare polyacrylonitrile/carbon nano tube composite fibre;
The filament number of the polyacrylonitrile/carbon nano tube composite fibre of gained is 1.0～3.3dtex, and breaking tenacity is 3～6.5cN/dtex, and specific conductivity is 10
-8～10
-2S/cm; The orientation degree of carbon nanotube＞70%, the radially cohesive size of carbon nanotube is 10～150nm;
Described alkyl imidazole ionic liquid is made up of positively charged ion and negatively charged ion, and wherein positively charged ion is the alkyl imidazole ion, and its structural formula is as follows:
Wherein, R
1, R
2Be respectively that H or carbonatoms are 1～8 alkyl;
Negatively charged ion selects Cl
-, Br
-In a kind of.
2. according to claim 1 a kind of be the method that solvent prepares polyacrylonitrile/carbon nano tube compound material with the ionic liquid, it is characterized in that the purity of described carbon nanotube 〉=90%; Described carbon nanotube is Single Walled Carbon Nanotube and/or multi-walled carbon nano-tubes; Wherein, the diameter 0.75～3nm of described Single Walled Carbon Nanotube, length 1～5 μ m; Diameter 20～the 30nm of described multi-walled carbon nano-tubes, length 0.5～5 μ m.
3. according to claim 1 a kind of be the method that solvent prepares polyacrylonitrile/carbon nano tube compound material with the ionic liquid, it is characterized in that at room temperature the settling time is more than 5 days to described carbon nanotube.
4. according to claim 1 a kind of be the method that solvent prepares polyacrylonitrile/carbon nano tube compound material with the ionic liquid, it is characterized in that, described monomer is except that comprising first monomer, also comprise second monomer, described second monomer is a kind of in acrylamide, methyl acrylate, methyl methacrylate, methacrylonitrile, the vinyl acetate.
5. according to claim 4 a kind of be the method that solvent prepares polyacrylonitrile/carbon nano tube compound material with the ionic liquid, it is characterized in that, the massfraction of the relative total monomer of first monomer is that the massfraction of 80～99%, the second relative total monomer of monomer is 1～20%.
6. according to claim 1 a kind of be the method that solvent prepares polyacrylonitrile/carbon nano tube compound material with the ionic liquid, it is characterized in that, described monomer comprises first monomer, second monomer and the 3rd monomer, and what described the 3rd monomer was methylene-succinic acid, sodium allylsulfonate, methylpropene sodium sulfonate, methacrylic benzene sulfonic acid sodium salt, vinyl pyridine, dimethylaminoethyl acrylate methyl in the amino ethyl ester is a kind of.
7. according to claim 6 a kind of be the method that solvent prepares polyacrylonitrile/carbon nano tube compound material with the ionic liquid, it is characterized in that, the massfraction of the relative total monomer of first monomer is 80～98%, the massfraction of the relative total monomer of second monomer is that the massfraction of the 1～17%, the 3rd relative total monomer of monomer is 1～3%.
8. according to claim 1 a kind of be the method that solvent prepares polyacrylonitrile/carbon nano tube compound material with the ionic liquid, it is characterized in that described initiator is a kind of in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide, dilauroyl peroxide, the di-isopropyl peroxydicarbonate.
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| TWI422633B (en) * | 2010-11-09 | 2014-01-11 | Ind Tech Res Inst | Polyacrylonitrile-based copolymer/cnt composites, carbon fibers and fabrication method of carbon fiber |
| CN102181116B (en) * | 2011-03-25 | 2013-01-02 | 杭州师范大学 | Carbon-nanotube-containing polymer nanocomposite and preparation method thereof |
| CN102391618A (en) * | 2011-08-11 | 2012-03-28 | 复旦大学 | Preparation method of alignment carbon nano tube/polymer composite membrane |
| CN102953137B (en) * | 2011-08-18 | 2014-08-27 | 香港理工大学 | High-elasticity conductive fiber and preparation method thereof |
| CN103219065B (en) * | 2013-03-28 | 2016-04-06 | 山西森达源科技有限公司 | A kind of environmental-friendly conductive sizing agent based on carbon nanotube-nano copper powder |
| CN104892866B (en) * | 2014-03-05 | 2017-07-07 | 中国科学院大连化学物理研究所 | A kind of magnetic carbon nano-tube of polymeric ionic liquid grafting and preparation method thereof |
| CN104594077B (en) * | 2015-01-14 | 2017-06-13 | 中国科学院过程工程研究所 | The preparation method of ionic liquid carbon conductive nano solution and conductive fiber |
| CN104630923A (en) * | 2015-01-26 | 2015-05-20 | 中复神鹰碳纤维有限责任公司 | Method for preparing carbon nano tube modified polyacrylonitrile fibers with solution in-situ polymerization technology |
| JP2016216863A (en) * | 2015-05-22 | 2016-12-22 | 国立研究開発法人産業技術総合研究所 | Production method of spun carbon nanotube fiber, spun carbon nanotube fiber, carbon nanotube dispersion, and evaluation method of carbon nanotube dispersion |
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| CN105254993B (en) * | 2015-11-17 | 2018-05-04 | 张建刚 | A kind of conducting polymer composite and preparation method thereof |
| CN106519363B (en) * | 2016-10-19 | 2020-06-26 | 中国石油化工股份有限公司 | Hydrogenated nitrile rubber composition |
| CN107286492A (en) * | 2017-06-28 | 2017-10-24 | 常州欣彬纺织品有限公司 | A kind of antistatic film and preparation method thereof |
| CN108912577A (en) * | 2018-07-11 | 2018-11-30 | 桐城市新瑞建筑工程有限公司 | A kind of shielding new material and preparation method thereof |
| CN111285949B (en) * | 2020-02-13 | 2021-07-06 | 山东大学 | Polyacrylonitrile-coated graphene composite material and preparation method and application thereof |
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| CN101250770B (en) * | 2008-03-11 | 2010-07-21 | 东华大学 | Method for manufacturing polyacrylonitrile-based carbon fiber with enganced carbon nano-tube |
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