CN107057176A - A kind of carbon nanotube masterbatch and preparation method thereof - Google Patents
A kind of carbon nanotube masterbatch and preparation method thereof Download PDFInfo
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- CN107057176A CN107057176A CN201710258580.8A CN201710258580A CN107057176A CN 107057176 A CN107057176 A CN 107057176A CN 201710258580 A CN201710258580 A CN 201710258580A CN 107057176 A CN107057176 A CN 107057176A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/04—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention provides a kind of carbon nanotube masterbatch and preparation method thereof, the component and its percentage by weight that the carbon nanotube masterbatch is included are：CNT 10% ~ 40%, coupling agent 1% ~ 5%, polymeric carrier material 40 ~ 80%, compatilizer 20 ~ 30%, lubricant 10 ~ 20%.Using technical scheme, further disperseing when can promote the masterbatch to use, obtain that resistivity is low, thermal conductivity is high and the high masterbatch of conductance,, can be to finally use high polymer material is extra, preferably produce toughening effect and the carrier of masterbatch used is elastomer polymer；Wettability treatment is first carried out to CNT, CNT apparent density can be reduced, the harm of its airborne dust is reduced.
Description
Technical field
The invention belongs to conduction/antistatic macromolecule material field, more particularly to a kind of carbon nanotube masterbatch and its preparation
Method.
Background technology
In CNT/polymer composite, CNT assigns material high intensity, high conductivity, high heat stability
Property etc. excellent physical property, and macromolecule assigns material flexibility, low cost, the excellent performance such as easy processing.In fact, these
Composite has begun to apply in the life of people.Use at present is more widely to introduce CNT system in the plastic
Standby anlistatig composite.Some high-end sport-specific products such as tennis racket introduces carbon nano tube compound material, improves the machine of product
Tool performance.In 21 century, the main application direction of CNT/polymer composite two is high performance structures material and the energy
Field.
On the one hand, due to the apparent density very little of CNT, it can everywhere be flown upward when directly using, cause environmental pollution tight
Weight.Working condition is poor, and labor strength is big, and operating environment dust is exceeded for a long time, seriously endangers workers ' health.On the other hand,
Because the apparent density of CNT is small, the density difference with other plastic grains is very big, disperses uneven when directly adding, under
Material is difficult.
At present, prior art typically use solvent method, high polymer material is first dissolved completely in good solvent, then again with carbon
Nanotube is mixed and made into masterbatch.High polymer material is dissolved completely in good solvent, carbon nanometer is added under conditions of ultrasonic agitation
Pipe is well mixed.Treat that good solvent volatilization is complete, then, the CNT mother for obtaining high content of carbon nanotubes is crushed in pulverizer
Material.However, needing to consume substantial amounts of solvent and energy in this preparation process, when solvent volatilizees, environmental pollution is serious.Moreover,
Be only suitable for those and hold diffluent high polymer materials, for some insoluble high polymer materials, it is necessary to the quantity of solvent used more
Greatly.For some special solvent or the high polymer material of dangerous solvents need to be used to bring certain harmfulness.
Also using chemical synthesis process is first used, CNT is coated with polymer, then with vector resin
It is mixed and made into masterbatch.This method will first carry out synthesis cladding, it is also desirable to consume substantial amounts of solvent and energy；And by twice
Prepare, complex process, products obtained therefrom content of carbon nanotubes is low, the resistivity of masterbatch is high.
The content of the invention
For above technical problem, the invention discloses a kind of carbon nanotube masterbatch and preparation method thereof, by CNT
Masterbatch pellet is prepared into, except with good electric conductivity, resistivity is low, moreover it is possible to which enhancing increasing is carried out to corresponding high polymer material
It is tough；Avoid CNT from flying upward everywhere simultaneously, working condition and labor intensity can be significantly improved；And the CNT of the present invention
The electric conductivity and thermal conductivity of material are more excellent obtained by masterbatch makes.
In this regard, the technical solution adopted by the present invention is：
A kind of carbon nanotube masterbatch, its component included and its percentage by weight are：CNT 10%~40%, coupling
Agent 1%~5%, polymeric carrier material 40~80%, compatilizer 20~30%, lubricant 10~20%.
As a further improvement on the present invention, CNT 15%~25%, coupling agent 2%~4%, high polymer material is carried
Body 50~70%, compatilizer 22~26%, lubricant 13~18%.
As a further improvement on the present invention, the lubricant is ethylene bis-fatty acid amides (EBS), ethylene bis-fatty acid
It is the derivative of acid amides, diffusing oil, atoleine, PE waxes, oxidation PE waxes, spermaceti, stearic acid, butyl stearate, zinc stearate, hard
One or more of mixtures in resin acid calcium.
As a further improvement on the present invention, the polymeric carrier material be EVA, ethylene propylene diene rubber (EPDM),
POE, high glue powder, butadiene rubber, natural rubber, MBS terpolymer (MBS), benzene second
Block copolymer, the block copolymer of styrene ethylene butadiene-styrene, the esters of acrylic acid of alkene-butadiene-styrene
One or more of mixtures in series modified dose.
As a further improvement on the present invention, the compatilizer is maleic anhydride grafts, the acrylic acid of high polymer material
One or more of mixtures of graft or methacrylic acid graft.
As a further improvement on the present invention, the compatilizer be HDPE-g-MAH, PP-g-MAH, SAN-g-MAH,
One or more of mixtures in EPDM-g-MAH, SEBS-g-MAH, PS-g-MAH, EVA-g-MAH, POE-g-MAH.
As a further improvement on the present invention, the carbon nanotube masterbatch is prepared using following steps：
Step S1, first dilutes the coupling agent after coupling agent is diluted, then using the coupling agent pair after dilution with solvent
CNT is soaked, wherein, the weight of the solvent is 8~15 times of carbon nanotubes；
Step S2, after the solvent is volatilized, by the CNT after wetting and polymeric carrier material and other auxiliary agents according to
Proportioning is kneaded, after mixing is uniform, by extruding pelletization or directly broken, obtains masterbatch pellet.
As a further improvement on the present invention, in step S1, the weight of the solvent is the 10~12 of carbon nanotubes
Times.
As a further improvement on the present invention, in step S1, the solvent is at least the one of alcohol, acetone or hexamethylene
Kind.
As a further improvement on the present invention, in step S2, the equipment of the mixing is double screw extruder, banbury or
Mill.
The invention also discloses a kind of preparation method of carbon nanotube masterbatch as described above, it is characterised in that：It includes
Following steps：
Step S1, first dilutes the coupling agent after coupling agent is diluted, then using the coupling agent pair after dilution with solvent
CNT is soaked, wherein, the weight of the solvent is 8~15 times of carbon nanotubes；
Step S2, after the solvent is volatilized, by the CNT after wetting and polymeric carrier material and other auxiliary agents according to
Proportioning is kneaded, after mixing is uniform, by extruding pelletization or directly broken, obtains masterbatch pellet.
As a further improvement on the present invention, in step S1, the weight of the solvent is the 10~12 of carbon nanotubes
Times.
As a further improvement on the present invention, in step S1, the solvent is at least the one of alcohol, acetone or hexamethylene
Kind.
As a further improvement on the present invention, in step S2, the equipment of the mixing is double screw extruder, banbury or
Mill.
Compared with prior art, beneficial effects of the present invention are：
First, using technical scheme, further disperseing when can promote the masterbatch to use, obtain resistivity
It is low, the high masterbatch of conductance, and the carrier of masterbatch used is elastomer polymer, can to it is final using high polymer material it is extra,
Toughening effect is preferably produced, the electric conductivity and thermal conductivity of final material can be significantly improved.
Second, using technical scheme, coupling agent is first diluted using solvent, then CNT moistened
It is wet, CNT apparent density can be reduced, the harm of its airborne dust is reduced.Pass through the strong of double screw extruder, banbury or mill
Power is kneaded, and is conducive to CNT to be uniformly dispersed.
Embodiment
The preferably embodiment to the present invention is described in further detail below.
Embodiment 1
A kind of carbon nanotube masterbatch formula, its part by weight is CNT 20%, and coupling agent 2%, high polymer material is carried
Body 50%, compatilizer 20%, lubricant 8%.Wherein coupling agent is KH590, and macromolecule carrier is EVA, and compatilizer is EVA-g-
MAH, lubricant is EBS.
Its preparation method is：Coupling agent first is diluted with the alcohol of 10 times of carbon nanotubes, then CNT is carried out
Wetting.Treat that solvent volatilizees, by the CNT after wetting and high polymer material and other auxiliary agents according to certain formula add to
Kneaded in double screw extruder, banbury or mill, further extruding pelletization is taken out after mixing is uniform or is directly broken
It is broken, obtain masterbatch pellet.
Its gained masterbatch is added into PC, when adding 10% masterbatch, i.e., the content of CNT is 2%, gained PC
The sheet resistance of material is less than 107Ω/sqr, other performances are shown in Table 1
Embodiment 2
A kind of carbon nanotube masterbatch formula, its part by weight is CNT 20%, and coupling agent 2%, high polymer material is carried
Body 50%, compatilizer 20%, lubricant 8%.Wherein coupling agent is KH580, and macromolecule carrier is EVA, and compatilizer is EVA-g-
MAH, lubricant is EBS.
Its preparation method is：Coupling agent first is diluted with the alcohol of 10 times of carbon nanotubes, then CNT is carried out
Wetting.Treat that solvent volatilizees, by the CNT after wetting and high polymer material and other auxiliary agents according to certain formula add to
Kneaded in double screw extruder, banbury or mill, further extruding pelletization is taken out after mixing is uniform or is directly broken
It is broken, obtain masterbatch pellet.
Its gained masterbatch is added into PC, when adding 10% masterbatch, i.e., the content of CNT is 2%, gained PC
The sheet resistance of material is less than 107Ω/sqr, other performances are shown in Table 1.
Embodiment 3
A kind of carbon nanotube masterbatch formula, its part by weight is CNT 20%, and coupling agent 2%, high polymer material is carried
Body 50%, compatilizer 20%, lubricant 8%.Wherein coupling agent is KH580, and macromolecule carrier is POE, and compatilizer is POE-g-
MAH, lubricant is EBS.
Then its preparation method moistens first to dilute coupling agent with the alcohol of 10 times of carbon nanotubes to CNT
It is wet.Treat that solvent volatilizees, the CNT after wetting is added to double with high polymer material and other auxiliary agents according to certain formula
Kneaded in screw extruder, banbury or mill, further extruding pelletization taken out after mixing is uniform or is directly crushed,
Obtain masterbatch pellet.
Its gained masterbatch is added into PC, when adding 10% masterbatch, i.e., the content of CNT is 2%, gained PC
The sheet resistance of material is less than 107Ω/sqr, other performances are shown in Table 1.
Embodiment 4
A kind of carbon nanotube masterbatch formula, its part by weight is CNT 20%, and coupling agent 2%, high polymer material is carried
Body 50%, compatilizer 20%, lubricant 8%.Wherein coupling agent is KH590, and macromolecule carrier is MBS, and compatilizer is MBS-g-
MAH, lubricant is EBS.
Its preparation method is：Coupling agent first is diluted with the alcohol of 10 times of carbon nanotubes, then CNT is carried out
Wetting.Treat that solvent volatilizees, by the CNT after wetting and high polymer material and other auxiliary agents according to certain formula add to
Kneaded in double screw extruder, banbury or mill, further extruding pelletization is taken out after mixing is uniform or is directly broken
It is broken, obtain masterbatch pellet.
Its gained masterbatch is added into PC, when adding 10% masterbatch, i.e., the content of CNT is 2%, gained PC
The sheet resistance of material is less than 107Ω/sqr, other performances are shown in Table 1.
Embodiment 5
A kind of carbon nanotube masterbatch formula, its part by weight is CNT 10%, and coupling agent 2%, high polymer material is carried
Body 60%, compatilizer 20%, lubricant 8%.Wherein coupling agent is KH580, and macromolecule carrier is MBS, and compatilizer is MBS-g-
MAH, lubricant is EBS.
Then its preparation method moistens first to dilute coupling agent with the alcohol of 10 times of carbon nanotubes to CNT
It is wet.Treat that solvent volatilizees, the CNT after wetting is added to double with high polymer material and other auxiliary agents according to certain formula
Kneaded in screw extruder, banbury or mill, further extruding pelletization taken out after mixing is uniform or is directly crushed,
Obtain masterbatch pellet.
Its gained masterbatch is added into PC, when adding 20% masterbatch, i.e., the content of CNT is 2%, gained PC
The sheet resistance of material is less than 106Ω/sqr, other performances are shown in Table 1.
Embodiment 6
A kind of carbon nanotube masterbatch formula, its part by weight is CNT 40%, and coupling agent 2%, high polymer material is carried
Body 30%, compatilizer 20%, lubricant 8%.Wherein coupling agent is KH580, and macromolecule carrier is MBS, and compatilizer is MBS-g-
MAH, lubricant is EBS.
Then its preparation method moistens first to dilute coupling agent with the alcohol of 10 times of carbon nanotubes to CNT
It is wet.Treat that solvent volatilizees, the CNT after wetting is added to double with high polymer material and other auxiliary agents according to certain formula
Kneaded in screw extruder, banbury or mill, further extruding pelletization taken out after mixing is uniform or is directly crushed,
Obtain masterbatch pellet.
Its gained masterbatch is added into PC, when adding 5% masterbatch, i.e., the content of CNT is 2%, gained PC materials
The sheet resistance of material is less than 107Ω/sqr, other performances are shown in Table 1.
Embodiment 7
A kind of carbon nanotube masterbatch formula, its part by weight is CNT 20%, and coupling agent 2%, high polymer material is carried
Body 50%, compatilizer 20%, lubricant 8%.Wherein coupling agent is KH580, and macromolecule carrier is MBS, and compatilizer is MBS-g-
MAH, lubricant is EBS.
Then its preparation method moistens first to dilute coupling agent with the alcohol of 10 times of carbon nanotubes to CNT
It is wet.Treat that solvent volatilizees, the CNT after wetting is added to double with high polymer material and other auxiliary agents according to certain formula
Kneaded in screw extruder, banbury or mill, further extruding pelletization taken out after mixing is uniform or is directly crushed,
Obtain masterbatch pellet.
Its gained masterbatch is added into nylon, when adding 10% masterbatch, i.e., the content of CNT is 2%, gained
The sheet resistance of nylon material is less than 108Ω/sqr, other performances are shown in Table 1.
Comparative example 1
2% CNT is directly added in PC, it is 10 that the sheet resistance of gained PC materials, which is higher than,9Ω/sqr, other property
1 can be shown in Table.
Comparative example 2
2% CNT is directly added in nylon, it is 10 that the sheet resistance of gained PA materials, which is higher than,10Ω/sqr, other
Performance is shown in Table 1.
The embodiment 1~6 of table 1 and the performance comparison table for contrasting comparative example 1~3
Comparison by above-described embodiment 1~5 and comparative example 1~2 is visible, using technical scheme
The mode of carbon nanotube masterbatch is added in polymer base material, with being directly added to the CNT containing identical mass ratio
In polymer base material, the former has more preferable electric conductivity, and resistivity is lower, and thermal conductivity is higher, and impact strength is higher.From table
As can be seen that the performance for obtaining material using mother material addition CNT obtains material property than direct addition method and has aobvious in 1
The rise of work, wherein impact strength lift about 300%-500%, and thermal conductivity lifts about 300%, and electric conductivity improves about 100 times
To 1000 times.
Above content is to combine specific preferred embodiment further description made for the present invention, it is impossible to assert
The specific implementation of the present invention is confined to these explanations.For general technical staff of the technical field of the invention,
On the premise of not departing from present inventive concept, some simple deduction or replace can also be made, should all be considered as belonging to the present invention's
Protection domain.
Claims (10)
1. a kind of carbon nanotube masterbatch, it is characterised in that its component included and its percentage by weight are：CNT 10% ~
40%, coupling agent 1% ~ 5%, polymeric carrier material 40 ~ 80%, compatilizer 20 ~ 30%, lubricant 10 ~ 20%.
2. carbon nanotube masterbatch according to claim 1, it is characterised in that its component included and its percentage by weight
For：CNT 15% ~ 25%, coupling agent 2% ~ 4%, polymeric carrier material 50 ~ 70%, compatilizer 22 ~ 26%, lubricant 13 ~
18%。
3. carbon nanotube masterbatch according to claim 1 or 2, it is characterised in that：The lubricant is ethylene bis-fatty acid
It is acid amides, the derivative of ethylene bis-fatty acid amides, diffusing oil, atoleine, PE waxes, oxidation PE waxes, spermaceti, stearic acid, hard
One or more of mixtures in resin acid butyl ester, zinc stearate, calcium stearate.
4. carbon nanotube masterbatch according to claim 1 or 2, it is characterised in that：The polymeric carrier material be EVA,
Ethylene propylene diene rubber, POE, high glue powder, butadiene rubber, natural rubber, methyl methacrylate-butadiene-polystyrene ternary
Copolymer, the block copolymer of styrene-butadiene-styrene, the block of styrene-ethene-butadiene-styrene
One or more of mixtures in series modified dose of copolymer, esters of acrylic acid.
5. carbon nanotube masterbatch according to claim 1 or 2, it is characterised in that：The compatilizer is high polymer material
One or more of mixtures of maleic anhydride grafts, acrylic acid-grafted thing or methacrylic acid graft.
6. carbon nanotube masterbatch according to claim 5, it is characterised in that：The compatilizer is HDPE-g-MAH, PP-g-
One kind or several in MAH, SAN-g-MAH, EPDM-g-MAH, SEBS-g-MAH, PS-g-MAH, EVA-g-MAH, POE-g-MAH
The mixture planted.
7. a kind of preparation method of carbon nanotube masterbatch as described in claim 1 ~ 6 any one, it is characterised in that：It includes
Following steps：
Step S1, is first diluted the coupling agent after coupling agent is diluted with solvent, then carbon is received using the coupling agent after dilution
Mitron is soaked, wherein, the weight of the solvent is 8 ~ 15 times of carbon nanotubes；
Step S2, after the solvent is volatilized, by the CNT after wetting and polymeric carrier material and other auxiliary agents according to proportioning
Kneaded, it is by extruding pelletization or directly broken after mixing is uniform, obtain masterbatch pellet.
8. the preparation method of carbon nanotube masterbatch according to claim 7, it is characterised in that：In step S1, the solvent
Weight be 10 ~ 12 times of carbon nanotubes.
9. the preparation method of carbon nanotube masterbatch according to claim 7, it is characterised in that：In step S1, the solvent
For at least one of alcohol, acetone or hexamethylene.
10. the preparation method of carbon nanotube masterbatch according to claim 7, it is characterised in that：In step S2, the mixing
Equipment be double screw extruder, banbury or mill.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108587166A (en) * | 2018-04-16 | 2018-09-28 | 张家港大塚化学有限公司 | High intensity heat conduction antistatic polyphenyl thioether composite material and preparation method thereof |
| CN108841151A (en) * | 2018-06-27 | 2018-11-20 | 深圳职业技术学院 | A kind of biodegradable conducing composite material and preparation method thereof |
| CN109251429A (en) * | 2018-08-08 | 2019-01-22 | 多凌新材料科技股份有限公司 | The graphene/carbon nano-tube master batch and its preparation method that are easily dispersed in PVC and application |
| CN109608859A (en) * | 2018-12-17 | 2019-04-12 | 特塑（大连）高分子材料有限公司 | A kind of carbon nano-tube modification engineering plastics and preparation method thereof |
| CN112831119A (en) * | 2020-12-30 | 2021-05-25 | 界首市旭升塑胶制品有限公司 | Preparation method of carboxyl carbon nanotube composite EVA rain boot material |
| CN114395176A (en) * | 2022-01-05 | 2022-04-26 | 张国祥 | Preparation process of PU-like material |
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| CN1456592A (en) * | 2003-03-25 | 2003-11-19 | 天津理工学院 | Preparing method for carbon nano-tube additive base metal and products thereof, rigid poly section material with said base metal |
| CN104513410A (en) * | 2013-09-30 | 2015-04-15 | 山东大展纳米材料有限公司 | Preparation method of pre-dispersed carbon nano-tube rubber masterbatches |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108587166A (en) * | 2018-04-16 | 2018-09-28 | 张家港大塚化学有限公司 | High intensity heat conduction antistatic polyphenyl thioether composite material and preparation method thereof |
| CN108841151A (en) * | 2018-06-27 | 2018-11-20 | 深圳职业技术学院 | A kind of biodegradable conducing composite material and preparation method thereof |
| CN109251429A (en) * | 2018-08-08 | 2019-01-22 | 多凌新材料科技股份有限公司 | The graphene/carbon nano-tube master batch and its preparation method that are easily dispersed in PVC and application |
| CN109608859A (en) * | 2018-12-17 | 2019-04-12 | 特塑（大连）高分子材料有限公司 | A kind of carbon nano-tube modification engineering plastics and preparation method thereof |
| CN112831119A (en) * | 2020-12-30 | 2021-05-25 | 界首市旭升塑胶制品有限公司 | Preparation method of carboxyl carbon nanotube composite EVA rain boot material |
| CN114395176A (en) * | 2022-01-05 | 2022-04-26 | 张国祥 | Preparation process of PU-like material |
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