CN116218100B - Method for dispersing graphene in PVC resin - Google Patents
Method for dispersing graphene in PVC resin Download PDFInfo
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- CN116218100B CN116218100B CN202310306328.5A CN202310306328A CN116218100B CN 116218100 B CN116218100 B CN 116218100B CN 202310306328 A CN202310306328 A CN 202310306328A CN 116218100 B CN116218100 B CN 116218100B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 172
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 136
- 239000011347 resin Substances 0.000 title claims abstract description 40
- 229920005989 resin Polymers 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000000498 ball milling Methods 0.000 claims abstract description 110
- 239000002131 composite material Substances 0.000 claims abstract description 32
- 239000006185 dispersion Substances 0.000 claims abstract description 31
- 239000002270 dispersing agent Substances 0.000 claims abstract description 8
- 239000011324 bead Substances 0.000 claims description 51
- 239000011812 mixed powder Substances 0.000 claims description 36
- 239000002245 particle Substances 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 17
- 239000004014 plasticizer Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000000080 wetting agent Substances 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 claims description 6
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 6
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 claims description 6
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 3
- VOWAEIGWURALJQ-UHFFFAOYSA-N Dicyclohexyl phthalate Chemical compound C=1C=CC=C(C(=O)OC2CCCCC2)C=1C(=O)OC1CCCCC1 VOWAEIGWURALJQ-UHFFFAOYSA-N 0.000 claims description 3
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 claims description 3
- 229960001826 dimethylphthalate Drugs 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims 2
- 238000002360 preparation method Methods 0.000 abstract description 13
- 239000002356 single layer Substances 0.000 abstract description 9
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003063 flame retardant Substances 0.000 abstract description 6
- 239000011159 matrix material Substances 0.000 abstract description 6
- 238000005054 agglomeration Methods 0.000 abstract description 5
- 230000002776 aggregation Effects 0.000 abstract description 5
- 229910002804 graphite Inorganic materials 0.000 abstract description 5
- 239000010439 graphite Substances 0.000 abstract description 5
- 239000002861 polymer material Substances 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 22
- 238000012512 characterization method Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000000465 moulding Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000007873 sieving Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 101100083446 Danio rerio plekhh1 gene Proteins 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 101100481028 Arabidopsis thaliana TGA2 gene Proteins 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention belongs to the technical field of high polymer materials, and particularly relates to a dispersion method of graphene in PVC resin. According to the invention, graphite is peeled by in-situ ball milling, and the obtained graphene is directly coated on the surface of the PVC resin for single-layer dispersion, so that the probability of further crushing the graphene can be reduced, and the preparation and dispersion integrated process of the graphene is realized. According to the dispersion method provided by the invention, the dispersing agent is not required to be added, so that the graphene is uniformly dispersed in the PVC resin, and the influence of the addition of the dispersing agent on the performance of the PVC is avoided. The invention not only solves the problem of agglomeration of graphene, but also realizes monolayer dispersion of graphene in the PVC matrix, and the thermal stability and flame retardance of the obtained graphene/PVC composite material are obviously improved. According to the invention, the monolayer dispersion of graphene in the PVC resin is realized, so that the thermal stability and flame retardant property of the PVC resin can be obviously improved under the condition of very low graphene content.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a dispersion method of graphene in PVC resin.
Background
Graphene is a two-dimensional lamellar material with very excellent properties. The graphene has good physical barrier property and thermal stability, and the thermal stability of the material can be improved by adding the graphene into a high polymer material. At present, the method for preparing graphene is mainly divided into a top-down method and a bottom-up method. The top-down method can be used for producing graphene on a large scale, but the controllability is not high, so that the particle size of the graphene is small, the graphene prepared by the mechanical stripping method is high in inertia and easy to agglomerate, and is difficult to uniformly disperse in a polymer matrix, so that the toughness of the material is reduced, and the material is easy to fracture.
In order to improve the dispersibility of graphene in a polymer material, researchers modify the graphene and strengthen the interaction force between the graphene and the polymer, but the method can damage the structure of the graphene and weaken the effect of the graphene on the material performance.
At present, most researches mainly divide the dispersion of graphene in a polymer matrix into two steps: (1) preparing graphene dispersion liquid; (2) And mixing the graphene dispersion liquid with a polymer matrix to prepare the graphene/polymer composite material.
Chinese patent CN113637273a discloses a graphene reinforced PVC pipe and a preparation method thereof: firstly preparing graphene dispersion liquid, then mixing the graphene dispersion liquid with materials such as PVC and the like through a mechanical high-speed mixing method, drying the mixture, and then putting the mixture into an extruder for extrusion and the like to obtain the graphene reinforced PVC pipe.
Chinese patent CN107129643a discloses a graphene/carbon nanotube synergistically modified PVC composite material, a preparation method and application thereof: the graphene powder, the carbon nano tube, the dispersing agent and the defoaming agent are uniformly mixed, and then the mixture is mixed with PVC and other additives and dried to obtain the graphene/carbon nano tube synergistic modified PVC composite material.
However, the steps of the two-step method are complex, and meanwhile, more agglomeration problems still exist in the PVC matrix.
Disclosure of Invention
The invention aims to provide a dispersion method of graphene in PVC resin, which has simple steps and can uniformly disperse graphene in PVC resin.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a dispersion method of graphene in PVC resin, which does not add a dispersing agent and comprises the following steps:
(1) Mixing PVC resin, graphite powder and a wetting agent, and sequentially performing ball milling and drying to obtain graphene/PVC mixed powder;
the ball-milling balls comprise small ball-milling balls, medium ball-milling balls and large ball-milling balls;
the particle size of the small ball-milling beads is 1-4 mm, the particle size of the medium ball-milling beads is 4.1-9.0 mm, and the particle size of the large ball-milling beads is 9.1-15.0 mm;
the mass ratio of the small ball-milling beads to the medium ball-milling beads is 1-10:5-20;
the mass ratio of the small ball-milling beads to the large ball-milling beads is 1-10:15-40;
(2) And mixing the graphene/PVC mixed powder with a plasticizer, and plasticizing to obtain the graphene/PVC composite material.
Preferably, the mass ratio of the graphite powder to the PVC resin is 0.1-4:80-120; the mass ratio of the graphene/PVC mixed powder to the plasticizer is 5-15:2-10.
Preferably, the particle size of the graphite powder is 325-8000 meshes; the polymerization degree of the PVC resin is 500-3000.
Preferably, the rotation speed of the ball milling is 400-1600 r/min, and the time is 12-48 h; the ball-milling wetting agent comprises one or more of absolute ethyl alcohol, acetone and methanol.
Preferably, the mass ratio of the graphite powder to the ball-milling beads is 0.1-4:40-80.
Preferably, the particle size of the graphene/PVC mixed powder is 325-8000 meshes.
Preferably, the drying temperature is 50-90 ℃, and the heat preservation time is 6-18 h.
Preferably, the mass ratio of the graphite powder to the wetting agent is 0.1-4.0:5-15.
Preferably, the plasticizer comprises one or more of dimethyl phthalate, dibutyl phthalate, dicyclohexyl phthalate, dioctyl phthalate, di (2-ethylhexyl) phthalate and diisobutyl phthalate.
Preferably, the plasticizing temperature is 120-160 ℃, and the heat preservation time is 6-14 min.
The invention provides a dispersion method of graphene in PVC resin. According to the invention, graphite powder and PVC resin powder are mixed and then sequentially subjected to ball milling and drying to obtain graphene/PVC composite powder, and then a plasticizer is added for mixing, plasticizing and molding to obtain the graphene/PVC composite material. According to the invention, graphite is peeled by in-situ ball milling, and the obtained graphene is directly coated on the surface of the PVC resin for single-layer dispersion, so that the probability of further crushing the graphene can be reduced, and the preparation and dispersion integrated process of the graphene is realized.
According to the dispersion method provided by the invention, the dispersing agent is not required to be added, so that the graphene is uniformly dispersed in the PVC resin, and the influence of the addition of the dispersing agent on the performance of the PVC is avoided.
The invention not only solves the problem of agglomeration of graphene, but also realizes monolayer dispersion of graphene in the PVC matrix, and the thermal stability and flame retardance of the obtained graphene/PVC composite material are obviously improved.
According to the invention, the monolayer dispersion of graphene in the PVC resin is realized, so that the thermal stability and flame retardant property of the PVC resin can be obviously improved under the condition of very low graphene content.
The dispersing method provided by the invention has the advantages of simple steps, convenient operation, low cost and environmental friendliness, and has the potential of large-scale industrial production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions of the prior art, the drawings that are needed in the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an XRD pattern of graphene/PVC mixed powder prepared in example 1 of the present invention;
FIG. 2 is an SEM image of graphene/PVC mixed powder prepared in example 1 of the present invention;
fig. 3 is a TEM image of graphene obtained after PVC etching of the graphene/PVC mixed powder prepared in example 1 of the present invention;
FIG. 4 is a TEM image of the graphene/PVC composite prepared in example 1 of the present invention;
FIG. 5 is a TGA graph of graphene/PVC composite prepared in example 1 of the present invention.
Detailed Description
The invention provides a dispersion method of graphene in PVC resin, which does not add a dispersing agent and comprises the following steps:
(1) Mixing PVC resin, graphite powder and a wetting agent, and sequentially performing ball milling and drying to obtain graphene/PVC mixed powder;
the ball-milling balls comprise small ball-milling balls, medium ball-milling balls and large ball-milling balls;
the particle size of the small ball-milling beads is 1-4 mm, the particle size of the medium ball-milling beads is 4.1-9.0 mm, and the particle size of the large ball-milling beads is 9.1-15.0 mm;
the mass ratio of the small ball-milling beads to the medium ball-milling beads is 1-10:5-20;
the mass ratio of the small ball-milling beads to the large ball-milling beads is 1-10:15-40;
(2) And mixing the graphene/PVC mixed powder with a plasticizer, and plasticizing to obtain the graphene/PVC composite material.
According to the invention, the PVC resin, the graphite powder and the wetting agent are mixed (marked as first mixing) and are sequentially subjected to ball milling and drying, so that graphene/PVC mixed powder is obtained. In the present invention, the particle size of the graphite powder is preferably 325 to 8000 mesh, more preferably 500 to 5000 mesh, still more preferably 1000 to 2000 mesh; the polymerization degree of the PVC resin is preferably 500 to 3000, more preferably 800 to 2500, still more preferably 1000 to 2000; the mass ratio of the graphite powder to the PVC resin is preferably 0.1-4:80-120, more preferably 0.5-3:85-105, and even more preferably 1.0-2.0:90-110; the first mixing means is preferably stirring.
In the invention, the rotation speed of the ball milling is preferably 400-1600 r/min, more preferably 600-1200 r/min, further preferably 800-1000 r/min, and the time is preferably 12-48 h, more preferably 18-42 h, further preferably 24-38 h; the ball-milling wetting agent preferably comprises one or more of absolute ethyl alcohol, acetone and methanol; the mass ratio of the graphite powder to the wetting agent is preferably 0.1-4.0:5-15, more preferably 0.5-3.0:8-12, and even more preferably 1.0-2.0:9-11.
In the present invention, the ball milling equipment is preferably a ball milling tank and a ball mill; the ball-milling balls comprise small ball-milling balls, medium ball-milling balls and large ball-milling balls; the particle size of the small ball-milling beads is 1.0-4.0 mm, preferably 1.5-3.5 mm, more preferably 2.0-3.0 mm; the particle size of the medium ball-milling beads is 4.1-9.0 mm, preferably 4.5-8.0 mm, more preferably 5.0-7.0 mm; the particle size of the large ball-milling beads is 9.1 to 15.0mm, preferably 9.5 to 14mm, more preferably 10.0 to 13.0mm.
In the invention, the mass ratio of the small ball-milling beads to the medium ball-milling beads is 1-10:5-20, preferably 2-9:8-18, more preferably 4-7:10-15; the mass ratio of the small ball-milling beads to the large ball-milling beads is 1-10:15-40, preferably 3-8:18-36, more preferably 5-7:25-32; the mass ratio of the graphite powder to the ball-milling beads is preferably 0.1-4:40-80, more preferably 0.5-3.0:50-70, and even more preferably 1.0-2.0:55-65.
In the present invention, the drying temperature is preferably 50 to 90 ℃, more preferably 60 to 80 ℃, and the heat preservation time is preferably 6 to 18 hours, more preferably 10 to 15 hours; the drying apparatus is preferably an oven. The wetting agent used for ball milling is removed cleanly by drying.
In the present invention, the dried product is preferably sieved after the drying. According to the preparation method, the graphene/PVC mixed powder with the target particle size is obtained through sieving. The target particle diameter of the graphene/PVC mixed powder is preferably 325 to 8000 mesh, more preferably 500 to 5000 mesh, and even more preferably 1000 to 2000 mesh.
After the graphene/PVC mixed powder is obtained, the graphene/PVC mixed powder and the plasticizer are mixed and plasticized, so that the graphene/PVC composite material is obtained. In the present invention, the plasticizer preferably includes one or more of dimethyl phthalate, dibutyl phthalate, dicyclohexyl phthalate, dioctyl phthalate, di (2-ethylhexyl) phthalate and diisobutyl phthalate.
In the present invention, the mass ratio of the graphene/PVC mixed powder to the plasticizer is preferably 5 to 15:2 to 10, more preferably 7 to 12:3 to 8, and even more preferably 9 to 10:5 to 7.
In the present invention, the plasticizing temperature is preferably 120 to 160 ℃, more preferably 130 to 150 ℃, further preferably 140 ℃, and the holding time is preferably 6 to 14min, more preferably 8 to 12min, further preferably 10min; the plasticization is preferably carried out in a mold.
The graphene/PVC composite material prepared by the invention has the advantages that a single layer or a few layers of graphene are uniformly coated on the surfaces of PVC resin particles, the coated PVC resin particles are uniform in size, the agglomeration phenomenon is avoided, and obvious structural defects are avoided.
The following detailed description of the embodiments of the invention is provided in connection with the accompanying drawings and examples to further illustrate the invention, but should not be construed as limiting the scope of the invention.
Example 1
(1) Preparing materials: placing 10g of PVC resin powder, 0.05g of graphite powder, 10g of absolute ethyl alcohol and 60g of ball-milling beads in a ball-milling tank, wherein the mass ratio of the small ball-milling beads to the medium ball-milling beads to the large ball-milling beads is 1:2:3, and uniformly stirring the materials by using a glass rod;
(2) Preparation of graphene/PVC mixed powder: placing the ball milling tank filled with the materials into a ball mill for ball milling, wherein the ball milling rotating speed is 800r/min, and the ball milling time is 36h; taking out the ball milling tank after ball milling, putting the ball milling tank into a baking oven at 60 ℃, drying for 12 hours to remove absolute ethyl alcohol, and then sieving by using a screen to obtain graphene/PVC mixed powder with the particle size of 325-8000 meshes;
(3) Preparation of graphene/PVC composite material: and mixing the graphene/PVC mixed powder with a plasticizer according to a mass ratio of 10:6, pouring the material into a mold after uniformly mixing, and then placing the mold with the sample into an oven for plasticizing and molding, wherein the plasticizing temperature is 140 ℃, and the plasticizing time is 10min, so as to obtain the graphene/PVC composite material.
XRD characterization and electron microscope scanning are carried out on the graphene/PVC mixed powder obtained in the step (2) of the embodiment, and the results are shown in fig. 1 and 2 respectively. As can be seen from fig. 1, the intensity of the graphite peaks after ball milling is very weak or even vanishes; according to fig. 2, it can be observed that the surface of the PVC resin is coated with graphene, and the thickness of the graphene is very thin, the transparency is high, and the outline of the PVC resin can be clearly seen, so that the graphite raw material in this embodiment has been converted into graphene, and the graphene is uniformly distributed in the PVC resin, and no agglomeration phenomenon occurs.
Adding the graphene/PVC mixed powder obtained in the step (2) of the embodiment into a beaker filled with cyclohexanone, fully stirring until PVC is dissolved in the cyclohexanone to obtain graphene dispersion liquid, fishing out graphene in the obtained graphene dispersion liquid by using a copper mesh, and then placing the copper mesh under an infrared lamp for drying treatment to obtain a graphene sample, and carrying out TEM characterization on the obtained graphene sample, wherein the result is shown in figure 3. According to fig. 3, it can be observed that graphite is exfoliated into graphene, only one edge line is observed by the graphene under a high-power transmission electron microscope, and the diffraction pattern can clearly observe the crystal face of the graphene, which proves that the graphene is single-layer graphene.
The graphene/PVC composite material obtained in this example was embedded and sliced, and then observed under a transmission electron microscope, and the result is shown in fig. 4. The distributed graphene lattice fringes can be clearly seen in the PVC resin through fig. 4, and are uniformly distributed as a monolayer.
Example 2
(1) Preparing materials: placing 10g of PVC resin powder, 0.10g of graphite powder, 10g of absolute ethyl alcohol and 60g of ball-milling beads in a ball-milling tank, wherein the mass ratio of the small ball-milling beads to the medium ball-milling beads to the large ball-milling beads is 1:2:3, and uniformly stirring the materials by using a glass rod;
(2) Preparation of graphene/PVC mixed powder: placing the ball milling tank filled with the materials into a ball mill for ball milling, wherein the ball milling rotating speed is 800r/min, and the ball milling time is 36h; taking out the ball milling tank after ball milling, putting the ball milling tank into a baking oven at 60 ℃, drying for 12 hours to remove absolute ethyl alcohol, and then sieving by using a screen to obtain graphene/PVC mixed powder with the particle size of 325-8000 meshes; the characterization result of the graphene/PVC mixed powder of the present embodiment is similar to that of embodiment 1;
(3) Preparation of graphene/PVC composite material: mixing the graphene/PVC mixed powder and a plasticizer according to a mass ratio of 10:6, pouring the materials into a mold after uniformly mixing, and then placing the mold with the sample into an oven for plasticizing and molding, wherein the plasticizing temperature is 140 ℃, and the plasticizing time is 10min, so as to obtain the graphene/PVC composite material; the characterization result of the graphene/PVC composite material of this example is similar to example 1.
Example 3
(1) Preparing materials: placing 10g of PVC resin powder, 0.15g of graphite powder, 10g of absolute ethyl alcohol and 60g of ball-milling beads in a ball-milling tank, wherein the mass ratio of the small ball-milling beads to the medium ball-milling beads to the large ball-milling beads is 1:2:3, and uniformly stirring the materials by using a glass rod;
(2) Preparation of graphene/PVC mixed powder: placing the ball milling tank filled with the materials into a ball mill for ball milling, wherein the ball milling rotating speed is 800r/min, and the ball milling time is 36h; taking out the ball milling tank after ball milling, putting the ball milling tank into a baking oven at 60 ℃, drying for 12 hours to remove absolute ethyl alcohol, and then sieving by using a screen to obtain graphene/PVC mixed powder with the particle size of 325-8000 meshes; the characterization result of the graphene/PVC mixed powder of the present embodiment is similar to that of embodiment 1;
(3) Preparation of graphene/PVC composite material: mixing the graphene/PVC mixed powder and a plasticizer according to a mass ratio of 10:6, pouring the materials into a mold after uniformly mixing, and then placing the mold with the sample into an oven for plasticizing and molding, wherein the plasticizing temperature is 140 ℃, and the plasticizing time is 10min, so as to obtain the graphene/PVC composite material; the characterization result of the graphene/PVC composite material of this example is similar to example 1.
Example 4
(1) Preparing materials: placing 10g of PVC resin powder, 0.20g of graphite powder, 10g of absolute ethyl alcohol and 60g of ball-milling beads in a ball-milling tank, wherein the mass ratio of the small ball-milling beads to the medium ball-milling beads to the large ball-milling beads is 1:2:3, and uniformly stirring the materials by using a glass rod;
(2) Preparation of graphene/PVC mixed powder: placing the ball milling tank filled with the materials into a ball mill for ball milling, wherein the ball milling rotating speed is 800r/min, and the ball milling time is 36h; taking out the ball milling tank after ball milling, putting the ball milling tank into a baking oven at 60 ℃, drying for 12 hours to remove absolute ethyl alcohol, and then sieving by using a screen to obtain graphene/PVC mixed powder with the particle size of 325-8000 meshes; the characterization result of the graphene/PVC mixed powder of the present embodiment is similar to that of embodiment 1;
(3) Preparation of graphene/PVC composite material: mixing the graphene/PVC mixed powder and a plasticizer according to a mass ratio of 10:6, pouring the materials into a mold after uniformly mixing, and then placing the mold with the sample into an oven for plasticizing and molding, wherein the plasticizing temperature is 140 ℃, and the plasticizing time is 10min, so as to obtain the graphene/PVC composite material; the characterization result of the graphene/PVC composite material of this example is similar to example 1.
The graphene/PVC composite materials prepared in examples 1 to 4 were subjected to thermogravimetric testing using a TGA2 (SF) thermogravimetric instrument at a temperature ranging from 30 to 800 ℃ and a temperature rising rate of 10 ℃/min under a nitrogen atmosphere, and the test results are shown in fig. 5 and table 1.
TABLE 1 thermal gravimetric test results for unmodified PVC and graphene/PVC composites prepared in examples 1-4
As can be seen from Table 1, the unmodified PVC thermally decomposes to 50% (T) 50 ) The corresponding temperature is 287 ℃, and the temperature (T) corresponding to the maximum thermal decomposition rate of the first stage of thermal decomposition max1 ) 288 ℃ and 3.18% of carbon residue; with the increase of the graphene content, T 50 、T max1 And the thermal heavy carbon residue are increased, and when the graphene content is increased to 2%, T 50 、T max1 Compared with unmodified PVC, the temperature is increased by 12 ℃ and the temperature is increased by 10 ℃, the thermal heavy carbon residual quantity is increased by 4.33% compared with the unmodified PVC, and the thermal heavy carbon residual quantity is higher than the addition quantity of graphene, which shows that the addition of the graphene is beneficial to improving the thermal stability of the PVC resin.
Unmodified PVC and graphene/PVC composites prepared in examples 1-4 of the present invention were tested for flame retardant properties using a mcc-2 microcalorimeter according to ASTM D7309-2007 test standard, the results of which are shown in Table 2.
TABLE 2 flame retardant test results for unmodified PVC and graphene/PVC composites prepared in examples 1-4
As can be seen from Table 2, the heat release capacity and the heat release rate of the unmodified PVC are 437J/g-K and 401.3W/g respectively, and the heat release capacity and the heat release rate of the graphene/PVC composite material are reduced along with the increase of the graphene content; when the graphene content is 2%, the thermal release capacity of the graphene/PVC composite material is reduced by 50J/g-K, and the thermal release rate is reduced by 47.9W/g, which indicates that the addition of the graphene is beneficial to improving the flame retardance of the PVC.
From the above examples, the graphene reinforced PVC composite material provided by the invention has excellent thermal stability and flame retardant property, and the T of the PVC composite material 50 Can reach 299 ℃, T max1 Can reach 298 ℃, has good thermal stability, and obviously improves PVC compoundingThe flame retardant property of the composite material greatly improves the application of PVC in the fields of chemical industry, building materials, packaging and the like.
Although the foregoing embodiments have been described in some, but not all embodiments of the invention, other embodiments may be obtained according to the present embodiments without departing from the scope of the invention.
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