CN108084627B - HIPS (high impact polystyrene) based conductive master batch based on carbon nano tube and graphene compound system and preparation method thereof - Google Patents
HIPS (high impact polystyrene) based conductive master batch based on carbon nano tube and graphene compound system and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 49
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 48
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 48
- 229920005669 high impact polystyrene Polymers 0.000 title claims abstract description 39
- 239000004797 high-impact polystyrene Substances 0.000 title claims abstract description 39
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 31
- -1 graphene compound Chemical class 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000006185 dispersion Substances 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 238000001125 extrusion Methods 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 4
- 229920005604 random copolymer Polymers 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 238000012545 processing Methods 0.000 claims description 8
- 238000013329 compounding Methods 0.000 claims description 7
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000004020 conductor Substances 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- YPNZYYWORCABPU-UHFFFAOYSA-N oxiran-2-ylmethyl 2-methylprop-2-enoate;styrene Chemical group C=CC1=CC=CC=C1.CC(=C)C(=O)OCC1CO1 YPNZYYWORCABPU-UHFFFAOYSA-N 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 8
- 238000012986 modification Methods 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 6
- 238000001746 injection moulding Methods 0.000 abstract description 3
- 239000012442 inert solvent Substances 0.000 abstract 1
- 239000011344 liquid material Substances 0.000 abstract 1
- 239000004033 plastic Substances 0.000 description 10
- 229920003023 plastic Polymers 0.000 description 10
- 239000003575 carbonaceous material Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000010410 layer Substances 0.000 description 5
- 239000002086 nanomaterial Substances 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- XHAFIUUYXQFJEW-UHFFFAOYSA-N 1-chloroethenylbenzene Chemical compound ClC(=C)C1=CC=CC=C1 XHAFIUUYXQFJEW-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical group CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
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- 239000002482 conductive additive Substances 0.000 description 1
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- 229920001197 polyacetylene Polymers 0.000 description 1
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- 239000000047 product Substances 0.000 description 1
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- 239000000243 solution Substances 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
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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
- 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
- C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
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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
- C08J2351/00—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
- C08J2351/04—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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- 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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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
The invention provides an HIPS-based conductive master batch based on a carbon nano tube and graphene compound system and a preparation method thereof; firstly, uniformly dispersing carbon nano tubes and graphene in a volatile inert solvent respectively, treating for 1h by an ultrasonic treatment device respectively, then stirring the treated dispersion liquid and raw materials in a high-speed stirrer according to a certain proportion, mixing the dispersion liquid and a compatilizer at room temperature according to a certain proportion, and then performing melt extrusion through a double screw to prepare the conductive master batch. The composite material prepared by the invention has excellent conductivity, is easy to add, and can be widely applied to the fields of injection molding, extrusion, modification and the like.
Description
Technical Field
The invention belongs to the field of macromolecules, and particularly relates to a conductive master batch of an HIPS (high impact polystyrene) base material based on a compounding system of carbon nanotubes and graphene and a preparation method of the conductive master batch.
Background
HIPS is a widely used plastic raw material, has wide application in the fields of electronic packaging, household appliances, plates, carrier tapes and the like, and has the characteristics of good processability and attractive appearance. However, plastics are generally insulated, and with the development of society and the progress of science and technology, the application range of plastics is wider and wider, and the requirements of people are higher and higher, and the insulation can cause that static charges accumulated on the surface of a plastic product can not be released, so that static voltage is formed, dirt such as dust and the like can be easily adsorbed, and after the static voltage reaches a certain degree, electrostatic discharge (ESD) and electric shock phenomena can be generated. In particular, in the electronic industry, various precision instruments and precision electronic components are damaged or even scrapped due to electrostatic breakdown, and in some industrial and mining enterprises contacting flammable and explosive substances, electrostatic discharge can have more serious consequences if the electrostatic discharge cannot be effectively protected, and the life of field workers can be endangered once an accident occurs, and serious economic loss is caused. On the other hand, with the development of modern electronics industry, electromagnetic interference (EMI) and Radio Frequency Interference (RFI) become new "environmental pollution" problems, and micro-current between precision electronic components is easily affected by such a complicated electromagnetic environment, resulting in malfunctions, image obstruction, and the like.
Therefore, studies have been made on how to improve the antistatic property of plastics. At present, two methods are mainly used, one is a polymerization stage, a conjugated structure is introduced to form a conductive path, so that the static dissipation is improved; and the other is compounded with conductive auxiliary agent to prepare the composite antistatic plastic. The conductive auxiliary agent has inorganic and organic structures: the compatibility of the organic conductive agent and plastics is excellent, but some points exist, for example, the antistatic rate of the iodine-doped polyacetylene is reduced by one order of magnitude after being exposed in air for 1000 hours, and the iodine-doped polyphenylacetylene basically loses the antistatic property after being exposed in air for 250 hours; the inorganic conductive additive is generally dispersed in plastic to form a through/semi-through structure, and the obtained conductive and antistatic composite material has a fatal defect of poor dispersibility, particularly in nano-structured carbon nanotubes and graphene.
As a novel nano material with the strongest electric conduction and heat conduction performance discovered at present, a small amount of carbon nano tubes and graphene are doped into the plastic, so that the plastic theoretically has good antistatic property; however, carbon materials are extremely difficult to disperse due to surface inertness and strong van der waals forces between sheets. How to effectively disperse carbon materials in composite materials becomes a hot spot for researching antistatic and even conductive materials, and the prior art has no effective solution for the problem.
Disclosure of Invention
Aiming at the problems in the antistatic composite material in the prior art and the difficulty in meeting the requirements of occasions with higher requirements and the requirements of stability, the invention provides the conductive master batch of the HIPS base material based on the compounding system of the carbon nano tube and the graphene, which is simple and effective, and the preparation method thereof; the composite material has the advantages of stable performance, simple and controllable processing technology, high safety and the like, and can be widely used on equipment such as communication terminals, computers, automobile telephones, cash registers and the like.
The purpose of the invention is realized by the following technical scheme:
the HIPS-based conductive master batch based on the carbon nanotube and graphene compound system is prepared from the following raw materials in percentage by weight:
HIPS 85~98%；
0.2-2% of carbon nano tube;
1-8% of graphene;
0.5-5% of a compatilizer;
the compatilizer is a random copolymer obtained by copolymerizing aromatic vinyl monomers and glycidyl methacrylate; the number average molecular weight of the random copolymer is 10000-90000.
Preferably, the aromatic vinyl monomer includes a styrene monomer, an α -methylstyrene monomer, an α -chlorostyrene monomer or a p-methylstyrene monomer; in the preparation of the random copolymer, the glycidyl methacrylate is used in an amount of 5 to 20 wt% based on the total amount of the aromatic vinyl monomer and the glycidyl methacrylate, and is preferably in the form of particles or powder, more preferably in the form of powder. If the molecular weight is too high, the polymerization process is not easy to control, and if the molecular weight is too low, the processing viscosity is not matched, and the stripping force is not enough to disperse the carbon nanotubes and the graphene; the content of glycidyl methacrylate is too low, the number of active functional groups is too small, the carbon nano material is not easy to infiltrate, the polymerization process is difficult if too much, and excessive functional group content can cause over reaction and is not easy to disperse.
Further preferably, the aromatic vinyl monomer is a styrene monomer; the random copolymer is an ST-GMA binary random copolymer.
Preferably, the melt index of the random copolymer at 190 ℃/5kg is 40-100 g/10 min.
Preferably, the carbon nanotubes have an average diameter of <20nm, an average length of 1-20 μm, and an average number of wall layers of < 15.
Preferably, the average number of wall layers of the graphene is < 15.
Preferably, the HIPS raw material is in the form of particles or powder, more preferably powder, and the average particle size is larger than 30 meshes.
The invention provides a preparation method of the HIPS-based conductive master batch based on the carbon nanotube and graphene compound system, which comprises the following steps:
(1) respectively dispersing carbon nanotubes and graphene in an inert volatile solvent, and stirring at normal temperature for 10-30 min to obtain a carbon nanotube suspension and a graphene suspension;
(2) respectively treating the carbon nanotube suspension and the graphene suspension for 1h by using an ultrasonic treatment device of 400-800W to obtain a carbon nanotube dispersion liquid and a graphene dispersion liquid;
(3) mixing and stirring the carbon nanotube dispersion liquid, the graphene dispersion liquid and HIPS to obtain a dispersing material; the stirring speed is 1300-2000 rpm;
(4) mixing the dispersing material with a compatilizer, and then carrying out melt extrusion through a double screw to obtain HIPS-based conductive master batch based on a carbon nano tube and graphene compound system; the processing temperature of the twin-screw melt extrusion is 190-230 ℃, and the rotating speed is 100-400 rpm.
Preferably, the twin-screw extruder has a length to diameter ratio of greater than 40, preferably 52.
The invention also discloses application of the carbon nano tube and graphene complex ligand system in preparation of the antistatic styrene-based polymer.
The invention also discloses an application of the HIPS-based conductive master batch based on the carbon nano tube and graphene compound system in preparing a conductive material.
In the HIPS-based conductive master batch based on the carbon nano tube and graphene compound system, P electrons of carbon atoms on the carbon nano tube form large-range delocalized pi bonds, the conjugation effect is obvious, the carbon nano tube has good antistatic performance, and meanwhile, the antistatic performance is related to the tube diameter and the helix angle of the tube wall, and the limited parameters of the HIPS-based conductive master batch have good antistatic performance; graphene is a honeycomb-shaped planar thin film formed by carbon atoms in an sp2 hybridization mode, wherein a single-layer graphene is a quasi-two-dimensional material with the thickness of only one atomic layer, and the quasi-two-dimensional thin film has very good strength, flexibility, electric conduction, heat conduction and optical characteristics, so that the prepared composite material has excellent electric conductivity, is convenient to manufacture and easy to add, can be widely applied to the fields of injection molding, extrusion, modification and the like, and has wide application space in the fields of physics, materials science, electronic information, computers, aerospace and the like. The composite material prepared by the invention has excellent conductivity, is convenient to manufacture and easy to add, and can be widely applied to the fields of injection molding, extrusion, modification and the like.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, the carbon nano tube and the graphene are effectively pre-dispersed through the ultrasonic device, so that the van der Waals force among nano structures is weakened, and a certain activation effect is achieved on the surface, so that the carbon nano material is ensured to have good dispersibility in the melting and extruding process.
2. The random copolymer with the compatibilization effect disclosed by the invention has high reaction activity, is thermodynamically compatible with HIPS, and has functional groups and molecular weight which are in the level of common polymers, so that the thermal stability of co-extrusion with the polymers in the subsequent process is good.
3. The preparation method of the HIPS-based conductive master batch based on the carbon nano tube and graphene compounding system is convenient to use, does not have secondary pollution, and provides an applicable method for preparing the efficient antistatic master batch.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
The raw material composition of the master batches of examples and comparative examples is shown in table 1.
Wherein the carbon nanotubes have an average diameter of less than 20nm, an average length of 1-20 μm, and an average number of wall layers of less than 15.
Wherein the average number of graphene wall layers is < 15.
The random copolymer is an ST-GMA binary random copolymer, the ST content is 95 wt%, the GMA content is 5 wt%, the number average molecular weight is 30000, and the melt index at 190 ℃/5kg is 40-100 g/10 min.
Wherein the HIPS is powder with the particle size of 50 meshes.
The preparation method of the HIPS-based conductive master batch based on the carbon nanotube and graphene compound system comprises the following steps:
(1) respectively dispersing carbon nanotubes and graphene in an inert volatile solvent butanone, and stirring at normal temperature for 10-30 min to obtain a carbon nanotube suspension and a graphene suspension;
(2) respectively treating the carbon nanotube suspension and the graphene suspension according to an ultrasonic treatment device in table 1 to obtain a carbon nanotube dispersion liquid and a graphene dispersion liquid;
(3) mixing and stirring the carbon nanotube dispersion liquid, the graphene dispersion liquid and HIPS to obtain a dispersing material;
(4) mixing the dispersing material with a compatilizer, and then carrying out melt extrusion through a double screw to obtain HIPS-based conductive master batch based on a carbon nano tube and graphene compound system; the processing temperature of the twin-screw melt extrusion is 190-230 ℃, the rotating speed is 100-400 rpm, and the length-diameter ratio of the twin-screw extruder is 55.
Table 1 conductive masterbatch embodiment ratio
Effect verification:
the master batch samples manufactured in the above examples and comparative examples were mixed with HIPS to prepare a conductive material, the content of the conductive carbon material in the final product was guaranteed to be 1%, then the final product was pressed into a sheet by a flat-plate vulcanizer at a pressing temperature of 220 ℃ for 30 seconds, and then the surface resistance was measured, and the results are shown in Table 2, and the stability of the granulation was observed according to the extrusion process, which was classified into good, normal, and poor, and the stability of the properties was observed according to the conductivity of the sheet measured at multiple points.
Table 2 comparison of embodiment properties
As can be seen from the results in Table 2, the HIPS conductive master batch with excellent conductivity and stable processing can be obtained by combining the carbon material and the compatilizer according to the process disclosed by the invention; the electrical property is reduced due to the excessively high or excessively low content of the compatilizer, the electrical property is reduced due to the excessively high content of the carbon material, the processing stability is poor although the electrical conductivity is good, and the electrical conductivity effect is poor due to the excessively low content of the carbon material; meanwhile, a sheet prepared from the master batch in example 5 is taken, and a sample is taken at each of four corners and the middle of the sheet; and (3) taking the sheet prepared from the master batch in the comparative example 2, and taking a sample at each of four corners and the middle of the sheet, wherein the test shows that the resistance and the fluctuation reach 3-4 orders of magnitude.
In conclusion, the conductive master batch of the HIPS base material based on the compounding system of the carbon nano tube and the graphene and the preparation method thereof provided by the invention can obtain the conductive master batch with excellent conductive performance, and are stable in processing and simple in use.
The invention has many applications, and the above description is only a preferred embodiment of the invention. It should be noted that the above examples are only for illustrating the present invention, and are not intended to limit the scope of the present invention. It will be apparent to those skilled in the art that various modifications can be made without departing from the principles of the invention and these modifications are to be considered within the scope of the invention.
Claims (5)
1. The HIPS-based conductive master batch based on the carbon nanotube and graphene compound system is characterized by being prepared from the following raw materials in percentage by weight:
HIPS 85~98%；
1% of carbon nano tube;
5% of graphene;
0.5-5% of a compatilizer;
the compatilizer is a styrene-glycidyl methacrylate random copolymer; the number average molecular weight of the random copolymer is 10000-90000; the amount of the glycidyl methacrylate is 5 wt% of the total amount of the styrene and the glycidyl methacrylate; the melt index of the random copolymer at 190 ℃/5kg is 40-100 g/10 min;
the preparation method of the HIPS-based conductive master batch based on the carbon nanotube and graphene compound system comprises the following steps:
(1) respectively dispersing carbon nanotubes and graphene in an inert volatile solvent, and stirring at normal temperature for 10-30 min to obtain a carbon nanotube suspension and a graphene suspension;
(2) respectively treating the carbon nanotube suspension and the graphene suspension for 1h by an ultrasonic treatment device of 800W to obtain a carbon nanotube dispersion liquid and a graphene dispersion liquid;
(3) mixing and stirring the carbon nanotube dispersion liquid, the graphene dispersion liquid and HIPS to obtain a dispersing material; the rotating speed of the stirring is 1600 revolutions per minute;
(4) mixing the dispersing material with a compatilizer, and then carrying out melt extrusion through a double screw to obtain HIPS-based conductive master batch based on a carbon nano tube and graphene compound system; the processing temperature of the twin-screw melt extrusion is 190-230 ℃, and the rotating speed is 100-400 rpm.
2. The HIPS-based conductive masterbatch based on the carbon nanotube and graphene compound system of claim 1, wherein the average diameter of the carbon nanotube is less than 20nm, the average length is 1-20 μm, and the average number of wall layers is less than 15; the average number of wall layers of the graphene is < 15.
3. The HIPS-based conductive masterbatch based on the carbon nanotube and graphene compounding system according to claim 1, wherein the HIPS is in the form of particles or powder; the average particle size of the HIPS is more than 30 meshes.
4. The HIPS-based conductive masterbatch based on the carbon nanotube and graphene compounding system according to claim 1, wherein the length-diameter ratio of the twin-screw extruder is greater than 40.
5. The application of the HIPS-based conductive master batch based on the carbon nanotube and graphene compounding system in the preparation of the HIPS conductive material in claim 1.
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| CN110698801A (en) * | 2019-11-26 | 2020-01-17 | 江苏新奥碳纳米材料应用技术研究院有限公司 | High-fluidity graphene modified polystyrene composite material and preparation method thereof |
| CN111019283A (en) * | 2019-12-27 | 2020-04-17 | 新奥石墨烯技术有限公司 | Graphene modified conductive polystyrene composite material for precise electronic carrier tape and preparation method thereof |
| CN114573894B (en) * | 2020-12-01 | 2024-03-01 | 中国石油天然气股份有限公司 | Carbon nano tube master batch and preparation method and application thereof |
| CN114083851A (en) * | 2021-12-27 | 2022-02-25 | 苏州盎世新材料有限公司 | Semitransparent sheet and processing technology thereof |
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