CN107312328B - A kind of method that solid state shear prepares polymer grafting carbon nanomaterial - Google Patents

A kind of method that solid state shear prepares polymer grafting carbon nanomaterial Download PDF

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CN107312328B
CN107312328B CN201710560297.0A CN201710560297A CN107312328B CN 107312328 B CN107312328 B CN 107312328B CN 201710560297 A CN201710560297 A CN 201710560297A CN 107312328 B CN107312328 B CN 107312328B
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carbon nanomaterial
polymer
carbon
solid state
dispersion aids
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张兴祥
高雪峰
陈甜
刘海辉
王学晨
王宁
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Tianjin Polytechnic University
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Abstract

The invention discloses a kind of methods that solid state shear prepares polymer grafting carbon nanomaterial, including 1) are uniformly mixed carbon nanomaterial with dispersion aids, so that carbon nanomaterial surface is coated with dispersion aids；The carbon nanomaterial for being enclosed with dispersion aids that step 1) is obtained uniformly is mixed with polymer, obtains mixture；The mixture that step 2) is obtained is added among the discoidal shearing disk of two panels, until entire mixture passes through；4) process of step 3) is repeated；5) collection of products made from step 4) is grafted carbon nanomaterial to get to polymer.This method realizes that polymer is mixed with the uniform of carbon nanomaterial by the method for solid state shear, not only it is obviously improved the degree of scatter of carbon nanomaterial in the polymer, and the mass fraction of carbon nanomaterial in polymer composites can be improved significantly, and then improve the physical and mechanical property and electric property of polymer.

Description

A kind of method that solid state shear prepares polymer grafting carbon nanomaterial
Technical field
The present invention relates to high-performance polymer field of material preparation, specifically a kind of solid state shear prepares polymer grafted carbon The method of nano material.
Background technique
At the end of the 20th century, the carbon nanotube and graphene successively found at the beginning of 21 century has excellent physical mechanics and electrical property Energy.Graphene is one kind by sp2The carbon material of the monatomic lamella with two-dimentional planar structure of the carbon atom composition of hydridization, and Carbon nanotube then can be regarded as a kind of one-dimensional tubulose carbon material curled by graphene film.Carbon nanotube is according to its tube wall The difference of the number of plies can be divided into single-walled carbon nanotube, double-walled carbon nano-tube and multi-walled carbon nanotube.Both carbon nanomaterials are multiple The preparation field of condensation material has important application.
There are mainly three types of the methods for realizing both carbon nanomaterials and mixed with polymers at present: (1) situ aggregation method: benefit There are the characteristics that with carbon nanomaterial surface or there are free radical or oxygen-containing groups after physics, chemical method processing, by it Be regarded as it is a kind of can reaction monomers with the monomer that can form polymer Raolical polymerizable or polycondensation reaction, e.g., application number occurs 201410614121.5 the graphite oxide of phenylethylene-maleic anhydride grafting is added disclosed in during the polymerization of caprolactam Alkene, the method for preparing polyamide grafts grapheme material through polycondensation reaction；(2) solution blended process: polymer is dissolved in first molten Then certain mass carbon nanomaterial is added in agent, directly use after mixing, or be precipitated and polymerize in precipitating reagent Object/carbon nanomaterial mixture, such as " composite material journal (2010,27 (1): 12-17) " disclose polyamide 66 dissolving in first Solution is made in acid, and the formic acid dispersion liquid of multi-walled carbon nanotube is then added, and ultrasonication 2h again after merging delays under strong mixing Slow that dehydrated alcohol is added, polyamide/carbon nanotube is precipitated from solution, and suction filtration obtains mixture；(3) melt-blending process: will gather Melting extrusion after conjunction object powder or pelletizing are mixed with carbon nanomaterial utilizes the stirring of screw rod, twin-screw or mixer, shearing to make With the dispersion of carbon nanomaterial in the polymer is realized, such as " composite material journal (2011,28 (2): 16-21) " disclose will be poly- Slice is made in amide 66 and the mixing of the multi-walled carbon nanotube of different quality containing, the blending extrusion in twin-screw melt extruder, Then in 60 DEG C of vacuum drying 6h, mixture is obtained.
It is cumbersome that prior art preparation obtains polymer/carbon nanomaterial mixture technics comparing, or is related to organic Solvent using and removing, so that preparation process is not environmentally, and in addition to situ aggregation method, solution blended process and melt-blending process There was only Van der Waals force in obtained mixture between polymer molecular chain and carbon nanomaterial, interaction force is weaker, is easy to make Disperse in the polymer at carbon nanomaterial unevenly, to be difficult to reach ideal physical mechanics and the modified effect of electric property Fruit is very limited in practical applications.Further, these three current methods can not achieve high carbon nanomaterial matter The polymer composites preparation of score is measured, in general, the matter of carbon nanomaterial in the composite material of these three methods preparation It measures score and is no more than 3%, when continuing to improve carbon nanomaterial content, wound since the draw ratio of carbon nanotube is big, or It is stacked between graphene layer, causes carbon nanomaterial to disperse in the polymer irregular, and processing performance sharply declines, no legal system Standby required polymer composites out, or the physical mechanics of polymer composites or electric property prepared are not achieved Target can not achieve the purpose of the present invention.
Summary of the invention
In view of the deficiencies of the prior art, the technical issues of present invention intends to solve is to provide a kind of solid state shear preparation polymerization The method of object grafting carbon nanomaterial.This method realizes that polymer and the uniform of carbon nanomaterial mix by the method for solid state shear It closes, in carbon nanomaterial surface grafting polymerization object strand, is not only obviously improved the dispersion journey of carbon nanomaterial in the polymer Degree, and the method that chemical bond is further formed between polymer molecular chain and carbon nanomaterial, and can improve significantly The mass fraction of carbon nanomaterial in polymer composites, and then improve the physical and mechanical property and electric property of polymer.
The technical solution that the present invention solves the technical problem, which is to provide a kind of solid state shear and prepares polymer grafted carbon, to be received The method of rice material, it is characterised in that include the following steps:
1) carbon nanomaterial is uniformly mixed with dispersion aids, so that carbon nanomaterial surface is coated with dispersion aids； The quality of dispersion aids is 0.1~5wt% of carbon nanomaterial quality；
2) carbon nanomaterial for being enclosed with dispersion aids for obtaining step 1) is uniformly mixed with polymer, is mixed Object；The quality of the carbon nanomaterial for being enclosed with dispersion aids is 0.1~20wt% of polymer quality；
3) rate for 10~100g/min of mixture that step 2) obtains is added to the two of 30~200 turns/min rotation Among the discoidal shearing disk of piece, until entire mixture passes through；Processing temperature is 10~90 DEG C, processes side of the product from disk Edge or lower end are overflowed；
4) process for repeating step 3), the process for being often repeated once step 3) carry out a graft reaction Tachistoscope, directly To reaching requirement；
5) collection of products made from step 4) is grafted carbon nanomaterial to get to polymer.
Compared with prior art, the beneficial effects of the invention are that:
(1) simple process, without using polymerisable monomer and the carbon nanomaterial containing functional group is as raw material, also need not be in height Temperature is lower to react for a long time, and polymer grafting carbon nanomaterial can be realized, be not related to using and removing for organic solvent, so that system Standby process environmental protection, the interaction force between polymer molecular chain and carbon nanomaterial is strong, and carbon nanomaterial divides in the polymer It dissipates uniformly, ideal physical mechanics and electric property modified effect can be reached.
(2) applicable range of polymers is wide, is applicable not only to the polyester using polycondensation reaction preparation, polyamide, poly- carbonic acid Ester, polyphenylene sulfide, polyether-ether-ketone, polyether ketone ketone are also applied for the polyvinyl chloride of sudden reaction preparation, chliorinated polyvinyl chloride, gather Benzimidazole, polymethyl methacrylate, polystyrene, polyethylene, polypropylene.
(3) polymer grafting carbon nanomaterial is prepared relative to using situ aggregation method, method of the invention is more quick Ground realizes that polymer is grafted carbon nanomaterial, is suitble to the extensive modified production of existing polymer material, and can prepare The polymer composites of high carbon nanomaterial mass fraction, therefore method of the invention is particularly suitable for carbon nanomaterial quality Polymer/carbon nanomaterial compound preparation of the score 3% or more, highest carbon nanomaterial mass fraction can reach 20%.
(4) shortening and the multi-walled carbon nanotube portion outer layer of length of carbon nanotube be will cause in solid state shear engineering Damage, but also can prevent carbon nanotube from occurring tangling and reunite, promote the removing of multi-layer graphene.Therefore, method of the invention Especially suitable for the dispersion of the biggish carbon nanotube of length and multi-layer graphene in the polymer, and these are exactly existing molten Liquid blending method and the insurmountable problem of melt-blending process, this is equally that situ aggregation method is insoluble.
Detailed description of the invention
Fig. 1 is the graphene that solid state shear of the present invention prepares that polymer is grafted in the embodiment of the method 1 of carbon nanomaterial Raman spectrogram；
Fig. 2 is the polyamide 66 that solid state shear of the present invention prepares that polymer is grafted in the embodiment of the method 1 of carbon nanomaterial The Raman spectrogram of graft grapheme；
Specific embodiment
Specific embodiments of the present invention are given below.Specific embodiment is only used for that present invention be described in more detail, unlimited The protection scope of the claim of this application processed.
It is special the present invention provides a kind of method (abbreviation method) that solid state shear prepares polymer grafting carbon nanomaterial Sign is to include the following steps:
1) carbon nanomaterial is uniformly mixed with dispersion aids, so that carbon nanomaterial surface is coated with dispersion aids； The quality of dispersion aids is 0.1~5wt% of carbon nanomaterial quality；
2) carbon nanomaterial for being enclosed with dispersion aids for obtaining step 1) is uniformly mixed with polymer, is mixed Object；The quality of the carbon nanomaterial for being enclosed with dispersion aids is 0.1~20wt% of polymer quality；
3) rate for 10~100g/min of mixture that step 2) obtains is added to the two of 30~200 turns/min rotation Among the discoidal shearing disk of piece, until entire mixture passes through, for primary grinding；The discoidal shearing disk of two panels is to mixture Solid state shear processing is carried out, so that partial polymer molecular chain rupture, forms free radical；Carbon nanomaterial is disconnected in shear history It splits, graft reaction occurs for the free radical or active group and polymer on surface, forms polymer and is grafted carbon nanomaterial；Processing Temperature is 10~90 DEG C, and processing revolving speed is 30~200 turns/min, and processing product is overflowed from the edge of disk or lower end；
4) process for repeating step 3), the process for being often repeated once step 3) carry out a graft reaction Tachistoscope, directly To reaching requirement；
5) collection of products made from step 4) is grafted carbon nanomaterial to get to polymer, can according to need and is used for Melting extrusion, injection molding or hot-forming.
The carbon nanomaterial refers to single-walled carbon nanotube, double-walled carbon nano-tube, multi-walled carbon nanotube and its carboxylated, hydroxyl Base or amination modified derivative；Single-layer graphene, few layer graphene and multi-layer graphene and its oxidation, carboxylated, hydroxyl Change or amination modified derivative；Further it is also applied for carbon fiber or carbon nano-fiber powder.
The dispersion aids is to refer to form chemical bond or stronger van der Waals interaction with carbon nanomaterial, as π-π is total The substance of yoke effect, these substances include but is not limited to: polycyclic hexane ethylene-b- polyethylene-b- polycyclic hexane ethylene, polyoxy third Alkene-b- polyoxyethylene copolymer, polyoxyethylene-b- polyoxypropylene-b- polyoxyethylene, polyvinylpyrrolidone, polyethylene pyrrole Pyrrolidone-b- polyoxyethylene, neopelex, polyethyleneimine, poly- P-TOLUENE SULFO ACID 99's sodium, gathers poly- 1- vinyl imidazole Ethylene glycol octyl phenyl ether, polystyrene-maleic anhydride copolymer sodium salt or sodium carboxymethylcellulose.
The effect of the dispersion aids is that the dispersion of carbon nanomaterial in the polymer can be promoted, prevents carbon and receive The reunion again of rice material, reduces attrition process number.
In order to make dispersion aids be evenly coated at carbon nanomaterial surface, it is sometimes desirable to be dissolved dispersion aids using solvent The solution that concentration is 5~20wt% is made, concentration is too low, and it is more using solvent, it causes to waste, excessive concentration, viscosity is excessive, difficult To realize the uniform cladding on carbon nanomaterial surface；The solvent can dissolve dispersion aids according to the type of dispersion aids And it easily removes, specifically at least one of acetone, ethyl alcohol, hexamethylene, n-hexane, toluene or water.
The polymer refer to polyhexamethylene adipamide (polyamide 66), polycaprolactam (polyamide 6), poly- decanedioyl oneself Diamines (polyamide 610), polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, poly- naphthalene Dioctyl phthalate second diester, polycarbonate, polyethylene, polypropylene, polyvinyl chloride, chliorinated polyvinyl chloride, polyphenylene sulfide, polyether-ether-ketone, Polyether ketone ketone, polybenzimidazoles, polymethyl methacrylate or polystyrene；Preferred polyamide 66, is gathered to benzene two polyamide 6 Formic acid second diester, polytrimethylene terephthalate, polyethylene naphthalate, polyphenylene sulfide, polyether-ether-ketone or polyether ketone ketone.
The Mechanico-chemical reactor for realizing shearing is in the Chinese invention patent application No. is 95242817.2 It is open；The Mechanico-chemical reactor includes that the discoidal shearing disk of two panels is horizontally or vertically placed by two panels with fluted Turntable is constituted, wherein a piece of is fixed, and another is rotation.Fixinig plate has hollow structure, can be passed through recirculated water Or liquid CO 2, liquid nitrogen refrigerating, prevent temperature from increasing.
The solid state shear method prepares polymer grafting carbon nanomaterial and refers to that processing temperature is lower than the melting temperature of polymer Degree 30 DEG C or more, polymer is not in molten condition in process, due to the performance characteristics of polymer itself, in low temperature or Shearing is carried out under ultralow temperature, the efficiency of processing can be improved, but itself energy consumption can be caused to increase and freeze ice expense with anti-cold Increase, the present invention is not recommended to use.Currently preferred processing temperature is 10~90 DEG C, when being lower than 10 DEG C, is generally required Take refrigeration measure；And temperature is higher than 90 DEG C, it is difficult to using cheap water as cooling media, also not be recommended to use.One As for, relatively high processing temperature help to realize carbon nanomaterial dispersion in the polymer and polymer molecular chain with Graft reaction between carbon nanomaterial.
The slewing rate of rotatable disc of the discoidal shearing disk of two panels is related with the groove structure of panel surface and disk diameter, For revolving speed generally in 30~200 turns/min, slewing rate is too low, so that shear effect is bad, and slewing rate is excessively high, then is easy to make Too fast at heat production, temperature is difficult to control.
Polymer will appear molecular chain rupture during two panels discoidal shearing disk intermediate shear, generate free radicals or Reactive group, free radical or can reactive group and carbon nanomaterial surface free radical or epoxy group, carboxyl, hydroxyl or Amino chemically reacts, and forms chemical bond, to realize that polymeric solid phase is grafted carbon nanomaterial, this polymer grafted carbon Contain high performance carbon nanomaterial in nano material, be processed into after casting, fiber show more excellent physical mechanics and Electric property can widen the application field of polymer material.
The method of inspection whether polymer after solid state shear is grafted to carbon nanomaterial surface is generally dissolution-light scattering Method, Raman spectroscopy.Specifically, polymer grafting carbon nanomaterial has better solubility property, and stability of solution is better than poly- Object/carbon nanomaterial mixture is closed, deposit-free exists in light scattering test；The peak D is due to carbon nanomaterial in Raman spectrum Middle carbon atom sp3Caused by the defect of hydridization, and the peak G is then derived from sp2The carbon atom of hydridization, by comparing the intensity at the peak D and the peak G, It may determine that the defects of carbon nanometer degree, after carbon nanomaterial surface grafting polymerization object, ID/IGIncrease.
Embodiment 1
The preparation method of polyamide 66 graft grapheme, includes the following steps:
1) it weighs 285g graphene (1~10 layer, 8 μm of piece diameter size), the polyethylene pyrrole of 300g (concentration 5wt%) is added Pyrrolidone/ethanol solution is stirred to solution with the rate physical of 200 turns/min and is adsorbed by graphene；
2) it weighs by being dried in vacuo dewatered polyamide 66 powder 1700g, it is added in the graphene of step 1) In, physical agitation to polyamide 66 powder is uniformly mixed with graphene；
3) mixture that step 2) obtains is added to the two panels disk gone to 200 turns/min with the rate of 100g/min Among the shearing disk of shape, processing temperature is 60 DEG C, circular grinding 50 times；
4) mixture made from step 3) is collected, is dissolved in the solution that 15wt% is made in formic acid, observe the steady of solution Qualitative, polyamide 66/graphene is with good stability after solid state shear is processed, and storage does not observe that light dissipates for 72 hours It penetrates and changes significantly.In the Raman spectrum test of Fig. 1 and Fig. 2, ID/IGAfter being increased to grafting by 0.52 before processing 1.04, show sp after grafting3Hydbridized carbon atoms number increases, and surface defect degree increases.The mixture and first that step 3) is obtained Acid-mixed is closed, it is found that the mixture can be evenly dispersed in formic acid, light scattering test finds no sediment, shows polyamide 66 Covalent bond is formd between graphene.The solution is filtered with the polytetrafluoroethylene (PTFE) filter paper in 0.5 μm of aperture, with formic acid repeated flushing Gained black powder 4 times, with transmission electron microscopy observation, the number of plies of graphene is reduced to based on 1~5 layer, and scanning electron is aobvious Micro mirror observation, the piece diameter size reduction of graphene is to 4 μm or so.
5) the polyamide 66 graft grapheme that step 3) is collected is made after 280 DEG C of melting extrusions cuts on the twin screw extruder In 280 DEG C of melt spinnings fiber is made after dry in grain, and at 130 DEG C 4.5 times of drawing-off, and the conductivity of obtained fiber is 2.1x10-3S/cm, the conductivity for the Nylon66 tested under the conditions of are 10-16S/cm。
Embodiment 2
The preparation method of polyethylene terephthalate carboxyl grafting multi-walled carbon nano-tube, includes the following steps:
1) weighing the functionalized multi-wall carbonnanotubes of 20g, (average 15 layers of wall, 5 μm of average length, carboxylated carbon atom number accounts for The 1.2% of surface carbon atom number), the Triton X-100/methanol solution of 20g (concentration 0.5wt%) is added, with 50 Turn/rate physical of min stirs to Triton X-100 by carbon nanotube adsorption；
2) it weighs by being dried in vacuo dewatered polyethylene terephthalate particle 1880g, by the carbon of step 1) Nanotube is added thereto, and physical agitation to polyethylene terephthalate particle is uniformly mixed with carbon nanotube；
3) mixture of step 2) is added to the two panels gone to 50 turns/min is discoidal to cut with the rate of 50g/min Among cutting disc, processing temperature is 90 DEG C, circular grinding 30 times；
4) mixture made from step 3) is collected, is dissolved in tetrachloroethanes/phenol (mass ratio 6:4) mixed solution and makes At the solution of 15wt%, solution is with good stability.In Raman spectrum test, ID/IGIt is increased to by 0.75 before processing 1.23.The solution is filtered with the polytetrafluoroethylene (PTFE) filter paper in 0.5 μm of aperture, with tetrachloroethanes/phenol mixed solution repeated flushing institute It obtains mixture 4 times, with transmission electron microscopy observation, the number of plies of carbon nanotube is reduced to 12 layers or so, scanning electron microscope Observation, the length of carbon nanotube are reduced to 2 μm or so.
5) the polyethylene terephthalate grafting carbon nanotube powder that step 3) is collected melts on 300 DEG C of spinning machine Fiber is made in spinning, and at 135 DEG C 4.5 times of drawing-off, the tensile break strength of obtained fiber reaches 650MPa, Young's modulus 1.8GPa, elongation at break 23%.
Embodiment 3
The preparation method of polyethylene naphthalate grafted multi-wall carbon nanotube, includes the following steps:
1) multi-walled carbon nanotube (average 15 layers of wall, 5 μm of average length) for weighing 88.85g, 30g is added, and (concentration is Neopelex/ethanol solution 0.5wt%), is stirred with the rate physical of 80 turns/min to dodecyl benzene sulfonic acid Sodium is by carbon nanotube adsorption；
2) it weighs by being dried in vacuo dewatered polyethylene naphthalate particle 1910g, the carbon of step 1) is received Mitron is added thereto, and physical agitation to polyethylene naphthalate particle is uniformly mixed with carbon nanotube；
3) that the mixture of step 2) is added to the two panels gone to 200 turns/min with the rate of 100g/min is discoidal Among shearing disk, processing temperature is 90 DEG C, circular grinding 20 times；
4) the polyethylene naphthalate grafting carbon nanotube powder that step 3) is collected melts spinning on 300 DEG C of spinning machine Fiber is made in silk, and at 135 DEG C 4.5 times of drawing-off, the tensile break strength of obtained fiber reaches 340MPa, Young's modulus 1.2GPa, elongation at break 26%, conductivity 5.2x10-6S/cm。
Embodiment 4
The preparation method of polystyrene graft graphene, includes the following steps:
1) the few layer of graphene (1~5 layer, average 2 μm of piece diameter) for weighing 380g, is added the poly- of 200g (concentration 1wt%) Vinylpyrrolidone/aqueous solution is stirred to polyvinylpyrrolidone with the rate physical of 100 turns/min and is adsorbed by graphene, very Sky dries and removes moisture；
2) it weighs by being dried in vacuo dewatered granules of polystyrene 1600g, it is added in the graphene of step 1) In, physical agitation to granules of polystyrene is uniformly mixed with graphene；
3) that the mixture of step 2) is added to the two panels gone to 120 turns/min with the rate of 100g/min is discoidal Among shearing disk, processing temperature is 90 DEG C, circular grinding 25 times；
4) powder for taking 20g step 3) to obtain is dispersed with stirring in acetone, is examined and determine discovery using the method for embodiment 1, is gathered Styrene molecules chain is grafted to graphene surface, and graphene is averaged piece diameter size reduction to 1.2 μm.
5) 1.5mm thin slice, conductivity 128S/ is made in 220 DEG C of hot pressing in the polystyrene graft graphene powder collected Cm has electric conductivity.
Embodiment 5
Polycarbonate is grafted the preparation method of hydroxylated multi-walled carbon nanotubes, includes the following steps:
1) weigh 194g hydroxylated multi-walled carbon nanotubes (average 15 layers of wall, 8 μm of average length, hydroxylating carbon atom number Account for the 1.5% of surface carbon atom number), be added 100g (concentration 3wt%) polyoxyethylene-b- polyoxypropylene-b- polyoxyethylene/ Aqueous solution is stirred to polyoxyethylene-b- polyoxypropylene-b- polyoxyethylene with the rate physical of 50 turns/min and is inhaled by carbon nanotube It is attached；
2) it weighs by being dried in vacuo dewatered polycarbonate pellets 1800g, the carbon nanotube of step 1) is added Wherein, physical agitation is uniformly mixed to polycarbonate pellets with carbon nanotube；
3) that the mixture of step 2) is added to the two panels gone to 300 turns/min with the rate of 200g/min is discoidal Among shearing disk, processing temperature is 70 DEG C, circular grinding 45 times；
4) 10mm × 5mm is made on 300 DEG C of extruder in the polycarbonate grafting carbon nanotube powder that step 3) is collected The plate of (width x thickness), the conductivity of the plate are 3.4S/cm, 15 orders of magnitude high compared with polycarbonate plate.
Embodiment 6
The preparation method of polyether-ether-ketone grafted multi-wall carbon nano tube/graphene, includes the following steps:
1) graphene (1~10 layer, 8 μm of piece diameter size), 14.7g hydroxylating single-walled carbon nanotube (5 μ of length of 15g are weighed M, hydroxylating carbon atom number account for the 1.2% of surface carbon atom number), the polycyclic hexane ethylene-b- of 0.3g (concentration 1wt%) is added Polyethylene-b- polycyclic hexane ethylene is stirred with the rate of 200 turns/min to polycyclic hexane ethylene-b- polyethylene-b- polycyclic hexane Vinyl solution is adsorbed by graphene and single-walled carbon nanotube；
2) it weighs by being dried in vacuo dewatered polyether-ether-ketone powder 2970g, by the graphene and single wall of step 1) Carbon nanotube is added thereto, and physical agitation to polyether-ether-ketone powder is uniformly mixed with graphene and single-walled carbon nanotube；
3) that the mixture of step 2) is added to the two panels gone to 150 turns/min with the rate of 80g/min is discoidal Among shearing disk, processing temperature is 90 DEG C, circular grinding 30 times；
4) polyether-ether-ketone grafting carbon nanotube/graphene that step 2) is collected on the twin screw extruder squeeze by 365 DEG C of meltings Be made pelletizing after out, it is dry after 365 DEG C of melt spinnings be made fiber, and at 180 DEG C 4.5 times of drawing-off, the physics of obtained fiber Mechanical property is obviously improved.
Comparative example 1
1) graphene (8 μm of piece diameter size) of 285g1~5 layer is weighed, the polyethylene pyrrole of 15g (concentration 5wt%) is added Pyrrolidone is stirred to polyvinylpyrrolidone with the rate physical of 200 turns/min and is adsorbed by graphene；
2) it weighs by being dried in vacuo dewatered polyamide 66 powder 1700g, it is added in the graphene of step 1) In, physical agitation to polyamide 66 powder table is uniformly mixed with graphene；
3) pelletizing will be made after the mixture of step 2) on the twin screw extruder 280 DEG C of melting extrusions, 280 after drying DEG C melt spinning, it is difficult to form continuous fiber, pelletizing does not have spinnability.
Comparative example 2
1) weighing the functionalized multi-wall carbonnanotubes of 20g, (average 15 layers of wall, 5 μm of average length, carboxylated carbon atom number accounts for The 1.2% of surface carbon atom number), the Triton X-100/methanol solution of 20g (concentration 0.5wt%) is added, with 50 Turn/rate physical of min stirs to Triton X-100 solution by carbon nanotube adsorption；
2) it weighs by being dried in vacuo dewatered polyethylene terephthalate particle 1880g, by the carbon of step 1) Nanotube is added thereto, and physical agitation to polyethylene terephthalate particle is uniformly mixed with carbon nanotube；
3) fiber is made in the mixture of step 2) melt spinning on 300 DEG C of spinning machine, and at 135 DEG C 4.5 times of drawing-off, The tensile break strength of obtained fiber reaches 540MPa, Young's modulus 1.5GPa, elongation at break 26%.
The present invention does not address place and is suitable for the prior art.

Claims (5)

1. a kind of method that solid state shear prepares polymer grafting carbon nanomaterial, it is characterised in that include the following steps:
1) carbon nanomaterial is uniformly mixed with dispersion aids, so that carbon nanomaterial surface is coated with dispersion aids；It helps point The quality of powder is 0.1~5wt% of carbon nanomaterial quality；
2) carbon nanomaterial for being enclosed with dispersion aids for obtaining step 1) is uniformly mixed with polymer, obtains mixture；Institute State be enclosed with the carbon nanomaterial of dispersion aids quality be polymer quality 0.1~20wt%；
3) rate for 10~100g/min of mixture that step 2) obtains is added to the two panels circle with 30~200 turns/min rotation Among the shearing disk of dish type, until entire mixture passes through；Processing temperature is 10~90 DEG C, processing product from the edge of disk or It overflows lower end；
4) process for repeating step 3), the process for being often repeated once step 3) carries out a graft reaction Tachistoscope, until reaching To requirement；
5) collection of products made from step 4) is grafted carbon nanomaterial to get to polymer；
The dispersion aids is that polycyclic hexane ethylene-b- polyethylene-b- polycyclic hexane ethylene, polyoxypropylene-b- polyoxyethylene are total Polymers, polyoxyethylene-b- polyoxypropylene-b- polyoxyethylene, polyvinylpyrrolidone, polyvinylpyrrolidone-b- polyoxy second Alkene, poly- 1- vinyl imidazole, neopelex, polyethyleneimine, poly- P-TOLUENE SULFO ACID 99's sodium, polyethylene glycol octyl phenyl Ether, polystyrene-maleic anhydride copolymer sodium salt or sodium carboxymethylcellulose.
2. the method that solid state shear according to claim 1 prepares polymer grafting carbon nanomaterial, it is characterised in that institute It states carbon nanomaterial and refers to single-walled carbon nanotube, double-walled carbon nano-tube, multi-walled carbon nanotube and its carboxylated, hydroxylating or amino Change modification derivant；Or single-layer graphene, less layer graphene and multi-layer graphene and its oxidation, carboxylated, hydroxylating or ammonia Base modification derivant.
3. the method that solid state shear according to claim 1 prepares polymer grafting carbon nanomaterial, it is characterised in that step It is rapid 1) in dispersion aids be concentration be 5~20wt% solution.
4. the method that solid state shear according to claim 1 prepares polymer grafting carbon nanomaterial, it is characterised in that institute Stating polymer is polyhexamethylene adipamide, polycaprolactam, polyhexamethylene sebacamide, polyethylene terephthalate, gathers to benzene Dioctyl phthalate propylene diester, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyethylene, polypropylene, polychlorostyrene Ethylene, chliorinated polyvinyl chloride, polyphenylene sulfide, polyether-ether-ketone, polyether ketone ketone, polybenzimidazoles, polymethyl methacrylate or poly- Styrene.
5. the method that solid state shear according to claim 4 prepares polymer grafting carbon nanomaterial, it is characterised in that institute Stating polymer is polyhexamethylene adipamide, polycaprolactam, polyethylene terephthalate, polytrimethylene terephthalate, gathers Polyethylene naphthalate, polyphenylene sulfide, polyether-ether-ketone or polyether ketone ketone.
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CN2217463Y (en) * 1995-03-06 1996-01-17 四川联合大学 Dynamic chemical reactor
CN1130545A (en) * 1995-03-06 1996-09-11 四川联合大学 Mechanico-chemical reactor
CN1410475A (en) * 2002-03-14 2003-04-16 四川大学 Polymer/carbon nano pipe composite powder and its solid phase shear break up preparation method

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