CN105601909A - Conductive MC nylon/graphene composite material and preparation method thereof - Google Patents
Conductive MC nylon/graphene composite material and preparation method thereof Download PDFInfo
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- CN105601909A CN105601909A CN201511019805.1A CN201511019805A CN105601909A CN 105601909 A CN105601909 A CN 105601909A CN 201511019805 A CN201511019805 A CN 201511019805A CN 105601909 A CN105601909 A CN 105601909A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
- C08G69/16—Preparatory processes
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- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
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- 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
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
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- 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
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- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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Abstract
The invention discloses a preparation method of a conductive MC nylon/graphene composite material. The method takes graphene and caprolactam as raw materials, and caprolactam open loop in-situ polymerization is taken as the preparation method; a conductive filler is added into the raw material formula, a conductive network is formed by the interaction between the conductive filler and the graphene, and the conductive MC nylon/graphene composite material is formed after caprolactam polymerization. The composite material prepared by the method has the advantages of being low in graphene adding amount and good in conductivity.
Description
Technical field
The invention belongs to the technical field of graphene composite material, particularly, the present invention relates to a kind of conductive MC nylon/stoneChina ink alkene composite and preparation method thereof.
Background technology
The nanostructured of Graphene is very unique, and specific area is very large, and the electric property of Graphene, heat conductivility and powerLearn performance all very excellent. In polymer, add a small amount of Graphene and just can produce significant shadow to polymeric matrix performanceRing. Utilize the electric conductivity of Graphene excellence can significantly improve the electrical property of Graphene/polymer conducting material, can be used as spyPlanting functional polymer filler uses. But Graphene surface is inert condition, poor with the interface compatibility of other media. AndGraphene has stronger Van der Waals force between layers, the same with other nano materials, and Graphene is easily generation each otherPoly-.
Research Graphene mainly adopts blending extrusion method at the process for dispersing of polymer at present, and the feature of the method is simpleFast energy rapid batch, but Graphene is mainly mixing batch mixing stage and melt blending in the dispersion process of fluoropolymer resinIn the stage, in these two processes, the dispersion of Graphene is relatively difficult to reach the dispersion of strand rank, in current research itsThe electrical property that improves Graphene/polymeric material is very limited. The raising master of the polymer-modified composite electrical property of GrapheneTo be determined by Graphene deployment conditions in polymeric system. And than other Graphene/nylon materials, MC nylon/graphiteAlkene material is formed by caprolactam monomer ring-opening polymerisation, and main preparation methods is situ aggregation method.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of conductive MC nylon/graphene composite material and preparation side thereofMethod. The inventive method is in conjunction with MC nylon/graphene composite material formula, MC nylon/graphene composite material with caprolactam andGraphene is base stock, improves the electric conductivity of composite itself by adding the additives such as conductive filler. Side of the present inventionThe composite that method prepares has advantages of that Graphene interpolation content is low, conductivity of composite material can be good.
The present invention solves the problems of the technologies described above adopted technical scheme: a kind of conductive MC nylon/Graphene composite woodThe preparation method of material, selects Graphene, caprolactam as raw material, with caprolactam open loop in-situ polymerization in material manufacture processFor preparation method; In composition of raw materials, add conductive filler, interact and form conductive network with Graphene, poly-at caprolactamClose rear formation conductive MC nylon/graphene composite material.
Further, the preparation method of a kind of conductive MC nylon/graphene composite material of the present invention, comprises followingStep:
The pretreatment of step 1, Graphene: Graphene passes through ultrasonic pretreatment in advance in alcohol solvent, forms graphiteAlkene predispersion;
The open loop of step 2, caprolactam: heating caprolactam and conductive filler formation caprolactam and conductive fillerMixed molten liquid adds the pretreated Graphene of described step 1 to divide in advance in the mixed molten liquid of described caprolactam and conductive fillerA prose style free from parallelism, opens high speed agitator and stirs after 10～20min, and alcohol solvent is removed in heating, controls temperature at 120-130 DEG C; ThenAdd NaOH to activate, control soak time at 10～25min, activation temperature is at 120～150 DEG C, and vacuumize remove anti-The water that should produce, makes reaction carry out to direction of polymerization; In performed polymer after activation completes, add curing agent, system is produced and hand overConnection reaction, prepares described MC nylon/graphene composite material after cross-linking reaction.
Further, in described step 1, the pretreated concrete grammar of Graphene is: first Graphene and ethanol are enteredRow premixed, and with high speed agitator stir 10～20min; Then in ultrasonic disperser, disperse to obtain after 10～20minGraphene predispersion.
Further, in described step 2, described curing agent is PAPI.
Further, in described step 2, described conductive filler be electrically conductive graphite, conductive black, conductive carbon nanotube andOne or more in conductive carbon fibre.
Further, the preparation method of a kind of conductive MC nylon/graphene composite material of the present invention, described raw materialComprise the component of following parts by weight:
Further, the preparation method of a kind of conductive MC nylon/graphene composite material of the present invention, described raw materialComprise the component of following parts by weight:
Further, the preparation method of a kind of conductive MC nylon/graphene composite material of the present invention, described raw materialComprise the component of following parts by weight:
Beneficial effect: the present invention and prior art compare and have the following advantages:
(1) grapheme material that conductive filler selection electric conductivity of the present invention is high, specific surface is large is as conductive filler modificationWhen high molecular polymer, in the time adding a small amount of Graphene (can be low to moderate 0.5%), just can form effective conductive network, promote multipleThe electrical property of condensation material, composite material surface resistivity can reach 105Ω. And the present invention selects electrically conductive graphite, conduction charcoalThe electric conductivity of other conductive fillers such as black, conductive carbon nanotube, conductive carbon fibre and the compound raising material of Graphene, at presentIn the expensive situation of Graphene, reduce production costs, contribute to apply.
(2) preparing in conducing composite material process, Graphene process for dispersing other Graphene/high polymers different from the pastComposite, is chosen in caprolactam open loop process and adds Graphene, and the Graphene after ultrasonic wave is pre-dispersed is stirringAfter, in caprolactam liquation, form the dispersion of molecular level, after caprolactam polymerization, form conducing composite material.
(3) the present invention selects Graphene to have reasonable electric conductivity as conductive filler. Due to Graphene itselfSpecific area is larger, and in polymeric system, good dispersion easily forms conductive network; Select other conductive filler and graphiteAlkene is composite, is conducive to the formation of conductive network in polymer, also contributes to reduce costs; The dispersion of Graphene in polymer isRelatively have feature, because the preparation process of MC nylon is a ring-opening polymerisation process, be one by little molecule to macromolecularForming process, Graphene in system along with the raising of MC nylon polymerization degree, the formation of strand and form effective conductive meshNetwork, than disperseing the efficiency of formation conductive network high by screw rod shearing under normal circumstances.
Brief description of the drawings
Fig. 1 MC nylon/graphene composite material synthesizer schematic diagram.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the present invention will be further described. But embodiments of the present invention also not onlyBe limited to this.
MC nylon/graphene composite material adopts in-situ polymerization technology preparation, by the ring-opening reaction system of caprolactamStandby. In caprolactam liquation, add pretreated Graphene, open after high speed agitator stir about 10～20min, heating removesDesolventizing, controls temperature at 120-130 DEG C; Then add NaOH to activate, control soak time at 10～25min, activationTemperature is at 120～150 DEG C, and vacuumizes the water producing except dereaction, and reaction is carried out to direction of polymerization; After activation completesIn performed polymer, adding the curing agent such as PAPI, make system produce cross-linking reaction, is also in this stage, and Graphene is along with MC nylonThe formation of strand and form stable conductive network structure in MC nylon system, improves the electric conductivity of composite.
Graphene passes through ultrasonic pretreatment in advance in alcohol solvent, forms Graphene/ethanolic solution. Dividing of GrapheneLoose mainly two stages, first stage is the pre-dispersed stage, adopts ultrasonic wave to disperse; Second stage is at caprolactamIn melt, by high speed agitator stir and MC nylon building-up process in molecular motion disperse, can obtain like this graphiteAlkene forms the conducing composite material of strand degree of scatter in MC nylon.
Embodiment 1
(1) preparation of Graphene predispersion.
First Graphene and ethanol are carried out to premixed, and stir 10min with high speed agitator. Then by Graphene/secondAlcohol be blended in ultrasonic disperser, disperse after 15min for subsequent use. To prepare at any time at any time to use in principle.
(2) synthesis technique of MC nylon is undertaken by following technique:
Preparation MC nylon/graphene composite material main raw material(s) specification used and producer, as shown in table 1.
Table 1 specifications of raw materials and producer
Preparation MC nylon/graphene composite material process conditions are as shown in table 2, and formula rate is as table 2:
Table 2 is prepared MC nylon/graphene composite material preparation process condition
Table 3 is prepared MC nylon/graphene composite material preparation formula
First take each component in table 3 ratio, after melting completely under table 2 technique; Add pretreated Graphene, addHeat vacuumizes the alcohol solvent in the system of removing; With table 2 technology controlling and process system temperature, vacuumize after adding NaOH, technique is by table2; Add after PAPI, after firmly shaking up, transfer in mould, be then placed in baking oven, after reaction 30min, close baking oven, allowIt is naturally cooling.
Properties of sample detects
(1) surface resistivity and specific insulation test
Adopt MC nylon casting method, become the standard sample of frosting specific insulation in die for molding, with GB/TThe performance of 1410-2006 " material volume resistivity and surface resistivity test method " test material.
The surface resistivity of the composite sample that after measured, embodiment 1 prepares is 104Ω, specific insulation is104Ω·m。
(2) sample Micro-Structure Analysis
With transmission electron microscope, sample is observed, observed the distribution of Graphene in plastics in sample.
Embodiment 2.
Substantially the same manner as Example 1, its difference is that MC nylon/graphene composite material formula is as shown in table 4.
(1) preparation of Graphene predispersion is with embodiment 1.
(2) synthesis technique of MC nylon is with embodiment 1 preparation process.
MC nylon/graphene composite material formula is as following table 4:
Table 4 is prepared MC nylon/graphene composite material preparation formula
Take each component in table 4 ratio, synthetic method is with embodiment 1.
Preparation standard print is with embodiment 1.
Surface resistivity and specific insulation are tested with embodiment 1. After measured, the composite that embodiment 2 preparesThe surface resistivity of sample is 105Ω, specific insulation is 105Ω·m。
Above embodiment is specifically described the present invention, and these embodiment are only for doing to be used as furtherly to the present inventionBright, can not be interpreted as limiting the scope of the invention, those skilled in the art's content according to the present invention is madeNon-intrinsically safe sexually revises, and all belongs to protection domain of the present invention.
Claims (9)
1. a preparation method for conductive MC nylon/graphene composite material, is characterized in that, selects Graphene, caprolactamAs raw material, taking caprolactam open loop in-situ polymerization as preparation method; In composition of raw materials, add conductive filler, with Graphene phaseMutual effect forms conductive network, forms conductive MC nylon/graphene composite material after caprolactam polymerization.
2. according to the preparation method of a kind of conductive MC nylon/graphene composite material described in right 1, it is characterized in that: compriseFollowing steps:
The pretreatment of step 1, Graphene: Graphene passes through ultrasonic pretreatment in advance in alcohol solvent, forms Graphene pre-Dispersion;
The open loop of step 2, caprolactam: heating caprolactam and conductive filler form the mixing of caprolactam and conductive fillerLiquation adds the pretreated Graphene of described step 1 pre-dispersed in the mixed molten liquid of described caprolactam and conductive fillerBody, opens high speed agitator and stirs after 10～20min, and alcohol solvent is removed in heating, controls temperature at 120-130 DEG C; Then addEnter NaOH and activate, control soak time at 10～25min, activation temperature is at 120～150 DEG C, and vacuumizes except dereactionThe water producing, makes reaction carry out to direction of polymerization; In performed polymer after activation completes, add curing agent, system is produced crosslinkedReaction, prepares described MC nylon/graphene composite material after cross-linking reaction.
3. according to the preparation method of a kind of conductive MC nylon/graphene composite material described in right 2, it is characterized in that, described inIn step 1, the pretreated concrete grammar of Graphene is: first Graphene and ethanol are carried out to premixed, and use high-speed stirredDevice stirs 10～20min; Then in ultrasonic disperser, disperse to obtain Graphene predispersion after 10～20min.
4. according to the preparation method of a kind of conductive MC nylon/graphene composite material described in right 2, it is characterized in that its spyLevy and be: in described step 2, described curing agent is PAPI.
5. according to the preparation method of a kind of conductive MC nylon/graphene composite material described in right 2, it is characterized in that, described inIn step 2, described conductive filler is a kind of or many in electrically conductive graphite, conductive black, conductive carbon nanotube and conductive carbon fibreKind.
6. according to the preparation method of a kind of conductive MC nylon/graphene composite material described in right 1～5 any one, its spyLevy and be, described raw material comprises the component of following parts by weight:
1275～1453.5 parts of caprolactams;
7.5～76.5 parts of Graphenes;
15～76.5 parts of conductive blacks;
15～76.5 parts of electrically conductive graphites;
1.5～15.3 parts of conductive carbon nanotubes;
NaOH5～10 part;
PAPI10～20 part.
7. according to the preparation method of a kind of conductive MC nylon/graphene composite material described in right 1～5 any one, its spyLevy and be, described raw material comprises the component of following parts by weight:
1453.5 parts of caprolactams;
15 parts of Graphenes;
15 parts of conductive blacks;
15 parts of electrically conductive graphites;
1.5 parts of conductive carbon nanotubes;
NaOH5.8 part;
PAPI12 part.
8. according to the preparation method of a kind of conductive MC nylon/graphene composite material described in right 1～5 any one, its spyLevy and be, described raw material comprises the component of following parts by weight:
1438.5 parts of caprolactams;
7.5 parts of Graphenes;
30 parts of conductive blacks;
22.5 parts of electrically conductive graphites;
1.5 parts of conductive carbon nanotubes;
NaOH5.8 part;
PAPI12 part.
9. conductive MC nylon/graphene composite material, is characterized in that, adopts side described in claim 1～8 any oneMethod prepares.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101928457A (en) * | 2010-05-18 | 2010-12-29 | 赵明久 | Carbon-based nano cast nylon composite material and in-situ polymerization preparation method thereof |
| CN102260406A (en) * | 2011-07-05 | 2011-11-30 | 南京理工大学 | Methyl cellulose (MC) nylon nano conductive composite material and preparation method thereof |
| US20130242578A1 (en) * | 2011-12-21 | 2013-09-19 | Industrial Technology Research Institute | High thermally conductive composites and illumination device |
| CN105001601A (en) * | 2015-06-19 | 2015-10-28 | 周焕民 | Spinning conductive masterbatch containing graphene and preparation method thereof |
-
2015
- 2015-12-30 CN CN201511019805.1A patent/CN105601909A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101928457A (en) * | 2010-05-18 | 2010-12-29 | 赵明久 | Carbon-based nano cast nylon composite material and in-situ polymerization preparation method thereof |
| CN102260406A (en) * | 2011-07-05 | 2011-11-30 | 南京理工大学 | Methyl cellulose (MC) nylon nano conductive composite material and preparation method thereof |
| US20130242578A1 (en) * | 2011-12-21 | 2013-09-19 | Industrial Technology Research Institute | High thermally conductive composites and illumination device |
| CN105001601A (en) * | 2015-06-19 | 2015-10-28 | 周焕民 | Spinning conductive masterbatch containing graphene and preparation method thereof |
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| 卓昌明，陈炎嗣: "《塑料应用技术手册》", 31 May 2013 * |
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Application publication date: 20160525 |