CN110698801A - High-fluidity graphene modified polystyrene composite material and preparation method thereof - Google Patents
High-fluidity graphene modified polystyrene composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical application field of high-molecular nano composite materials, in particular to a high-fluidity graphene modified polystyrene composite material and a preparation method thereof. The composite material is composed of the following components: polystyrene, a conductive material, a toughening agent, an antioxidant, a flow modifier, a coupling agent and other auxiliary agents. The high-fluidity graphene modified polystyrene composite material and the preparation method thereof provide a polystyrene composite material for improving the processing performance and the electrical conductivity, and the fully-peeled and uniformly-dispersed graphene nanosheets are prepared in situ in the solution by combining the moderate oxidation technology and the liquid phase peeling technology, so that the production process is simple, convenient and easy to implement, and has the effects of safety, environmental protection and low production cost.
Description
Technical Field
The invention relates to a polystyrene composite material, in particular to a high-fluidity graphene modified polystyrene composite material for improving the processing performance and the electrical conductivity and a preparation method thereof, belonging to the technical application field of polymer nano composite materials.
Background
Polystyrene (PS) is one of five general-purpose resins, and the demand of the PS is continuously increased along with the development of science and technology and the continuous progress of society; the traditional application field is nearly saturated, so the application range of the polystyrene is greatly expanded by a modification technology, and the conductive polystyrene is also different from the army bump.
Conventional conductive polystyrenes achieve lower electrical resistance by incorporating high loadings of conventional conductive fillers including conductive carbon black, conductive graphite, carbon fibers and the like, and a series of more complex processing procedures. Due to the fact that the conductive material with high filling amount has a series of production problems of poor mechanical property, poor flowability, high processing difficulty and the like, the cost of a manufacturer is increased, profits are reduced, and the continuous development of the conductive material is not facilitated.
The appearance of the graphene perfectly solves the problems brought by the traditional conductive filler. The graphene has excellent mechanical properties, electrical properties and self-structure. The high-fluidity graphene modified conductive polystyrene utilizes the ultrahigh electrical property of graphene to replace the traditional conductive filler, achieves the same conductive property, reduces the addition of carbon, and avoids the defect of material mechanics caused by overhigh carbon content; meanwhile, other auxiliary agents are matched, so that the high-conductivity composite material has high conductivity, the fluidity of the composite material is increased, the processing difficulty is reduced, and the application range of the composite material in the field of injection molding is expanded. The two are combined, thereby making up the defects brought by the traditional conductive filler.
The Lijunfeng et al of Jilin university discloses a method for preparing core-shell structure conductive polystyrene particles by using waste polystyrene (Chinese patent publication No. CN 109280285A), and the adopted technical scheme is as follows: firstly, taking a certain proportion of benzene or halogenated hydrocarbon and alcohol, stirring and mixing to form a mixed solution; then dispersing the conductive material in the mixed solution; then adding polystyrene particles, adding excessive absolute ethyl alcohol or methanol, filtering and drying to obtain the polystyrene particles with the shell containing the conductive material. However, this technical path has significant drawbacks: the quality of raw materials cannot be guaranteed by waste plastics, so that the quality of a final product is greatly influenced, and the yield is worried; the low yield increases the production cost to a great extent, so the method is not suitable for batch production; reagents such as benzene or halogenated hydrocarbon used in the preparation process have negative effects on human bodies and the environment to different degrees, so that the environmental protection pressure and the risk coefficient of the preparation process are increased; the conductive particles with the core-shell structure are obtained by the technology, the outer shell is really conductive, and the polystyrene at the central part still has no conductivity, so that the application limitation is increased; the core and the shell in the core-shell structure are two different materials, the two materials have different mechanical properties, and the phenomenon that the appearance is complete but the internal material is broken or the internal material is intact and the single-surface structure is damaged to lose conductivity can be possibly generated, so that the quality of a final product is influenced; the conductive materials added in the preparation process of the technology are conductive carbon black, graphite, carbon nano tubes and other materials, and are not greatly different from other modified conductive plastics, so the improvement of the fluidity of plastic particles is to be proved.
European Jade spring, et al, the institute of chemistry of the Chinese academy of sciences, disclose a polystyrene/graphite conductive composite material and a method for preparing the same (Chinese patent publication No. CN 1166732C), which comprises soaking graphite in a mixed solution of strong sulfuric acid and strong nitric acid for 10-24 hours, and then heating the graphite at 1100 ℃ through a muffle furnace to obtain expanded graphite; then stirring the obtained expanded graphite and polystyrene, and standing for 10-24 hours; finally adding the mixture into a reactor containing an initiator, a suspending agent and water, and starting polymerization reaction for 6-10 hours at the temperature of 60-100 ℃ under the protection of nitrogen to obtain the polystyrene/graphite conductive composite material. The method has the defects that the strong nitric acid and the strong sulfuric acid can damage the structure of the graphite, so that the conductivity of the final material is influenced; the preparation process is complex and is not suitable for industrial large-scale production; the preparation time is too long, the preparation cost is increased, and the method is more suitable for laboratory experiments rather than industrial production requiring efficiency.
In the prior art, the defects are as follows:
in the current process of preparing the conductive modified polystyrene, the fluidity of polystyrene particles is increased by reducing the filling amount of the conductive material, and the conductive property is poor and the application range is small because the filling amount of the conductive material is reduced.
In the prior process of preparing the conductive modified polystyrene, in order to ensure the conductivity, the filling amount of the conductive filler is large, so that the mechanical property of the conductive polystyrene particles is poor, the fluidity is low, and the processability is poor.
At present, conductive carbon black is used as a conductive material to modify polystyrene, but in order to improve the fluidity of the material and ensure the good dimensional stability of the material, the addition amount of the conductive carbon black needs to be greatly reduced, but the dimensional stability is difficult to control due to the limit of the performance of the carbon black.
Disclosure of Invention
The invention aims to solve the defects and provides a high-fluidity graphene modified polystyrene composite material and a preparation method thereof.
In order to overcome the defects in the background art and achieve the purposes that:
the graphene has extremely strong conductive performance, and the addition amount of the graphene is far smaller than that of the traditional conductive filler when the same conductive effect is achieved; meanwhile, the adoption of the phase-melting agent can increase the fluidity of the particles, reduce the processing difficulty and increase the dispersion uniformity of the conductive material in the polystyrene, so that the resistance of the conductive polystyrene particles is more uniform.
The high-fluidity graphene modified polystyrene composite material is high in fluidity, low in processing difficulty of particles, capable of improving the processing performance of the particles, and capable of greatly expanding the application range of the material in the field of injection molding.
The high-fluidity graphene modified polystyrene composite material is provided, and the final product has higher dimensional stability due to the structural characteristics and the super-strong rigidity of graphene.
The high-fluidity graphene modified polystyrene and the preparation method thereof are provided: the graphene is uniformly dispersed in the polystyrene matrix by using a stepwise blending technical process so as to ensure uniform resistance, excellent mechanical properties and high material flowability.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a high-fluidity graphene modified polystyrene composite material is composed of the following components:
polystyrene 60% ~ 70%;
conductive material 1% ~ 5%;
5% of a toughening agent 5 ~ 10%;
0.1 percent of antioxidant ~ 5 percent;
flow modifier 1% ~ 5%;
coupling agent 0.1% ~ 5%;
1% of other auxiliary agents ~ 10%.
According to another embodiment of the present invention, the toughening agent is one or more of styrene-butadiene-styrene copolymer (SBS), K-glue, ethylene-vinyl acetate copolymer (EVA), polyolefin elastomer (POE), and hydrogenated styrene-butadiene block copolymer (SEBS);
according to another embodiment of the present invention, further comprising the antioxidants are antioxidant 1010 and antioxidant 168;
according to another embodiment of the present invention, it is further included that the coupling agent is one of a silane coupling agent and a phthalate coupling agent.
According to another embodiment of the present invention, the conductive material is one or more of graphene, conductive carbon black, carbon nanotubes, carbon fibers, and ultra-fine graphite.
According to another embodiment of the present invention, further comprising the flow modifier is at least one of polyethylene wax, paraffin wax, white oil, EBS;
according to another embodiment of the present invention, further comprising the other adjuvant comprises maleic anhydride and dicumyl peroxide (DCP).
A preparation method of a high-fluidity graphene modified polystyrene composite material comprises the following steps:
firstly, mixing a toughening agent, a coupling agent, an antioxidant, a flow modifier and polystyrene together, putting the mixture into a high-speed mixer, and mixing for 3 minutes at a high speed to obtain a uniformly mixed mixture;
secondly, adding a conductive material into the mixture obtained in the first step, putting the mixture into a high-speed mixer, and mixing the mixture for 3 minutes at a high speed to obtain a mixed base material;
thirdly, adding a flow modifier and other additives into the base material obtained in the second step, and mixing at high speed for 3 minutes again to obtain a raw material of the high-fluidity conductive polystyrene which can be processed and produced;
and fourthly, granulating the raw material of the high-fluidity conductive polystyrene obtained in the third step by a double-screw extruder and a granulator.
The invention has the beneficial effects that: the high-fluidity graphene modified polystyrene composite material and the preparation method thereof provide a polystyrene composite material for improving the processing performance and the electrical conductivity, and the fully-peeled and uniformly-dispersed graphene nanosheets are prepared in situ in the solution by combining the moderate oxidation technology and the liquid phase peeling technology, so that the production process is simple, convenient and easy to implement, and has the effects of safety, environmental protection and low production cost.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A high-fluidity graphene modified conductive polystyrene and a preparation method thereof comprise the following steps:
firstly, putting High Impact Polystyrene (HIPS), 7% hydrogenated styrene-butadiene block copolymer (SEBS), 0.2% antioxidant and 3% paraffin oil into a high-speed mixer, and mixing for 3 minutes at high speed to uniformly mix, wherein the antioxidant is antioxidant 1010 and antioxidant 168 according to a mass ratio of 1: 1, compounding;
secondly, sequentially adding 2% of graphene and 1% of carbon nano tubes into a high-speed mixer, blending the graphene and the carbon nano tubes with the material obtained in the first step again, and leaving the mixture in the high-speed mixer after mixing for 3 minutes at a high speed for the next step; the graphene and the carbon nano tube are combined to form a network structure by facial lines, so that the self-dispersion is promoted, and the self-structure and mechanical properties can be better exerted;
thirdly, putting 2% oxidized polyethylene wax powder, 2% maleic anhydride and 1% dicumyl peroxide (DCP) into a high-speed mixer in the second step, and mixing for 3 minutes at high speed, wherein the temperature is controlled at 70 ℃ of ~ 90 ℃, so that uniformly mixed raw materials can be obtained;
and fourthly, adding the uniformly mixed raw materials into a double-screw extruder, and extruding and granulating under the conditions that the temperature is 230 ℃ and the rotating speed of a main machine is 350rpm to obtain the high-fluidity graphene modified conductive polystyrene special material.
Example 2
A high-fluidity graphene modified conductive polystyrene and a preparation method thereof comprise the following steps:
firstly, putting High Impact Polystyrene (HIPS), 7% hydrogenated styrene-butadiene block copolymer (SEBS), 0.2% antioxidant and 3% paraffin oil into a high-speed mixer, and mixing for 3 minutes at high speed to uniformly mix, wherein the antioxidant is antioxidant 1010 and antioxidant 168 according to a mass ratio of 1: 1, compounding;
secondly, adding 3% of graphene into a high-speed mixer, blending the graphene with the material obtained in the first step again, mixing the graphene and the material for 3 minutes at a high speed, and leaving the mixture in the high-speed mixer for the next step; by utilizing the high conductivity of the graphene, the flowability of the material is greatly improved while the same conductivity is achieved; the graphene is superior to the self-structural characteristics of carbon black, and the dimensional stability of the material is improved;
thirdly, putting 2% of oxidized polyethylene wax powder, 2% of maleic anhydride and 1% of dicumyl peroxide (DCP) into the high-speed mixer in the second step, mixing for 3 minutes at high speed, and controlling the temperature at ~ 90 ℃ at 70 ℃ to obtain uniformly mixed raw materials;
and fourthly, adding the uniformly mixed raw materials into a double-screw extruder, and extruding and granulating under the conditions that the temperature is 230 ℃ and the rotating speed of a main machine is 350rpm to obtain the high-fluidity graphene modified conductive polystyrene special material.
Example 3
A high-fluidity graphene modified conductive polystyrene and a preparation method thereof comprise the following steps:
firstly, putting High Impact Polystyrene (HIPS), 7% hydrogenated styrene-butadiene block copolymer (SEBS), 0.2% antioxidant and 3% paraffin oil into a high-speed mixer, and mixing for 3 minutes at high speed to uniformly mix, wherein the antioxidant is antioxidant 1010 and antioxidant 168 according to a mass ratio of 1: 1, compounding;
secondly, sequentially adding 2% of graphene and 1% of carbon nano tubes into a high-speed mixer, blending the graphene and the carbon nano tubes with the material obtained in the first step again, mixing the graphene and the carbon nano tubes for 3 minutes at a high speed, and leaving the mixture in the high-speed mixer for the next step;
thirdly, putting 2% of amine distearate wax powder, 2% of maleic anhydride and 1% of dicumyl peroxide (DCP) into a high-speed mixer, and mixing at high speed for 3 minutes at the temperature of 70 ℃ ~ 90 ℃ to obtain uniformly mixed raw materials;
and fourthly, adding the uniformly mixed raw materials into a double-screw extruder, and extruding and granulating under the conditions that the temperature is 230 ℃ and the rotating speed of a main machine is 350rpm to obtain the high-fluidity graphene modified conductive polystyrene special material.
Comparative example 1
Firstly, putting High Impact Polystyrene (HIPS), 7% hydrogenated styrene-butadiene block copolymer (SEBS), 0.2% antioxidant and 3% paraffin oil into a high-speed mixer, and mixing for 3 minutes at high speed to uniformly mix, wherein the antioxidant is antioxidant 1010 and antioxidant 168 according to a mass ratio of 1: 1, compounding;
secondly, sequentially adding 2% of carbon nano tubes and 8% of conductive carbon black into a high-speed mixer, blending the carbon nano tubes and the conductive carbon black with the material obtained in the first step again, mixing the carbon nano tubes and the conductive carbon black for 3 minutes at a high speed, and leaving the mixture in the high-speed mixer to prepare for the next step;
thirdly, putting 2% oxidized polyethylene wax powder, 2% maleic anhydride and 1% dicumyl peroxide (DCP) into a high-speed mixer, mixing for 3 minutes at high speed, and controlling the temperature at ~ 90 ℃ to obtain uniformly mixed raw materials;
and fourthly, adding the uniformly mixed raw materials into a double-screw extruder, and extruding and granulating at the temperature of 230 ℃ and the rotating speed of a main machine of 350rpm to obtain the high-fluidity graphene modified conductive polystyrene special material.
Comparative example 2
Firstly, putting High Impact Polystyrene (HIPS), 7% hydrogenated styrene-butadiene block copolymer (SEBS), 0.2% antioxidant and 3% paraffin oil into a high-speed mixer, and mixing for 3 minutes at high speed to uniformly mix, wherein the antioxidant is antioxidant 1010 and antioxidant 168 according to a mass ratio of 1: 1, compounding;
secondly, adding 10% of conductive carbon black into a high-speed mixer, blending the conductive carbon black with the material obtained in the first step again, mixing the conductive carbon black and the material for 3 minutes at a high speed, controlling the temperature to be at 70 ℃ and ~ 90 ℃, and leaving the conductive carbon black in the high-speed mixer to prepare for the next step;
thirdly, putting 2% of oxidized polyethylene wax powder, 2% of maleic anhydride and 1% of dicumyl peroxide (DCP) into a high-speed mixer, and mixing for 3 minutes at high speed to obtain uniformly mixed raw materials;
and fourthly, adding the uniformly mixed raw materials into a double-screw extruder, and extruding and granulating at the temperature of 230 ℃ and the rotating speed of a main machine of 350rpm to obtain the high-fluidity graphene modified conductive polystyrene special material.
Table 1 shows experimental data of high-fluidity graphene-modified polystyrene:
the comparative example shows that the graphene can still achieve the conductive effect of the high-filling-amount carbon black under the condition of low addition amount, and is even better than the conductive performance of the carbon black under the high filling amount.
The high-fluidity graphene modified polystyrene composite material utilizes the high conductivity of graphene, achieves the same conductivity, and reduces the filling amount of the conductive material, thereby avoiding the influence of the traditional conductive filler on the fluidity of the material, and greatly improving the fluidity of the material; the structural characteristics of graphene superior to carbon black are utilized, so that the carbon content is reduced, and the dimensional stability of the material is improved; the graphene and the carbon nano tube are in line combination to form a network structure better, so that the self dispersion can be promoted, and the self structure and mechanical property can be better exerted; by means of step-by-step mixing, the conductive material, the processing aid and the polystyrene raw material are fully and uniformly mixed, and the performances of the graphene, the carbon tube and the processing aid are utilized to the maximum extent.
The above description is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can substitute or change the technical solution and the inventive concept of the present invention within the technical scope of the present invention, and the technical solution and the inventive concept thereof should be covered by the scope of the present invention, and if they are used in the injection molding field, they should fall within the scope of the claims of the present invention.
Claims (8)
1. The high-fluidity graphene-modified polystyrene composite material is characterized by being composed of the following components:
polystyrene 60% ~ 70%;
conductive material 1% ~ 5%;
5% of a toughening agent 5 ~ 10%;
0.1 percent of antioxidant ~ 5 percent;
flow modifier 1% ~ 5%;
coupling agent 0.1% ~ 5%;
1% of other auxiliary agents ~ 10%.
2. The high-fluidity graphene-modified polystyrene composite material of claim 1, wherein the toughening agent is one or more of styrene-butadiene-styrene copolymer (SBS), K-glue, ethylene-vinyl acetate copolymer (EVA), polyolefin elastomer (POE) and hydrogenated styrene-butadiene block copolymer (SEBS).
3. The high-fluidity graphene-modified polystyrene composite material of claim 1, wherein the antioxidant is antioxidant 1010 and antioxidant 168.
4. The high-fluidity graphene-modified polystyrene composite material of claim 1, wherein the coupling agent is one of a silane coupling agent and a phthalate coupling agent.
5. The high-fluidity graphene-modified polystyrene composite material of claim 1, wherein the conductive material is one or more of graphene, conductive carbon black, carbon nanotubes, carbon fibers and ultrafine graphite.
6. The high-fluidity graphene-modified polystyrene composite material of claim 1, wherein the flow modifier is at least one of polyethylene wax, paraffin wax, white oil, and EBS.
7. The high-flow graphene-modified polystyrene composite material of claim 1, wherein the other auxiliaries comprise maleic anhydride and dicumyl peroxide (DCP).
8. The method for preparing the high-fluidity graphene-modified polystyrene composite material according to claim 1, wherein the preparation method comprises the following steps:
firstly, mixing a toughening agent, a coupling agent, an antioxidant, a flow modifier and polystyrene together, putting the mixture into a high-speed mixer, and mixing for 3 minutes at a high speed to obtain a uniformly mixed mixture;
secondly, adding a conductive material into the mixture obtained in the first step, putting the mixture into a high-speed mixer, and mixing the mixture for 3 minutes at a high speed to obtain a mixed base material;
thirdly, adding a flow modifier and other additives into the base material obtained in the second step, and mixing at high speed for 3 minutes again to obtain a raw material of the high-fluidity conductive polystyrene which can be processed and produced;
and fourthly, granulating the raw material of the high-fluidity conductive polystyrene obtained in the third step by a double-screw extruder and a granulator.
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| CN112876781A (en) * | 2021-01-20 | 2021-06-01 | 江苏中信国安新材料有限公司 | Conductive polystyrene composite material and preparation method and application thereof |
| CN114621533A (en) * | 2022-03-25 | 2022-06-14 | 浙江大晋新材料科技有限公司 | Electroplatable high-impact conductive ps material, preparation method and application |
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