CN107746519A - A kind of CNT composite plastic and preparation method thereof - Google Patents
A kind of CNT composite plastic and preparation method thereof Download PDFInfo
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Abstract
The present invention proposes a kind of CNT composite plastic and preparation method thereof, is related to field of compound material.CNT composite plastic is formed by the Raw material processing including plastics and CNT compound, and the preparation method of the carbon nanotube powders is：Carbon nanometer pipe catalytic element is formed nanomorphic distribution on medical stone surface, obtain catalyst precursor；The catalyst for CNT production is obtained after high-temperature calcination；Catalyst is placed in high-temperature service, is passed through the mixed gas containing seven carbon and following organic gas and inert gas and reducibility gas, at 500 DEG C 1200 DEG C, mixed gas air speed controls in the 100h 1 of 0.1h 1 control temperature, and carbon nanotube powders are prepared.Obtain phase and connect excellent CNT compound, applied in above-mentioned plastics, give full play to the excellent properties of CNT and medical stone, overcome the shortcomings of that existing CNT and medical stone are applied in composite plastic.
Description
Technical field
The invention belongs to field of compound material.
Background technology
CNT is a kind of One-dimensional Quantum material with special construction.CNT is mainly by hexagonal arrangement
Several layers to tens of layers of coaxial pipe of carbon atom composition is formed.Fixed distance, about 0.34nm, diameter are kept between layers
Generally 2~20nm.By the difference of the graphite number of plies, CNT can be divided into single-walled carbon nanotube (SWNTs) and more wall carbon are received
Mitron (MWNTs).CNT has good mechanical property, and its tensile strength is 100 times of steel, and density but only has the 1/ of steel
6, modulus of elasticity is about 5 times of steel.Although the structure of CNT is similar to the structure of high polymer material, its structure is than high
Molecular material is more stable, is one of material with highest specific strength that can be prepared at present.The hardness of CNT and gold
Hard rock is suitable, but possesses good pliability.The draw ratio of CNT is typically 1000:More than 1, it is preferable high strength fiber
Tie up material.Therefore, as the strengthening of plastic substrate, conductive and heat conduction improvement in terms of be considered to have wide application prospect.
Medical stone is a kind of subvolcano rock ore, belong to " biotite beschtauite " silicate mineral, containing iron, magnesium,
More than 20 kinds of potassium, sodium, calcium, manganese, zinc, phosphorus, silicon, sulphur etc. is to health healthy trace elements with household.Medical stone structure is spongy porous
Property, the big adsorption capacity of specific surface area are very strong, have exchange interaction to harmful ion.
CN201611153303.2 discloses a kind of fire-retardant compound tablecloths of medical stone powder PVC, includes counterdie, facial mask, institute
Facial mask is stated to be made from the following raw materials in parts by weight：PVC50~54, plasticizer 24~28, heat stabilizer 1~2, lubricant 0.1~
0.5th, medical stone 50~55, Lavender 2~2.5, vinyl acetate 25~27, calgon 0.3~0.5, lignin
Sodium sulfonate 0.4~0.6, azo-bis-isobutyrate hydrochloride 0.3~0.4, aluminum glycinate 12~13, appropriate amount of water, multi-walled carbon nanotube 2
~2.5, ferrocene 1.8~2.2, magnesium hydroxide 2~2.5.Conventional method is used using PVC as base material, medical stone, CNT etc.
Add auxiliary agent and prepare PVC composite plastics.
CN201510335156.X discloses a kind of CNT based polyalcohol and colored CABLE MATERIALS and preparation method thereof is blended：
Corvic 66-69, HDPE10-13, CNT 13-15,4-Xenyl acrylate 13-14, magnesium hydroxide 5.6-
7th, azo-bis-iso-dimethyl 0.02-0.03, silane coupling A -172 are 1-1.5, epoxy Linseed oil 3-5, itaconate
6-8, medical stone powder 6-8, colored Masterbatch 1-1.4, nimbin 0.1-0.2, auxiliary agent 7-9；Carbon is made in CNT by the present invention
The polymer such as nanotube based polyalcohol, HDPE with it is polychloroethylene blended, modified polyvinyl chloride CABLE MATERIALS is made.
Above-mentioned patent uses conventional method with PVC etc. for base material, and the addition auxiliary agent such as medical stone, CNT prepares composite plastic
Material, belong to simple physical Mechanical Method mixed material, it is impossible to make full use of CNT excellent mechanical performance and medical stone suction-operated.
The content of the invention
The present invention proposes a kind of CNT composite plastic and preparation method thereof, is provided in particular in and polyethylene, poly- third
At least one of alkene, polyvinyl chloride, polystyrene, ethylene-vinyl acetate copolymer, nylon, polyester, ABS are formed compound
Formula, preparation and its application of plastic material, the carbon nanotube powders containing medical stone directly are prepared by catalyst carrier of medical stone,
Then prepare phase and connect excellent CNT complex, applied in above-mentioned plastics, making the excellent of CNT and medical stone
The opposite sex can all be not fully exerted, and overcome the shortcomings of existing CNT composite plastic.
The present invention provides a kind of CNT composite plastic, by the Raw material processing including plastics and CNT compound
Into by weight ratio, the plastics include 100 parts of polyvinyl chloride and 1~95 part of the plasticizer to match to following raw material, stable
2~7 parts of agent；Or the plastics be 100 parts polyethylene, polypropylene, polystyrene, ethylene-vinyl acetate copolymer, nylon,
At least one of polyester, ABS；The CNT compound parts by weight are 0.1-200 parts, and the CNT compound is
Carbon nanotube powders surface covers dispersant or the product after being surface-treated with Grafting-coupling Agent；The system of the carbon nanotube powders
Preparation Method is：(1) carbon nanometer pipe catalytic element is formed nanomorphic distribution on medical stone surface, obtain catalyst precursor；
(2) catalyst precursor that step (1) obtains obtains the catalyst for CNT production after high-temperature calcination；(3)
Catalyst prepared by step (2) is placed in high-temperature service, be passed through containing seven carbon and following organic gas and inert gas and
The mixed gas of reducibility gas, at 500 DEG C -1200 DEG C, mixed gas air speed controls in 0.1h-1-100h-1 control temperature,
Carbon nanotube powders are prepared.
The present invention also provides a kind of preparation method of above-mentioned CNT composite plastic, will include plastics and CNT
The raw material hybrid process of compound is prepared into CNT composite plastic, and by weight ratio, the plastics include following raw material
100 parts of polyvinyl chloride and 1~95 part of the plasticizer to match, 2~7 parts of stabilizer；Or the plastics be 100 parts polyethylene,
At least one of polypropylene, polystyrene, ethylene-vinyl acetate copolymer, nylon, polyester, ABS；The CNT is answered
It is 0.1-200 parts with thing parts by weight, the CNT compound is that carbon nanotube powders surface covers dispersant or even with grafting
Join the product after agent is surface-treated；It is characterized in that：The preparation method of the carbon nanotube powders is：(1) CNT is made
Catalytic elements form nanomorphic distribution on medical stone surface, obtain catalyst precursor；(2) catalyst that step (1) obtains
Presoma obtains the catalyst for CNT production after high-temperature calcination；(3) catalyst prepared by step (2) is put
Put in high-temperature service, be passed through the mixed gas containing seven carbon and following organic gas and inert gas and reducibility gas, control
At 500 DEG C -1200 DEG C, mixed gas air speed controls in 0.1h-1-100h-1 temperature processed, and carbon nanotube powders are prepared.
The preparation method step (1) of the carbon nanotube powders is specially：Medical stone powder adds water to be made into medical stone powder suspension,
The solution or suspension of the material of carbon nanotubes catalytic elements are added, is prepared by one kind in ion-exchange or infusion process
The mixture of carbon nanotubes catalytic elements, said mixture is spray-dried, filtering, press filtration, one kind in rotary process or
Two or more removal solvents, obtain the catalyst precursor that catalytic elements nanomorphic is distributed on medical stone surface.
The preparation method step (1) of the carbon nanotube powders can also be specially：Medical stone powder adds water to be made into medical stone powder
Suspension, precipitating reagent and dispersant are added while the solution or suspension of the material for adding carbon nanotubes catalytic elements, is led to
A kind of mixture for preparing carbon nanotubes catalytic elements crossed in coprecipitation, hydro-thermal method, sol-gal process, said mixture
Solvent more than one or both of spray-dried, filtering, press filtration, rotary process is removed, obtains catalytic elements nanomorphic point
Catalyst precursor of the cloth on medical stone surface.
The preparation method step (1) of the carbon nanotube powders can be specially again：Medical stone powder adds water to be made into medical stone powder
Suspension, complexing agent and dispersant are added while the solution or suspension of the material for adding carbon nanotubes catalytic elements, is led to
Cross the mixture that complexometry prepares carbon nanotubes catalytic elements, said mixture is spray-dried, filtering, press filtration, centrifugation work
Solvent more than one or both of sequence is removed, obtains the complex catalyst precursor that catalytic elements nanomorphic is distributed on medical stone surface
Body.
In the preparation method of the carbon nanotube powders, the medical stone powder suspension solid content is 1%~60%；The carbon
Nanotube catalytic elements be iron, cobalt, nickel, chromium, molybdenum, it is more than one or both of tungsten, the carbon nanotubes catalytic elements
Material refers to the oxide containing iron, cobalt, nickel, chromium, molybdenum or tungsten, hydroxide, chloride, cyanide, fluoride, nitrate, sulphur
More than one or both of hydrochlorate, silicate, acylate, chromate, molybdate, tungstates compound or they answer
Compound；In the solution or suspension of the material of the carbon nanotubes catalytic elements, the solute matter of above-claimed cpd or compound
It is 0.5%-95% to measure concentration or solid content；The temperature of the high-temperature calcination is 300 DEG C -1200 DEG C, and calcination time is that 1-24 is small
When；The spray drying, spray dryer are that drying machine with centrifugal spray, Pressuresprayingdrier or two/tri- fluid sprays are dried
One kind in machine, the temperature of spray dryer is 120 DEG C -400 DEG C；The catalyst precursor particle size range 50-1000 microns.
In the preparation method of the carbon nanotube powders, the medical stone powder suspension solid content is 5%~40%；It is described to contain
In the solution or suspension of the material of carbon nanometer pipe catalytic element, the Solute mass concentration of the compound or compound or contain admittedly
Measure as 2%-50%；The spray drying, the temperature of spray dryer is 200 DEG C -300 DEG C.
In the preparation method of the carbon nanotube powders, the precipitating reagent be soluble hydroxide, soluble carbonate salt or
It is more than one or both of bicarbonate, soluble ammonium salt, ammonia, urea；The dispersant is sodium metaphosphate, alkyl benzene sulphonate
Sodium, polyvinyl alcohol, polyethylene glycol oxide, polyoxyethylene-poly-oxypropylene polyoxyethylene type three sections of copolymers, polyvinylpyrrolidones
Middle one or more；The precipitating reagent dosage is the 50%-150% of carbon nanometer pipe catalytic element theory mole；It is scattered
Agent dosage is the 0.1%-10% of system gross mass.
In the preparation method of the carbon nanotube powders, the complexing agent is citric acid, tartaric acid, glycine, the amine four of second two
One or two or more kinds in acetic acid；The dispersant be sodium metaphosphate, sodium alkyl benzene sulfonate, polyvinyl alcohol, polyethylene glycol oxide,
It is one or more kinds of in polyoxyethylene-poly-oxypropylene polyoxyethylene type three sections of copolymers, polyvinylpyrrolidones；Complexing agent
Dosage is the 20%-300% of catalytic elements theoretical molar amount；Dispersant dosage is the 0.1%-10% of system gross mass.
In the preparation method of the carbon nanotube powders, step (3) described high-temperature service be roller kilns, rotary furnace, fixed bed,
One kind in moving bed or fluid bed.
Carbon nanotube powders of the present invention, wherein containing catalyst carrier medical stone.
The physical and chemical index of the carbon nanotube powders is：Phosphorus content：>=10%, specific surface area：>=5 ㎡/g, preferably phosphorus content：
>=20%, specific surface area：≥10㎡/g；
The described CNT compounds composition formula：100 parts of carbon nanotube powders, coupling agent or dispersant are titanate esters
One kind in 0~20 part of 0~20 part of coupling agent, 0~20 part of aluminate coupling agent, 0~20 part of acid anhydrides fluidized polymer or dispersant
Or more than two kinds of mixture, wherein it is preferred that 0.1~5.0 part of titanate coupling agent, 0.1~5.0 part of aluminate coupling agent, acid anhydrides
A kind of or their mixture in fluidized polymer 0.1~5.0.
The raw material can also include following additive：Calcium carbonate, talcum powder, wood powder, antioxidant, dispersant, lubricant
In one or two or more kinds.
It is described that the raw material hybrid process including plastics and CNT compound is prepared into CNT composite plastic, make
Equipment is the one or two or more kinds in following equipment：Low speed mixer, high-speed mixer, screw extruder, injection machine,
Banbury, kneading machine, moulding press, grinder, pulverizer, tank reactor.
Described CNT composite plastic product is following typical products but is not limited to following product：
(1) a kind of ethylene-vinyl acetate copolymer functional master batch, the basic recipe of masterbatch is as follows, and number is parts by weight：
100 parts of ethylene-vinyl acetate copolymer, 1~200 part of CNT compound, antioxidant B215 or 1,010 0.2
~1 part；
And the formula of CNT compound is：Phosphorus content 98%, 1000 ㎡ of specific surface area/g carbon nanotube dust 100
Part, 0.1~2 part of titanate coupling agent, dispersant is OPE, ethylene bis stearamide or microcrystalline wax 0.1~2
Part.
(2) it is used for the artificial polyvinyl chloride leather of inner lining of automobile leather or ornamental strip, formula is as follows, and number is parts by weight：
100 parts of polyvinyl chloride, plasticizer 10-60 parts, organic tin stabilizer TM181 or lead salt stabilizer 1-7 parts, carbon nanometer
Pipe compound 1-100 parts, toughener ABS10~40 part, 0.8~1.0 part of lubricant stearic acid, lubricant polyethylene wax 0.5~
0.8 part；
And the formula of CNT compound is：Phosphorus content 95%, 1000 ㎡ of specific surface area/g carbon nanotube dust 100
Part, 0.1~2 part of titanate coupling agent, 0.1~2 part of aluminate coupling agent, dispersant is OPE, the double tristearin of ethylene
0.1~2 part of acid amides or microcrystalline wax.
(3) polyvinyl chloride balck cable material, formula is as follows, and number is parts by weight：
100 parts of polyvinyl chloride, plasticizer 50-75 parts, lead salt stabilizer 5-10 parts, CNT compound 1-100 parts, stone
1~1.6 part of wax, antimony oxide 1-8 parts；
And the formula of CNT compound is：Phosphorus content 98%, 500 ㎡ of specific surface area/g carbon nanotube dust 100
Part, 0.1~1 part of titanate coupling agent, 0.1~1 part of acid anhydrides fluidized polymer, dispersant is OPE, the double tristearin of ethylene
0.1~2 part of acid amides or microcrystalline wax.
(4) polyethylene balck cable protective cover material, formula is as follows, and number is parts by weight：
100 parts of polyethylene, antioxidant B215, CA or 1,010 0.4~0.8 part, 10~25 parts of CNT compound；
And the formula of CNT compound is：Phosphorus content 95%, 100 ㎡ of specific surface area/g carbon nanotube dust 100
Part, 0.1~1 part of acid anhydrides fluidized polymer, 0.1~1 part of aluminate coupling agent, dispersant is OPE, the double tristearin of ethylene
0.1~2 part of acid amides or microcrystalline wax.
(5) Special PP Compound for Car Bumper, formula is as follows, and number is parts by weight：
It is molded 100 parts of grade polypropylene, 1~25 part of CNT compound, 10~20 parts of 10~30 parts of SBS, HDPE；
And the formula of CNT compound is：Phosphorus content 97%, 1200 ㎡ of specific surface area/g carbon nanotube dust 100
Part, 0.1~1 part of titanate coupling agent, 0.1~1 part of aluminate coupling agent, dispersant is OPE, the double tristearin of ethylene
0.1~2 part of acid amides or microcrystalline wax.
(6) polyvinyl piping materials functional master batch, the basic recipe of polyvinyl piping materials dedicated parent material is as follows, and number is parts by weight：
HDPE：100 parts, 0.1~1 part of titanate coupling agent, 0.1~1 part of aluminate coupling agent, dispersant is the poly- second of oxidation
0~2 part of alkene wax, ethylene bis stearamide or microcrystalline wax；50~200 parts of CNT compound.
And the formula of CNT compound is：Phosphorus content 95%, 100 parts of the carbon nanotube dust than 800 ㎡ of surface/g,
0.1~1 part of titanate coupling agent, 0.1~1 part of aluminate coupling agent, 0.1~1 part of acid anhydrides fluidized polymer, dispersant are that oxidation is poly-
0.1~2 part of ethylene waxes, ethylene bis stearamide or microcrystalline wax.
(7) HDPE or PVC cable material, it is formulated as (number is mass parts)：
The weight of HDPE or PVC cable material is 100 parts, adds above-mentioned (1) described masterbatch (ethylene-vinyl acetate copolymer
Functional master batch), 1~50 part of dosage.
(8) polyethylene pipe material, the masterbatch (polyvinyl piping materials functional master batch) described in above-mentioned (6) is used for polyethylene ground source
Heat pump pipe, polyethylene water drinking tube, polyethylene gas pipe, polyethylene buried drain pipe or polyethylene silicon core pipe, addition are every 100
The polyethylene of part weight adds 1~50 part of the masterbatch.
In CNT composite plastic provided by the invention, catalyst of the carbon nanotube powders using medical stone for carrier, this
Catalytic elements are evenly distributed on kind of catalyst, and preparation process environmental protection is suggested, and can efficient catalytic prepare CNT；It is prepared into
Medical stone need not be separated after to CNT, you can be directly used in the preparation of plastics, while saving technique, can give full play to
The excellent properties of medical stone and CNT.
Embodiment
Illustrate technical scheme below by way of specific instantiation.
Embodiment 1：
Ethylene-vinyl acetate copolymer functional master batch
Medical stone powder adds water to be made into the suspension of solid content 20%, adds the iron nitrate aqueous solution of mass fraction 30%, quality point
Several 30% sodium hydroxides are water-soluble and the neopelex solution of mass fraction 5%, using medical stone suspension quality as 100%
Calculate, iron nitrate solution is the 5% of medical stone suspension quality, sodium hydroxide solution 1%, neopelex solution
For 0.5%, it is well mixed, by 40 DEG C of ion-exchange, the mixed liquor of iron-containing catalyst precursor is made in ion-exchange reactions 3h,
Mixed liquor is added in drying machine with centrifugal spray, is spray-dried at a temperature of 240 DEG C, the cyclone separator of drying machine with centrifugal spray
With sack cleaner collection catalyst precursor, catalyst precursor particle diameter 60-150 microns, after by rotary furnace in 450 DEG C of temperature
The lower calcining of degree 3 hours, obtains particle diameter 50-120 microns, specific surface area 90m2/g catalyst granules.
Catalyst apply when, above-mentioned catalyst is placed in fixed bed, temperature control at 600-800 DEG C, be passed through methane and
Argon gas volume ratio 1：4 mixed gas, air speed 0.5h-1, through pickling, filtering, obtained carbon nanotube powders are dried, wherein including carbon
Nanotube and catalyst carrier medical stone.Its physical and chemical index is：Phosphorus content 15%, 80 ㎡ of specific surface area/g；
Above-mentioned 100 parts of carbon nanotube powders, 2 parts of titanate coupling agent, 2 parts of dispersant OPE, number is weight
Part, above-mentioned substance 30 DEG C~60 DEG C of graft and surface modification temperature in ball mill, reaction time 2h, obtain CNT
Compound；
100 parts of ethylene-vinyl acetate copolymer, above-mentioned 100 parts of CNT compound, 1 part of antioxidant B215, number
For parts by weight, above-mentioned substance is successively mediated in height mixer in mixing, banbury, (height is mixed for granulation in screw extruder
Conjunction machine：Incorporation time 1h；Banbury：1h；Screw extruder：120 DEG C~200 DEG C) produce product, gram/cube li of density 1.1
Rice, tensile strength 15MPa.
Embodiment 2：
For inner lining of automobile leather or the artificial polyvinyl chloride leather of ornamental strip
Medical stone powder adds water to be made into the suspension of solid content 30%, adds the iron nitrate aqueous solution of mass fraction 20%, quality point
Several 5% ammonium molybdate aqueous solutions, the ammonium carbonate solution of mass fraction 20% and the ammonium acetate aqueous solution of mass fraction 10%, with medical stone
Suspension quality is 100% calculating, and the quality of iron nitrate solution is the 50% of medical stone suspension, ammonium molybdate solution 5%, carbon
Acid ammonium solution is 50%, sodium radio-phosphate,P-32 solution 10%；After well mixed, by 30 DEG C~50 DEG C of coprecipitation, reaction 2h, which is made, to be contained
The mixed liquor of iron, molybdenum catalyst precursor, mixed liquor are added in twin-fluid spray dryer, are sprayed at a temperature of 220 DEG C dry
It is dry, the cyclone separator and sack cleaner collection catalyst precursor of twin-fluid spray dryer, catalyst precursor particle diameter
70-40 microns, after by rotary furnace in 400 DEG C of temperature lower calcinations 2 hours, obtain 50~110 microns of particle diameter, specific surface area
100m2/g catalyst granules.
When catalyst is applied, above-mentioned catalyst is placed in fixed bed, temperature control is passed through propane, nitrogen at 700-900 DEG C
Gas, hydrogen product ratio 30：65：5 mixed gas, air speed 80h-1, through pickling, filtering, obtained carbon nanotube powders are dried, wherein wrapping
Carbon nanotubes and catalyst carrier medical stone.Its physical and chemical index is：Phosphorus content 30%, 100 ㎡ of specific surface area/g；
Above-mentioned 100 parts of carbon nanotube powders, 1 part of titanate coupling agent, 1 part of aluminate coupling agent, dispersant are that ethylene is double hard
1 part of acyl amine, number are parts by weight, and above-mentioned substance graft in kneading machine is modified (condition is with embodiment 1) with surface, obtained
To CNT compound；
100 parts of polyvinyl chloride, 60 parts of plasticizer, 7 parts of organic tin stabilizer TM181, above-mentioned CNT compound 50
Part, toughener ABS40 parts, 1.0 parts of lubricant stearic acid, 0.8 part of lubricant polyethylene wax, number is parts by weight, above-mentioned substance
Successively mediated in high-speed mixer in mixing, banbury, calendering formation (height mixer in roll squeezer：Incorporation time 1h；It is close
Mill：1h；Screw extruder：140 DEG C~190 DEG C) produce product, 1.3 grams/cc of density, tensile strength 85MPa.
Embodiment 3：
Polyvinyl chloride balck cable material,
Medical stone powder adds water to be made into the suspension of solid content 10%, adds the cobalt nitrate aqueous solution of mass fraction 30%, quality point
Several 5% ammonium molybdate aqueous solutions, the ammonium carbonate solution of mass fraction 15%, the ammonium acetate aqueous solution of mass fraction 5%, mass fraction
The 5% APEO aqueous solution, is calculated using medical stone suspension quality as 100%, and the quality of cobalt nitrate solution is hanged for medical stone
The 30% of supernatant liquid, ammonium molybdate solution 5%, sal volatile 40%, ammonium acetate solution 10%, polyoxyethylene ethereal solution are
4%；After well mixed, by 30 DEG C~50 DEG C of coprecipitation, the mixed liquor of precursor is made in reaction 2h, and mixed liquor is added to three streams
In spray body drying machine, it is spray-dried at a temperature of 300 DEG C, the cyclone separator and sack cleaner of three fluid spray dryers
Collection catalyst precursor, catalyst precursor particle diameter 50-150 microns, after it is small in 600 DEG C of temperature lower calcinations 2 by rotary furnace
When, obtain particle diameter 50-100 microns, specific surface area 90m2/g catalyst granules.
Catalyst apply when, above-mentioned catalyst is placed in fixed bed, temperature control at 700-1000 DEG C, be passed through acetone,
Nitrogen, hydrogen product are than being 25：65：10 mixed gas, air speed 20h-1, through pickling, filtering, obtained carbon nanotube powders are dried, its
In include CNT and catalyst carrier medical stone.Its physical and chemical index is：Phosphorus content 10%, 50 ㎡ of specific surface area/g；
Above-mentioned 100 parts of carbon nanotube powders, 0.1 part of titanate coupling agent, 0.1 part of acid anhydrides fluidized polymer, dispersant is crystallite
0.1 part of paraffin, number are parts by weight, and above-mentioned substance graft in high-speed mixer is modified with surface, obtains CNT
Compound；
100 parts of polyvinyl chloride, 50 parts of plasticizer, 5 parts of lead salt stabilizer, above-mentioned 10 parts of CNT compound, paraffin 1
Part, 1 part of antimony oxide, number is parts by weight, and above-mentioned substance is successively extruded in height mixer in mixing, conical double-screw
It is granulated (height mixer：Incorporation time 1h；Conical screw extruder：140 DEG C~190 DEG C) produce product, 1.3 grams of density/vertical
Square centimetre, tensile strength 90MPa.
Embodiment 4：
Polyethylene balck cable protective cover material
Medical stone powder adds water to be made into the suspension of solid content 40%, adds the nickel nitrate aqueous solution of mass fraction 40%, quality point
Several 10% ammonium tungstate aqueous solutions, 20% sodium hydroxide and 5% neopelex, using medical stone suspension quality as
100% calculates, and the quality of nickel nitrate solution is the 60% of medical stone suspension, ammonium tungstate solution 5%, and sodium hydroxide solution is
80%, neopelex solution is 5%；After well mixed, by high pressure hydro-thermal method 0.26MPa~1.6MPa, 120 DEG C~
200 DEG C, the mixed liquor of nickeliferous tungsten catalyst precursor is made in reaction 2h, and the percentage of above material is that mass percent is dense
Degree, mixed liquor is added in pressure flame filter press, and by rotary furnace in 400 DEG C of temperature lower calcinations 2 hours, grain is obtained after crushing
Footpath 50-110 microns, specific surface area 180m2/g catalyst granules.
When catalyst is applied, above-mentioned catalyst is placed in fixed bed, temperature control is passed through acetylene, argon at 650-850 DEG C
Gas, hydrogen volume are than 20：75：5 mixed gas, air speed 40h-1, through pickling, filtering, obtained carbon nanotube powders are dried, wherein
Include CNT and catalyst carrier medical stone.Its physical and chemical index is：Phosphorus content 50%, 150 ㎡ of specific surface area/g；
Above-mentioned 100 parts of carbon nanotube powders, 0.5 part of acid anhydrides fluidized polymer, 0.5 part of aluminate coupling agent, dispersant are oxidations
0.5 part of Tissuemat E, number are parts by weight, and above-mentioned substance graft in ball mill is modified (the same embodiment of condition with surface
1) CNT compound, is obtained；
100 parts of polyethylene, antioxidant B2150.5 parts, above-mentioned 18 parts of CNT compound, number is parts by weight, above-mentioned
Material is successively kneaded in banbury, extruding pelletization (banbury in parallel double-screw：1h；Screw extruder：140 DEG C~280
DEG C) produce product, 0.96 gram/cc of density, tensile strength 20MPa.
Embodiment 5：
Special PP Compound for Car Bumper
Medical stone powder adds water to be made into the suspension of solid content 25%, by ferric nitrate, ammonium chromate, citric acid in mass ratio 1：3：10
The aqueous solution of total soluble matters content mass fraction 40% is made, the latter's mass is 10% mixing of medical stone suspension quality, is mixed
After uniformly, by sol-gal process 0.48MPa~1.6MPa, 150 DEG C~200 DEG C, body before iron content, chrome catalysts is made in reaction 4h
The suspension of body, the pressure spray dryer at a temperature of 240 DEG C, cyclone separator and sack cleaner collection catalyst precursor,
The particle diameter 90-200 microns of catalyst precursor, after by rotary furnace in 400 DEG C of temperature lower calcinations 2 hours, obtain particle diameter 70-
150 microns, specific surface area 70m2/g catalyst granules.
When catalyst is applied, above-mentioned catalyst is placed in fixed bed, temperature control is passed through ethane, nitrogen at 600-800 DEG C
Air volume is than 2：3 mixed gas, air speed 80h-1, through pickling, filtering, obtained carbon nanotube powders are dried, wherein including carbon nanometer
Pipe and catalyst carrier medical stone.Its physical and chemical index is：Phosphorus content 70%, 200 ㎡ of specific surface area/g；
Above-mentioned 100 parts of carbon nanotube powders, 1 part of titanate coupling agent, 1 part of aluminate coupling agent, dispersant are the poly- second of oxidation
1 part of alkene wax, number are parts by weight, and above-mentioned substance graft in high-speed mixer is modified (condition is with embodiment 1) with surface,
Obtain CNT compound；
100 parts of grade polypropylene is molded, above-mentioned 20 parts of CNT compound, 15 parts of 20 parts of SBS, HDPE, number is attached most importance to
Measure part, above-mentioned substance priority extruding pelletization (height mixer in height mixer, parallel double-screw：Incorporation time 1h；It is parallel
Screw extruder：140 DEG C~280 DEG C) produce product, 0.97 gram/cc of density, tensile strength 25MPa.
Embodiment 6：
Polyvinyl piping materials functional master batch
Medical stone powder adds water to be made into the suspension of solid content 50%, adds the iron nitrate aqueous solution of mass fraction 10%, quality point
Several 20% sodium hydrate aqueous solutions, the aqueous solution of urea of mass fraction 5% and mass fraction 5% PULLRONIC F68-polyoxy
Three sections of aqueous copolymers solutions of ethylene type, calculated using medical stone suspension quality as 100%, the quality of iron nitrate solution is medical stone
The 40% of suspension, sodium hydroxide solution 20%, urea liquid 5%, polyoxyethylene-poly-oxypropylene polyoxyethylene three are embedding
Section copolymer solution is 5%；After well mixed, by sol-gal process 0.48MPa~1.6MPa, 150 DEG C~200 DEG C, 3h is reacted
The mixed liquor of iron-containing catalyst precursor is made, mixed liquor is added to centrifugal filtration, by roller furnace in 400 DEG C of temperature lower calcinations
2 hours, obtain particle diameter 50-110 microns, specific surface area 200m2/g catalyst granules.
Catalyst apply when, above-mentioned catalyst is placed in fixed bed, temperature control at 700-1000 DEG C, be passed through methane and
Argon gas volume ratio is 4：6 mixed gas, air speed 60h-1, through pickling, filtering, obtained carbon nanotube powders are dried, wherein being received comprising carbon
Mitron and catalyst carrier medical stone.Its physical and chemical index is：Phosphorus content 90%, than 300 ㎡ of surface/g；
Above-mentioned 100 parts of carbon nanotube powders, 1 part of titanate coupling agent, 1 part of aluminate coupling agent, 1 part of acid anhydrides fluidized polymer,
Dispersant is 2 parts of OPE, and number is unit of weight, and above-mentioned substance graft in high-speed mixer changes with surface
Property (20 DEG C~90 DEG C of temperature, time 1h), obtains CNT compound；
HDPE100 parts, 1 part of titanate coupling agent, 1 part of aluminate coupling agent, dispersant are 2 parts of ethylene bis stearamide；
Above-mentioned 200 parts of CNT compound, above-mentioned substance are successively kneaded in height mixer, banbury, squeezed in parallel double-screw
Go out to be granulated (low mixer：Incorporation time 1h；Banbury：1h；Parallel screw extruder：140 DEG C~280 DEG C) product is produced, it is close
0.98 gram/cc of degree, tensile strength 25MPa.
Embodiment 7：
PVC cable material
The weight of PVC cable material is 100 parts, and 100 parts of masterbatch prepared by embodiment 1, above-mentioned substance successively mixes in height
Extruding pelletization (height mixer in machine, parallel double-screw：Incorporation time 1h；Banbury：1h；Screw extruder：140 DEG C~190
DEG C) product, 1.37 grams/cc, tensile strength 78MPa of density are produced, the resistivity of gained CABLE MATERIALS is not higher than 100 Ω
cm。
Embodiment 8：
Polyethylene pipe material
Masterbatch described in embodiment 6 is used for polyethylene ground source heat pump line, polyethylene water drinking tube, polyethylene gas pipe, polyethylene
Buried drain pipe or polyethylene silicon core pipe, addition adds 1~50 part of the masterbatch for the polyethylene of every 100 parts of weight, above-mentioned
Material priority extrusion molding (height mixer in height mixer, single screw rod：Incorporation time 1h；Single screw rod screw extruder：
140 DEG C~190 DEG C) product i.e., 0.97 gram/cc, tensile strength 22MPa of density, wherein polyethylene ground source heat pump line
Mechanics of Machinery, thermal property are excellent, and thermal conductivity reaches as high as 30W/m/K.
Claims (10)
1. a kind of CNT composite plastic, is formed by the Raw material processing including plastics and CNT compound, following raw material
By weight ratio, the plastics include 100 parts of polyvinyl chloride and 1~95 part of the plasticizer to match, 2~7 parts of stabilizer；Or
The plastics is in 100 parts of polyethylene, polypropylene, polystyrene, ethylene-vinyl acetate copolymer, nylon, polyester, ABS
It is at least one；The CNT compound parts by weight are 0.1-200 parts, and the CNT compound is carbon nanotube powders table
Face covers dispersant or the product after being surface-treated with Grafting-coupling Agent；It is characterized in that：The system of the carbon nanotube powders
Preparation Method is：(1) carbon nanometer pipe catalytic element is formed nanomorphic distribution on medical stone surface, obtain catalyst precursor；
(2) catalyst precursor that step (1) obtains obtains the catalyst for CNT production after high-temperature calcination；(3)
Catalyst prepared by step (2) is placed in high-temperature service, be passed through containing seven carbon and following organic gas and inert gas and
The mixed gas of reducibility gas, at 500 DEG C -1200 DEG C, mixed gas air speed controls in 0.1h control temperature-1-100h-1, system
It is standby to obtain carbon nanotube powders.
2. CNT composite plastic according to claim 1, it is characterised in that the preparation method of the carbon nanotube powders
Step (1) is specially：Medical stone powder adds water to be made into medical stone powder suspension, add carbon nanotubes catalytic elements material it is molten
Liquid or suspension, it is above-mentioned by a kind of mixture for preparing carbon nanotubes catalytic elements in ion-exchange or infusion process
Mixture is spray-dried, filtering, press filtration, more than one or both of rotary process removes solvent, obtains catalytic elements and receives
Rice state is distributed in the catalyst precursor on medical stone surface.
3. CNT composite plastic according to claim 1, it is characterised in that the preparation method of the carbon nanotube powders
Step (1) is specially：Medical stone powder adds water to be made into medical stone powder suspension, add carbon nanotubes catalytic elements material it is molten
Precipitating reagent and dispersant are added while liquid or suspension, is prepared by one kind in coprecipitation, hydro-thermal method, sol-gal process
The mixture of carbon nanotubes catalytic elements, said mixture is spray-dried, filtering, press filtration, one kind in rotary process or
Two or more removal solvents, obtain the catalyst precursor that catalytic elements nanomorphic is distributed on medical stone surface.
4. CNT composite plastic according to claim 1, it is characterised in that the preparation method of the carbon nanotube powders
Step (1) is specially：Medical stone powder adds water to be made into medical stone powder suspension, add carbon nanotubes catalytic elements material it is molten
Complexing agent and dispersant are added while liquid or suspension, the mixture of carbon nanotubes catalytic elements is prepared by complexometry,
Said mixture is spray-dried, filtering, press filtration, more than one or both of rotary process removes solvent, obtains catalysis member
Plain nanomorphic is distributed in the catalyst precursor on medical stone surface.
5. according to the CNT composite plastic described in claim 2,3 or 4, it is characterised in that the system of the carbon nanotube powders
In Preparation Method, the medical stone powder suspension solid content is 1%~60%；The carbon nanometer pipe catalytic element be iron, cobalt, nickel,
It is more than one or both of chromium, molybdenum, tungsten, the materials of the carbon nanotubes catalytic elements refer to containing iron, cobalt, nickel, chromium, molybdenum or
Oxide, hydroxide, chloride, cyanide, fluoride, nitrate, sulfate, silicate, acylate, the chromic acid of tungsten
More than one or both of salt, molybdate, tungstates compound or their compound；The carbon nanotubes catalysis member
In the solution or suspension of the material of element, the Solute mass concentration or solid content of above-claimed cpd or compound are 0.5%-
95%；The temperature of the high-temperature calcination is 300 DEG C -1200 DEG C, and calcination time is 1-24 hours；The spray drying, spraying are dry
Dry machine is one kind in drying machine with centrifugal spray, Pressuresprayingdrier or two/tri- fluid spray dryers, spray dryer
Temperature is 120 DEG C -400 DEG C；The catalyst precursor particle size range 50-1000 microns.
6. CNT composite plastic according to claim 5, it is characterised in that the preparation method of the carbon nanotube powders
In, the medical stone powder suspension solid content is 5%~40%；The solution of the material of the carbon nanotubes catalytic elements is outstanding
In supernatant liquid, the Solute mass concentration or solid content of the compound or compound are 2%-50%；The spray drying, spraying are dry
The temperature of dry machine is 200 DEG C -300 DEG C.
7. CNT composite plastic according to claim 3, it is characterised in that the preparation method of the carbon nanotube powders
In, the precipitating reagent is one in soluble hydroxide, soluble carbonate salt or bicarbonate, soluble ammonium salt, ammonia, urea
Kind is two or more；The dispersant be sodium metaphosphate, sodium alkyl benzene sulfonate, polyvinyl alcohol, polyethylene glycol oxide, polyoxyethylene-
It is one or more kinds of in polyoxypropylene polyoxyethylene type three sections of copolymers, polyvinylpyrrolidones；The precipitating reagent dosage is
The 50%-150% of carbon nanometer pipe catalytic element theory mole；Dispersant dosage is the 0.1%-10% of system gross mass.
8. CNT composite plastic according to claim 4, it is characterised in that the preparation method of the carbon nanotube powders
In, the complexing agent is the one or two or more kinds in citric acid, tartaric acid, glycine, the amine tetraacethyl of second two；The dispersant
For sodium metaphosphate, sodium alkyl benzene sulfonate, polyvinyl alcohol, polyethylene glycol oxide, three sections of polyoxyethylene-poly-oxypropylene polyoxyethylene type
It is one or more kinds of in copolymer, polyvinylpyrrolidone；Amount of complex is the 20%- of catalytic elements theoretical molar amount
300%；Dispersant dosage is the 0.1%-10% of system gross mass.
9. CNT composite plastic according to claim 1, it is characterised in that：The preparation method of the carbon nanotube powders
In, step (3) described high-temperature service is one kind in roller kilns, rotary furnace, fixed bed, moving bed or fluid bed.
10. a kind of preparation method of the CNT composite plastic described in any one of claim 1-9, plastics will be included and carbon is received
The raw material hybrid process of mitron compound is prepared into CNT composite plastic, following raw material by weight ratio, the plastics
Including 1~95 part of 100 parts of polyvinyl chloride and the plasticizer to match, 2~7 parts of stabilizer；Or the poly- second that the plastics are 100 parts
At least one of alkene, polypropylene, polystyrene, ethylene-vinyl acetate copolymer, nylon, polyester, ABS；The CNT
Compound parts by weight are 0.1-200 parts, and the CNT compound is that carbon nanotube powders surface covers dispersant or with being grafted
Coupling agent be surface-treated after product；It is characterized in that：The preparation method of the carbon nanotube powders is：(1) carbon nanometer is made
Pipe catalytic elements form nanomorphic distribution on medical stone surface, obtain catalyst precursor；(2) catalysis that step (1) obtains
Agent presoma obtains the catalyst for CNT production after high-temperature calcination；(3) catalyst for preparing step (2)
It is placed in high-temperature service, is passed through the mixed gas containing seven carbon and following organic gas and inert gas and reducibility gas,
Controlling temperature, mixed gas air speed is controlled in 0.1h at 500 DEG C -1200 DEG C-1-100h-1, carbon nanotube powders are prepared.
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| CN111249765A (en) * | 2020-02-25 | 2020-06-09 | 中国科学院化学研究所 | Pressurized fluid extraction system and method for removing metal ions from carbon material |
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| CN108794874A (en) * | 2018-05-31 | 2018-11-13 | 哈尔滨金纳科技有限公司 | A kind of spiral carbon nanotubes hydridization graphene composite plastic and preparation method thereof |
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| WO2020180383A3 (en) * | 2018-12-28 | 2020-10-15 | Exxonmobil Research And Engineering Company | Plastics composite reinforced with carbon filler |
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