CN1303147C - Mother stock of polyvinyl carbon nanotube anti-static composite material and anti-static composite material based on mother stock - Google Patents
Mother stock of polyvinyl carbon nanotube anti-static composite material and anti-static composite material based on mother stock Download PDFInfo
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- CN1303147C CN1303147C CNB2005100245226A CN200510024522A CN1303147C CN 1303147 C CN1303147 C CN 1303147C CN B2005100245226 A CNB2005100245226 A CN B2005100245226A CN 200510024522 A CN200510024522 A CN 200510024522A CN 1303147 C CN1303147 C CN 1303147C
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Abstract
The present invention relates to a high concentration master material which uses carbon nanometer tubes (CNTs) as main antistatic modified material and processing the CNTs in an acid heating oxidation to combine ball milling surface processing and to be matched with using solution blending and melt blending by adding maleic anhydride graft polyethylene, a coupling agent and ethylene propylene terpolymer to prepare carbon nanometer tube/polyethylene antistatic composite material, the obtained master material and common polyethylene material are melted and blended to granulate according to certain proportion, and the carbon nanometer tube/polyethylene antistatic composite material finally obtained not only maintains the favorable antistatic performance but also has the very excellent mechanical properties. The method has the maximum advantage of less addition amount of the carbon nanometer tubes, and the surface resistivity and the volume resistivity can be bent to achieve the industrial anti-static material operating requirements when the content of the CNTs in the final polyethylene/carbon nanometer tube composite material is 0.3 wt%; furthermore, the present invention overcomes the universal problem that the mechanical strength is unavoidably lowered after the composite material is plasticized by the added ethylene propylene terpolymer, the preparation technology is simple, master granules and common polyethylene can be directly and simply proportioned according to the required product performance and can be directly melted and blended, and the present invention is suitable for various kinds of usual plastic shaping technique and technology.
Description
Technical field
The present invention relates to the anti-static composite material masterbatch and based on the anti-static composite material of masterbatch, specifically, be with carbon nanotube (CNTs) for main antistatic modified material, be the polyvinyl carbon nanotube anti-static composite material and the masterbatch thereof of main modification object with polyethylene.
Background technology
Polyethylene is cheap because of it, excellent performance, be easy to processing, be widely used in every field such as packing, daily necessities, chemical industry, automobile, medical treatment, become one of present most widely used plastics.Has excellent electric performance as polyethylene, this has had widely it and uses aspect electrically insulating material, yet the electrical insulating property just because of it makes it exist defective in application facet such as chemical pipeline, container, films---when rubbing with the external world or peeling off, easily produce static charge, and the difficult leakage of electric charge, can constantly gather on the surface.After polyethylene surface is charged, if there is not effective leakage path, dust and dirt in the meeting absorbed air.When human body touches the polyethylene of static electrification, can produce the sensation of getting an electric shock, and static can also cause the flase operation of electronics, more seriously electrostatic attraction (or repulsion), electric shock or spark discharge phenomenon will take place in electrostatic accumulation, and this can lead to huge disaster under inflammable, explosive material envrionment conditions.For fear of electrostatic influence, must carry out polyethylene antistatic modified, to adapt to some special occasions.For macromolecular material, prevent from and eliminate the electrostatic method to mainly contain: (1) adds static inhibitor; (2) with the conducting polymer blend; (3) add conductive filler material.
Nano material is the type material that very is much accounted of in recent years, and many excellent properties that it had can be applicable to many fields, comprising being applied to polymeric material field.Carbon nanotube is a kind of of nano material, carbon nanotube is the seamless hollow tube that is rolled into by the graphite flake that carbon atom forms, in carbon nanotube, because due to the quantum confinement of electronics, electronics can only be in graphite flake along the axial motion of CNT (carbon nano-tube), so carbon nanotube shows unique electric property.The research test result shows that the average conductivity of carbon pipe nanometer can reach 1000～2000S/cm, and every micron resistance is several kilohms, and the maximum current density that allows to pass through can reach 10
6A/cm
2Because carbon nanotube has certain conducting function, therefore, can consider to adopt carbon nanotube to use as the antistatic modifier of macromolecular material.Carbon nanotube also has higher intensity and modulus in addition, if the anti-static composite material made from it and polymkeric substance can properly settle carbon nanotube dispersion and with polyethylene interface bonded problem, also should have mechanical property preferably.Because carbon nanotube is the novel material that had just occurred in recent years, at present both at home and abroad to its application facet, be included in the polymer anti static aspect applied research seldom.
The theory of carbon nanotube mechanical property and experimental study show that carbon nanotube has good mechanical property, can be used as the enhancing body of matrix material.Because length of carbon nanotube very short (generally at the hundreds of micron), as the matrix material toughener time, not only need to consider carbon nanotube and matrix in conjunction with situation, and need to consider the length-to-diameter ratio of carbon nanotube.In order to make full use of its axial superstrength, need very fitly get up carbon nanotube in axial array, this is problem of difficulty.Simultaneously, the carbon nanotube production cost is still very high, if so carbon nano tube compound material can not greatly improve its performance, then its range of application is also just very limited.
The problem that the application of carbon nanotube in high polymer composite material at first will solve is exactly its dispersiveness, and can this be one of the prerequisite that give the matrix material premium properties.The CNTs caliber is little, and surface energy is big, therefore is easy to reunite, and influences its homodisperse in polymkeric substance, causes the composite property variation.In order to improve dispersive ability and to increase it and the bonding force of polymer interface, need carry out modification to its surface.Main purpose is to reduce its surperficial energy state, improves the avidity of it and organic phase, it can be applied in the matrix material with polymkeric substance better go.
Carbon nanotube is inorganic non-polar material, and polyethylene is an organic materials, directly adopts its interface of polyethylene/carbon nano tube compound material that general melt-mixing method makes in conjunction with relatively poor, is embodied in the poor toughness of material, occurs brittle rupture in the use easily.In the prior art, mostly be to add rubber or other elastomericss in polyethylene to poly blending toughening modification, wherein adopting maximum is to add terpolymer EP rubber.The blending toughening modification of polyethylene/terpolymer EP rubber commonly used and also the commercial run of comparative maturity be simple mechanical blending, being about to polyethylene and terpolymer EP rubber drops in the melt blending equipment (as single screw extrusion machine, twin screw extruder, open mill or closed plasticator) simultaneously, by the mechanical shearing effect, two kinds of polymkeric substance of polyethylene and terpolymer EP rubber are mutually disperseed under molten state and mixes, finally terpolymer EP rubber is scattered in the polyethylene external phase.Though the impelling strength of polyethylene/ethylene propylene diene monomer (EPDM) material that simple blend obtains increases, but because the terpolymer EP rubber molecular flexibility is very big and molecular chain is very long, molecule is usually and curls the winding aggregating state in the blend process and in the blended product that is obtaining, the blend shear-stress often can only make its lengthening deformation, diminishes and be difficult to it is broken.This just makes that terpolymer EP rubber phase particle size is relatively large in polypropylene/ethylene propylene diene monomer (EPDM) material, size distribution is inhomogeneous, thereby toughening effect performance is not obvious even agglomerating particles can become a focal point of stress, damage that so on the contrary can accelerated material; Another important defective is because the long flexible chain molecule of terpolymer EP rubber easily twines the mobile variation of the melt-processed that causes material mutually.As everyone knows, in the melt blending process, add linking agent, adopt the dynamic vulcanization technology can be so that crosslinked rubber is distributed in the plastics external phase with the uniform particles of appropriate particle size.Dynamic vulcanization technology tends to meet difficulty in the application of plastic toughening, particularly terpolymer EP rubber is to poly toughness reinforcing, this mainly is because linking agent can be simultaneously to terpolymer EP rubber and its effect of polypropylene, and poly amount is greatly more than terpolymer EP rubber, this just is difficult to guarantee that polyethylene is not crosslinked agent and acts on, and the external phase polyethylene is crosslinked or degrade all the mechanical property and the processing flowability of grievous injury tenacity-increased profax.
Existing studies show that, by adding terpolymer EP rubber or other elastomericss (as SEBS) or graft modification elastomerics (as MA-SEBS), can improve the toughness of polyethylene/carbon nano tube compound material greatly, but must be cost all with the intensity of sacrificing matrix material.
Thereby, need to explore by adding other suitable substances (as compatilizer, coupling agent etc.) and adopting suitable preparation for processing, reducing the carbon nanotube add-on as far as possible, when reducing cost, make polyethylene/carbon nano tube compound material both have the excellent antistatic energy, also have outstanding toughness, and also should keep higher mechanical strength simultaneously.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, provide a kind of new masterbatch that is used for polyvinyl carbon nanotube anti-static composite material and and based on the anti-static composite material of this masterbatch.
The present invention is achieved through the following technical solutions:
The present invention is a kind of masterbatch of polyvinyl carbon nanotube anti-static composite material, and this masterbatch prepares by the following method:
1, the surface modification treatment of carbon nanotube (CNTs)
(1) nitric acid oxidation is handled
With ecosystem CNTs, place 100 ℃ of baking ovens, dry 120min.Exsiccant CNTs press 1: 3 proportioning of mass ratio with the concentration that configures for the nitric acid of (1.0～6.0) mol/L mix, reflux under the agitator effect, treatment temp are (60～160) ℃, and the treatment time is (4～24) h.Take out handled thing, be washed with distilled water to PH=7 repeatedly, put into 100 ℃ of baking ovens and dry.
(2) ball-milling processing
Earlier coupling agent is configured to the ethanolic soln of 10wt%, and drips acetic acid the pH value of solution is transferred to 3.5～5.5.
(1) is handled the CNTs and the above-mentioned coupling agent-ethanolic soln that obtain mix at 1: 4 by mass ratio, the slurries of gained are put into planetary ball mill ball milling (5～90) min, and rotating speed is (200～500) r/min.Use vacuum drying oven at 100 ℃ the CNTs that obtains at last, vacuumize fully oven dry under the condition.
Described CNTs particle diameter is 5～20nm, and length is 0.5 ~ 500 μ m;
Described coupling agent is a vinyl silicane coupling agent, is specially a kind of in vinyl trichloro silane, vinyltrimethoxy silane and the vinyltriethoxysilane.
2, solution blending
CNTs and polyethylene, maleic anhydride grafted polyethylene, coupling agent and oxidation inhibitor that above-mentioned steps (2) obtains is fully mixed in proportion, and weight ratio is:
Polyethylene: CNTs: compatilizer: coupling agent: oxidation inhibitor=100: (5～30): (5～30): (1～10): (0.01～0.1)
Described compatilizer is modified by maleic acid anhydride graft polyethylene (MAH-g-PE), and percentage of grafting is (0.8～1.2) %.
Described oxidation inhibitor is BHT.
Said mixture is put into there-necked flask, add the dimethylbenzene of capacity, heated and stirred refluxes, and temperature is 120 ℃, leaches solid mixture after 3 hours, puts it into vacuumizing and drying in 100 ℃ of vacuum drying ovens.
3, melt blending
The compound that step 2 obtains, terpolymer EP rubber (EPDM), linking agent and additional crosslinker be thorough mixing in proportion, and weight ratio is:
Compound: EPDM: linking agent: additional crosslinker=100: (30～60): (0.01～0.1): (0.1～1)
Described linking agent is the organo-peroxide linking agent, is specially dicumyl peroxide (DCP) or di-isopropylbenzene hydroperoxide (DIP);
Described additional crosslinker is an allyl ester class additional crosslinker, is specially Phthalic acid, diallyl ester (DAP) or p-benzoqui(o)none dioxime (GM);
Because the linking agent add-on is less, be mixed in better in the system in order to make it, linking agent preferably is dissolved in earlier in the organic solvent and then solution and EPDM is mixed, treat organic solvent evaporation after, EPDM mixes with the compound that step 2 obtains again.The organic solvent that is used to dissolve linking agent can be toluene or dimethylbenzene.
Said mixture is added twin screw extruder melt blending and extruding pelletization, and the pellet that obtains is a masterbatch.The temperature of twin screw extruder and mouthful mould is controlled at 180～210 ℃, and screw speed is 50～200r/min, and is keeping under the screw rod rotating state constant temperature more than 20 minutes.The mixing melt by being loaded on forcing machine forward mouth model hole, is shaped to the identical bar of shape of cross section and is cut into particle after air-cooled solidifying under the squeezing action of forcing machine, promptly gets modified poly ethylene masterbatch product.
The present invention also provides a kind of carbon nano-tube/poly ethene anti-static composite material with this masterbatch preparation, and described matrix material makes by the following method:
Masterbatch and polyethylene particle that above-mentioned steps 3 obtains is fully mixed in proportion, and weight ratio is:
Polyethylene: masterbatch=100: (5～20)
Above-mentioned compound is added twin screw extruder melt blending and extruding pelletization.The temperature of twin screw extruder and mouthful mould is controlled at 180 ~ 210 ℃, and screw speed is 50 ~ 200r/min, and the residence time of mixture in twin screw extruder was controlled at 30 ~ 240 seconds, and extrusion moulding granulation then finally obtains the modified poly ethylene product.
Among the present invention, the preparation technology of solution blending and melt blending and prescription are very crucial.
In the solution blending process, polyethylene, surface be connected to active group carbon nanotube, maleic anhydride grafted polyethylene and coupling agent this can mutually take place a series of complexity chemical reaction (as on the carbon nanotube-OH ,-COOH and maleic anhydride grafted polyethylene-MAH, maleic anhydride grafted polyethylene-MAH and coupling agent-Si-OR, coupling agent-on Si-OR and the carbon nanotube-OH ,-COOH, the vinyl of polyethylene and coupling agent etc.), form stable and firm chemical bond.
In the melt blending, the existence of additional crosslinker is its key, and it can reconnect the polypropylene chains free radical that has been initiated, degrades thereby suppress polypropylene.Adding EPDM can improve the toughness of matrix material greatly, and again because firm chemical bond has appearred stablizing in a large number in the existence of solution blending in the interface of composite system, this can overcome the decline of the mechanics of materials intensity of bringing because introduce EPDM in system again.
Beneficial effect: the invention has the advantages that by the method for nitric acid oxidation and ball-milling processing carbon nanotube is carried out purifying and surface modification, introduce the active function (OH of group in carbon nano tube surface,-COOH,-C=O), and add suitable elastomerics (terpolymer EP rubber) accordingly, compatilizer (maleic anhydride grafted polyethylene) and coupling agent (vinyl silicane coupling agent), the carbon nano-tube/poly ethene anti-static composite material masterbatch that uses the preparation of solution blending and melt blending two-step approach to obtain can carry out the mixed granulation of fusion with the common polythene material easily, the carbon nano-tube/poly ethene anti-static composite material that finally obtains has good antistatic performance, have high simultaneously, comprehensive mechanical property, particularly impelling strength and mechanical strength
This method is also advantageous in that preparation technology is simple, can directly masterbatch and common polythene be carried out simple proportioning by the desired product performance, and directly melt blending is applicable to various plastics molding process commonly used and technology.And the carbon nano-tube/poly ethene anti-static composite material that makes by the masterbatch two-step approach makes carbon nano-tube/poly ethene anti-static composite material with adopting conventional melt-blending process, and other anti-static composite materials (PP antistatic material, common carbon black and other carbon as common static inhibitor modification are filler modified PP antistatic material or the like) also have the following advantages: combine with polyvinyl resin firmly, not because of friction, washing loss and forfeiture, good endurance; Antistatic effect is good, can be in low temperature, the medium-term and long-term use of low wet environment; Nontoxicity is not polluted goods; Can not make the polyvinyl resin thermolysis, the aerial decomposition temperature of carbon nanotube is far longer than poly processing temperature, good heat resistance; With other auxiliary agent (as lubricant, stablizer, pigment, weighting agent, fire retardant) and with not anti-mutually; Specific conductivity is because of environment for use, as humidity, and variation of temperature and fluctuating widely; The carbon nanotube add-on is few, and CNTs is when content is 0.3wt% in final polyethylene/carbon nano tube compound material, and the surface resistivity of material and volume specific resistance can both reach the service requirements of industry antistatic material (less than 10
9).
Employing is carried out sour heated oxide to CNTs and is handled in conjunction with the ball milling surface treatment, by adding maleic anhydride grafted polyethylene, coupling agent and terpolymer EP rubber, be used the method for solution blending and melt blending, not only properly settle the problem of the dispersion difficulty of carbon nanotube, carbon nanotube and polyethylene interface bonded problem have also been solved, thereby the carbon nano-tube/poly ethene anti-static composite material that finally makes also has very excellent mechanical property when keeping good antistatic performance.
Embodiment
Content of the present invention is further elaborated by following embodiment, but does not limit the scope of the invention.
Embodiment 1
1, the surface modification treatment of carbon nanotube (CNTs)
(1) nitric acid oxidation is handled
With ecosystem CNTs, place 100 ℃ of baking ovens, dry 120min.With exsiccant CNTs and the concentration that configures is that the nitric acid of 3.0mol/L is mixed by 1: 3 proportioning of mass ratio, and reflux under the agitator effect, treatment temp are 120 ℃, and the treatment time is 10h.Take out handled thing, be washed with distilled water to PH=7 repeatedly, put into 100 ℃ of baking ovens and dry.
(2) ball-milling processing
Earlier coupling agent is configured to the ethanolic soln of 10wt%, and drips acetic acid the pH value of solution is transferred to 3.5～5.5.
(1) is handled the CNTs and the above-mentioned coupling agent-ethanolic soln that obtain mix at 1: 4 by mass ratio, the slurries of gained are put into planetary ball mill ball milling 10min, and rotating speed is 400r/min.Use vacuum drying oven at 100 ℃ the CNTs that obtains at last, vacuumize fully oven dry under the condition.
Above-mentioned coupling agent is a vinyl trichloro silane.
2, solution blending
CNTs and polyethylene, maleic anhydride grafted polyethylene, coupling agent and oxidation inhibitor that step (2) obtains is fully mixed in proportion, and weight ratio is:
Polyethylene: CNTs: compatilizer: coupling agent: oxidation inhibitor=100: 20: 10: 3: 0.05
Above-mentioned polyethylene is polyethylene (PE);
Above-mentioned compatilizer is maleic anhydride grafted polyethylene (MAH-g-PE, a percentage of grafting 0.8%);
Above-mentioned oxidation inhibitor is BHT.
Said mixture is put into there-necked flask, add the dimethylbenzene of capacity, heated and stirred refluxes, and temperature is 120 ℃, leaches solid mixture after 3 hours, puts it into vacuumizing and drying in 100 ℃ of vacuum drying ovens.
3, melt blending
The compound that step 2 obtains, EPDM, linking agent and additional crosslinker be thorough mixing in proportion, and weight ratio is:
Compound: EPDM: linking agent: additional crosslinker=100: 30: 0.03: 1
Above-mentioned linking agent is dicumyl peroxide (DCP);
Above-mentioned additional crosslinker is Phthalic acid, diallyl ester (DAP);
Because the linking agent add-on is less, be mixed in better in the system in order to make it, linking agent preferably is dissolved in earlier in the organic solvent and then solution and EPDM is mixed, treat organic solvent evaporation after, EPDM mixes with the compound that step 2 obtains again.The organic solvent that is used to dissolve linking agent can be toluene or dimethylbenzene.
Said mixture is added twin screw extruder melt blending and extruding pelletization, and the pellet that obtains is a masterbatch.The temperature of twin screw extruder and mouthful mould is controlled at 180 ~ 210 ℃, and screw speed is 50 ~ 200r/min, and is keeping under the screw rod rotating state constant temperature more than 20 minutes.The mixing melt by being loaded on forcing machine forward mouth model hole, is shaped to the identical bar of shape of cross section and is cut into particle after air-cooled solidifying under the squeezing action of forcing machine, promptly gets modified poly ethylene masterbatch product.
4, the masterbatch and the polyethylene particle that obtain of step 3 is fully mixed in proportion, and weight ratio is:
Polyethylene: masterbatch=100: 10
5, the compound that obtains of step 4 adds twin screw extruder melt blending and extruding pelletization.The temperature of twin screw extruder and mouthful mould is controlled at 180 ~ 210 ℃, and screw speed is 50 ~ 200r/min, and the residence time of mixture in twin screw extruder was controlled at 30 ~ 240 seconds, and extrusion moulding granulation then finally obtains the modified poly ethylene product.
6, the modified poly ethylene particle that step 5 is obtained is put into screw-type injection machine and is molded as the standard testing batten, carries out performance test at last.
The performance test methods of the carbon nanotube/polypropylene composite materials that finally obtains in an embodiment, is:
Tensile strength:
Be molded as the standard testing batten by screw-type injection machine, the Z010 type universal electrical puller system that adopts German Zwick company to produce press ISO 527 and is stipulated the test compound tensile strength of material, test speed is 10mm/min, pneumatic clamping is 10kN, and spacing jig is from being 80mm, gauge length 20mm.23 ℃ of test ambient temperature, relative humidity 50%
Flexural strength:
Be molded as the standard testing batten by screw-type injection machine, use the Z010 type universal electrical puller system of German Zwick company, carry out (bikini) regulation test compound material bending intensity by ISO 178, test speed is 10mm/min, pneumatic clamping is 10kN, sample span 20mm, regulation amount of deflection 1.6mm.
Simple beam impact strength:
Be molded as the standard testing batten by screw-type injection machine, the XCJ-40 type charpy impact test machine that adopts Chengde trier factory to produce carries out composite material impact test by the GB1415-83 regulation, and the batten span is 40mm.
Antistatic property:
Be prepared into the standard testing print by vulcanizing press, use ZC46 high resistant instrument, press the volume resistance and the surface resistivity of GB1410-78 regulation test sample.
Embodiment 2:
As implement sharp 1 described preparation method, processing parameter changes as follows:
1, the surface modification treatment of carbon nanotube (CNTs)
Concentration of nitric acid: 4mol/L
Acid treatment temperature: 100 ℃
The acid treatment time: 18h
The ball milling time: 20min
Drum's speed of rotation: 300r/min
2, solution blending
Recipe ratio---polyethylene: CNTs: compatilizer: coupling agent: BHT=100: 25: 20: 8: 0.02
Compatilizer: MAH-g-PE, percentage of grafting are 1.2%
Coupling agent: vinyltrimethoxy silane
3, melt blending
Recipe ratio---compound: EPDM: linking agent: additional crosslinker=100: 60: 0.08: 0.6
Linking agent: DCP
Additional crosslinker: DAP
PE: masterbatch=100: 15
Embodiment 3:
As implement sharp 1 described preparation method, processing parameter changes as follows:
1, the surface modification treatment of carbon nanotube (CNTs)
Concentration of nitric acid: 2mol/L
Acid treatment temperature: 140 ℃
The acid treatment time: 24h
The ball milling time: 5min
Drum's speed of rotation: 400r/min
2, solution blending
Recipe ratio---polyethylene: CNTs: compatilizer: coupling agent: BHT=100: 8: 25: 4: 0.08
Compatilizer: MAH-g-PE, percentage of grafting are 1%
Coupling agent: vinyltrimethoxy silane
3, melt blending
Recipe ratio---compound: EPDM: linking agent: additional crosslinker=100: 45: 0.04: 0.2
Linking agent: DIP
Additional crosslinker: GM
PE: masterbatch=100: 20
Embodiment 4:
As implement sharp 1 described preparation method, processing parameter changes as follows:
1, the surface modification treatment of carbon nanotube (CNTs)
Concentration of nitric acid: 6mol/L
Acid treatment temperature: 100 ℃
The acid treatment time: 6h
The ball milling time: 90min
Drum's speed of rotation: 500r/min
2, solution blending
Recipe ratio---polyethylene: CNTs: compatilizer: coupling agent: BHT=100: 15: 8: 10: 0.06
Compatilizer: MAH-g-PE, percentage of grafting are 1%
Coupling agent: vinyltrimethoxy silane
3, melt blending
Recipe ratio---compound: EPDM: linking agent: additional crosslinker=100: 50: 0.1: 0.5
Linking agent: DCP
Additional crosslinker: GM
PE: masterbatch=100: 5
Embodiment 5:
As implement sharp 1 described preparation method, processing parameter changes as follows:
1, the surface modification treatment of carbon nanotube (CNTs)
Concentration of nitric acid: 2mol/L
Acid treatment temperature: 160 ℃
The acid treatment time: 12h
The ball milling time: 60min
Drum's speed of rotation: 300r/min
2, solution blending
Recipe ratio---polyethylene: CNTs: compatilizer: coupling agent: BHT=100: 30: 10: 5: 0.03
Compatilizer: MAH-g-PE, percentage of grafting are 1.2%
Coupling agent: vinyltriethoxysilane
3, melt blending
Recipe ratio---compound: EPDM: linking agent: additional crosslinker=100: 30: 0.02: 0.1
Linking agent: DIP
Additional crosslinker: GM
PE: masterbatch=100: 5
Embodiment 6:
As implement sharp 1 described preparation method, processing parameter changes as follows:
1, the surface modification treatment of carbon nanotube (CNTs)
Concentration of nitric acid: 4mol/L
Acid treatment temperature: 120 ℃
The acid treatment time: 16h
The ball milling time: 15min
Drum's speed of rotation: 200r/min
2, solution blending
Recipe ratio---polyethylene: CNTs: compatilizer: coupling agent: BHT=100: 20: 15: 8: 0.08
Compatilizer: MAH-g-PE, percentage of grafting are 0.8%
Coupling agent: vinyltrimethoxy silane
3, melt blending
Recipe ratio---compound: EPDM: linking agent: additional crosslinker=100: 40: 0.06: 0.6
Linking agent: DIP
Additional crosslinker: DAP
PE: masterbatch=100: 8
Embodiment 7:
As implement sharp 1 described preparation method, processing parameter changes as follows:
1, the surface modification treatment of carbon nanotube (CNTs)
Concentration of nitric acid: 1mol/L
Acid treatment temperature: 160 ℃
The acid treatment time: 20h
The ball milling time: 60min
Drum's speed of rotation: 300r/min
2, solution blending
Recipe ratio---polyethylene: CNTs: compatilizer: coupling agent: BHT=100: 10: 30: 3: 0.04
Compatilizer: MAH-g-PE, percentage of grafting are 1%
Coupling agent: vinyl trichloro silane
3, melt blending
Recipe ratio---compound: EPDM: linking agent: additional crosslinker=100: 55: 0.05: 0.3
Linking agent: DCP
Additional crosslinker: GM
PE: masterbatch=100: 20
Embodiment 8:
As implement sharp 1 described preparation method, processing parameter changes as follows:
1, the surface modification treatment of carbon nanotube (CNTs)
Concentration of nitric acid: 5mol/L
Acid treatment temperature: 80 ℃
The acid treatment time: 16h
The ball milling time: 90min
Drum's speed of rotation: 500r/min
2, solution blending
Recipe ratio---polyethylene: CNTs: compatilizer: coupling agent: BHT=100: 25: 20: 10: 0.08
Compatilizer: MAH-g-PE, percentage of grafting are 1.2%
Coupling agent: vinyl trichloro silane
3, melt blending
Recipe ratio---compound: EPDM: linking agent: additional crosslinker=100: 30: 0.02: 0.8
Linking agent: DIP
Additional crosslinker: DAP
PE: masterbatch=100: 20
Embodiment 9:
As implement sharp 1 described preparation method, processing parameter changes as follows:
1, the surface modification treatment of carbon nanotube (CNTs)
Concentration of nitric acid: 3mol/L
Acid treatment temperature: 140 ℃
The acid treatment time: 16h
The ball milling time: 30min
Drum's speed of rotation: 300r/min
2, solution blending
Recipe ratio---polyethylene: CNTs: compatilizer: coupling agent: BHT=100: 15: 8: 2: 0.04
Compatilizer: MAH-g-PE, percentage of grafting are 0.8%
Coupling agent: vinyltriethoxysilane
3, melt blending
Recipe ratio---compound: EPDM: linking agent: additional crosslinker=100: 35: 0.03: 0.4
Linking agent: DCP
Additional crosslinker: DAP
PE: masterbatch=100: 15
Embodiment 10:
As implement sharp 1 described preparation method, processing parameter changes as follows:
1, the surface modification treatment of carbon nanotube (CNTs)
Concentration of nitric acid: 4mol/L
Acid treatment temperature: 120 ℃
The acid treatment time: 12h
The ball milling time: 15min
Drum's speed of rotation: 400r/min
2, solution blending
Recipe ratio---polyethylene: CNTs: compatilizer: coupling agent: BHT=100: 10: 15: 6: 0.01
Compatilizer: MAH-g-PE, percentage of grafting are 1%
Coupling agent: vinyltrimethoxy silane
3, melt blending
Recipe ratio---compound: EPDM: linking agent: additional crosslinker=100: 40: 0.08: 0.4
Linking agent: DIP
Additional crosslinker: GM
PE: masterbatch=100: 10
The product performance test data of each embodiment correspondence sees Table 1
Table 1
| Surface resistivity (Ω) | Volume resistance (Ω * cm) | Tensile strength (MPa) | Flexural strength (MPa) | Simple beam impact strength (kJ/m 2) | |
| Embodiment 1 | 3.0E+07 | 2.0E+07 | 41.2 | 34.1 | 156.2 |
| Embodiment 2 | 6.2E+06 | 5.0E+06 | 32.3 | 22.2 | 527.3 |
| Embodiment 3 | 4.2E+08 | 2.5E+08 | 35.8 | 21.5 | 438.5 |
| Embodiment 4 | 9.5E+08 | 6.0E+08 | 44.9 | 32.6 | 232.5 |
| Embodiment 5 | 6.0E+07 | 8.4E+07 | 36.1 | 28.7 | 349.6 |
| Embodiment 6 | 3.4E+08 | 2.1E+08 | 36.8 | 28.4 | 247.5 |
| Embodiment 7 | 2.0E+07 | 3.0E+07 | 33.3 | 24.6 | 542.3 |
| Embodiment 8 | 1.0E+06 | 1.2E+06 | 38.2 | 29.8 | 331.1 |
| Embodiment 9 | 2.7E+07 | 1.0E+07 | 40.2 | 35.4 | 142.6 |
| Embodiment 10 | 6.6E+08 | 3.6E+08 | 35.1 | 29.5 | 442.5 |
Claims (2)
1, a kind of masterbatch of polyvinyl carbon nanotube anti-static composite material is characterized in that, this masterbatch prepares by the following method:
(1), the surface modification treatment of carbon nanotube CNTs
1. nitric acid oxidation is handled
With ecosystem CNTs, place 100 ℃ of baking ovens, dry 120min, with exsiccant CNTs and the concentration that configures is that the nitric acid of 1.0～6.0mol/L is mixed by 1: 3 proportioning of mass ratio, and reflux under the agitator effect, treatment temp are 60～160 ℃, treatment time is 4～24h, take out handled thing, be washed with distilled water to PH=7 repeatedly, put into 100 ℃ of baking ovens and dry;
2. ball-milling processing
Earlier coupling agent is configured to the ethanolic soln of 10wt%, and drips acetic acid the pH value of solution is transferred to 3.5～5.5;
1. step is handled the CNTs and above-mentioned coupling agent one ethanolic soln that obtain mixes by mass ratio at 1: 4, the slurries of gained are put into planetary ball mill ball milling 5～90min, rotating speed is 200～500r/min, use vacuum drying oven at 100 ℃ the CNTs that obtains at last, vacuumize fully oven dry under the condition;
Described CNTs particle diameter is 5～20nm, and length is 0.5～500 μ m;
Described coupling agent is to be selected from a kind of in vinyl trichloro silane, vinyltrimethoxy silane and the vinyltriethoxysilane;
(2), solution blending
CNTs and polyethylene, maleic anhydride grafted polyethylene, coupling agent and oxidation inhibitor that 2. above-mentioned steps obtains is fully mixed in proportion, and weight ratio is:
Polyethylene: CNTs: compatilizer: coupling agent: oxidation inhibitor
＝100∶(5～30)∶(5～30)∶(1～10)∶(0.01～0.1)，
Described compatilizer is modified by maleic acid anhydride graft polyethylene MAH-g-PE, and percentage of grafting is 0.8～1.2%,
Described oxidation inhibitor is BHT,
Said mixture is put into there-necked flask, add the dimethylbenzene of capacity, heated and stirred refluxes, and temperature is 120 ℃, leaches solid mixture after 3 hours, puts it into vacuumizing and drying in 100 ℃ of vacuum drying ovens;
(3), melt blending
The compound that step (2) obtains, terpolymer EP rubber EPDM, linking agent and additional crosslinker be thorough mixing in proportion, and weight ratio is:
Compound: EPDM: linking agent: additional crosslinker
＝100∶(30～60)∶(0.01～0.1)∶(0.1～1)
Described linking agent is to be selected from a kind of among dicumyl peroxide DCP or the di-isopropylbenzene hydroperoxide DIP;
Described additional crosslinker is to be selected from a kind of among Phthalic acid, diallyl ester DAP or the p-benzoqui(o)none dioxime GM.
2, a kind of carbon nano-tube/poly ethene anti-static composite material with the described masterbatch preparation of claim 1 is characterized in that described matrix material makes by the following method:
Masterbatch and polyethylene particle that claim 1 finally obtains is fully mixed in proportion, and weight ratio is:
Polyethylene: masterbatch=100: (5～20)
Above-mentioned compound is added twin screw extruder melt blending and extruding pelletization, it is 50～200r/min that the temperature of twin screw extruder and mouthful mould is controlled at 180～210 ℃ of screw speeds, the residence time of mixture in twin screw extruder was controlled at 30～240 seconds, extrusion moulding granulation then finally obtains the modified poly ethylene product.
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| CN103087553A (en) * | 2013-01-30 | 2013-05-08 | 北京化工大学常州先进材料研究院 | Maleic anhydride grafted modified halloysite nanotube and preparation method thereof |
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