CN110655742A - Modified PVC cable material and preparation method thereof - Google Patents
Modified PVC cable material and preparation method thereof Download PDFInfo
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- CN110655742A CN110655742A CN201910975702.4A CN201910975702A CN110655742A CN 110655742 A CN110655742 A CN 110655742A CN 201910975702 A CN201910975702 A CN 201910975702A CN 110655742 A CN110655742 A CN 110655742A
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/22—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers modified by chemical after-treatment
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K2003/329—Phosphorus containing acids
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Abstract
The invention provides a modified PVC cable material which is prepared from the following raw materials in parts by weight: 300 parts of modified PVC resin, 2-5 parts of ultraviolet absorbent, 3-6 parts of antioxidant, 2-7 parts of flame retardant, 1-3 parts of preservative, 10-20 parts of light calcium carbonate, 5-10 parts of graphene and 18-25 parts of turpentine. The cable material has the advantages of wide raw material source, simple preparation method and lower cost, and the prepared cable material has good mechanical property, high temperature resistance, aging resistance and flame retardant property, is safe and environment-friendly, and has wide application prospect.
Description
Technical Field
The invention relates to the technical field of wires and cables, in particular to a modified PVC cable material.
Background
At present, PVC cable materials in the market have the phenomena of no high temperature resistance, no aging resistance and yellowing and brittleness of the materials after an aging test. In order to solve the problems, a modified PVC cable material must be developed. The modified PVC cable material not only meets ROSH instruction and Reach regulation, but also is high temperature resistant and aging resistant, and the material does not turn yellow and become brittle after an aging test. The cable material has wide application and large using amount, can replace XLPE cable material with high price, and is widely used for producing internal and external connecting wires of electronic and electrical equipment such as power cables, computers, refrigerators, televisions, air conditioners and the like, instruments, instrument wires, automobile wires, motor leads, mobile phones and notebook computer wires.
Disclosure of Invention
In order to solve the technical problems, the invention provides a modified PVC cable material and a preparation method thereof, and aims to provide the modified PVC cable material which has good plasticizing performance by adopting modified PVC resin, can effectively reduce the glass transition temperature of the PVC resin, and effectively improves the service life, mechanical properties and heat-resistant stability of the PVC resin.
The invention provides a modified PVC cable material which is prepared from the following raw materials: modified PVC resin, an ultraviolet absorbent, an antioxidant, a flame retardant, a preservative, light calcium carbonate, graphene and turpentine oil;
the modified PVC resin is prepared by the following method: dissolving PVC resin in an organic solvent, adding potassium carbonate and thiosalicylic acid, reacting at 60 ℃ for 10-15h under the protection of nitrogen, pouring into a methanol/water mixed solution, drying in vacuum to obtain a white massive solid, dissolving the solid with tetrahydrofuran, adjusting the pH value to about 5 with hydrochloric acid, then pouring into methanol for precipitation, and drying in vacuum to obtain white powder; adding the obtained white powder, plasticizer DOP and maleic anhydride into a high-speed mixer, uniformly mixing, mixing for 3min at 160 ℃, then adding kaolin, and continuously mixing for 5min to obtain modified PVC resin;
the volume ratio of methanol to water in the methanol/water mixed solution is 1:1, the mass ratio of the PVC resin, the potassium carbonate and the thiosalicylic acid is 1:1.5:2, and the mass ratio of the white powder, the plasticizer DOP, the maleic anhydride and the kaolin is 10:2:5: 1.
As a further improvement of the invention, the health-care food is prepared from the following raw materials in parts by weight: 300 parts of modified PVC resin, 2-5 parts of ultraviolet absorbent, 3-6 parts of antioxidant, 2-7 parts of flame retardant, 1-3 parts of preservative, 10-20 parts of light calcium carbonate, 5-10 parts of graphene and 18-25 parts of turpentine.
As a further improvement of the invention, the health-care food is prepared from the following raw materials in parts by weight: 450 parts of modified PVC resin 350-5 parts of ultraviolet absorbent, 4-6 parts of antioxidant, 4-6 parts of flame retardant, 1-2 parts of preservative, 12-17 parts of light calcium carbonate, 7-9 parts of graphene and 20-24 parts of turpentine.
As a further improvement of the invention, the health-care food is prepared from the following raw materials in parts by weight: 400 parts of modified PVC resin, 4 parts of ultraviolet absorber, 5 parts of antioxidant, 5 parts of flame retardant, 1.5 parts of preservative, 16 parts of light calcium carbonate, 8 parts of graphene and 22 parts of turpentine.
As a further improvement of the invention, the flame retardant is prepared from the following raw materials in parts by weight: 10-15 parts of melamine, 40005-10 parts of polyethylene glycol, 2-5 parts of ammonium polyphosphate, 1-2 parts of red phosphorus and 2-5 parts of aluminum hydroxide.
As a further improvement of the invention, the ultraviolet absorbent is selected from one or more of ultraviolet absorbent 326, ultraviolet absorbent UV-P, ultraviolet absorbent UV-R, ultraviolet absorbent UV-1130, ultraviolet absorbent UV-9 and ultraviolet absorbent UV 531.
As a further improvement of the invention, the antioxidant is selected from one or more of antioxidant 1076, antioxidant 1010, antioxidant BHT, antioxidant 168, antioxidant 264 and antioxidant T501.
As a further improvement of the invention, the preservative is selected from one or more of dehydroacetic acid, sodium dehydroacetate, hydroxybenzoate, sodium diacetate, sodium lactate and calcium propionate.
The invention further provides a method for preparing the modified PVC cable material, which comprises the following steps:
s1, treating a flame retardant: weighing the components of the flame retardant, drying, grinding and uniformly mixing for later use;
s2, mixing: drying the modified PVC resin, adding an ultraviolet absorbent, an antioxidant, a preservative, light calcium carbonate, graphene and turpentine, heating to 50 ℃, uniformly stirring and mixing, adding the treated flame retardant, and mixing, extruding and granulating in a mixing extruder to obtain the modified PVC cable material.
As a further improvement of the invention, the drying temperature is 50 ℃, and the drying time is 2-5 h.
The invention has the following beneficial effects:
1. the modified PVC resin has good plasticizing performance, can effectively reduce the glass transition temperature of the PVC resin, and effectively improves the service life, mechanical property and heat-resistant stability of the PVC resin;
2. the added flame retardant is small in addition amount and good in flame retardant effect, and does not affect the mechanical property of a cable material, ammonium polyphosphate and red phosphorus generate phosphoric acid and polymetaphosphoric acid with a dehydration effect at high temperature, aluminum hydroxide generates a compact aluminum oxide film under the high temperature and dehydration effects and coats the surface of a cable, meanwhile, melamine and polyethylene glycol 4000 generate ammonia and water vapor, the water vapor generated by reaction and the ammonia gas form a porous carbon layer and are attached to the surface of the oxide film to play a heat insulation effect, and therefore high-efficiency flame retardance is achieved;
3. according to the invention, the graphene is added, so that the cable material has good conductivity; by adding the ultraviolet absorber, the antioxidant and the preservative, the cable material has good performances of oxidation resistance, aging resistance, corrosion resistance and the like;
4. the cable material has the advantages of wide raw material source, simple preparation method and lower cost, and the prepared cable material has good mechanical property, high temperature resistance, aging resistance and flame retardant property, is safe and environment-friendly, and has wide application prospect.
Drawings
FIG. 1 is a preparation process diagram of a modified PVC cable material of the invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is obvious that the embodiments described are only some representative embodiments of the present invention, rather than all embodiments, and all other embodiments obtained by a person skilled in the art without creative efforts belong to the protection scope of the present invention.
Example 1
The raw materials comprise the following components in parts by weight: 300 parts of modified PVC resin, 92 parts of ultraviolet absorber UV-92 parts, 1683 parts of antioxidant, 2 parts of flame retardant, 1 part of hydroxybenzoate, 10 parts of light calcium carbonate, 5 parts of graphene and 18 parts of turpentine.
The flame retardant is prepared from the following raw materials in parts by weight: 10 parts of melamine, 40005 parts of polyethylene glycol, 2 parts of ammonium polyphosphate, 1 part of red phosphorus and 2 parts of aluminum hydroxide.
The modified PVC resin is prepared by the following method: dissolving 100g of PVC resin in an organic solvent, adding 200g of potassium carbonate and 150g of thiosalicylic acid, reacting for 10h at 60 ℃ under the protection of nitrogen, pouring into a methanol/water mixed solution (the volume ratio of methanol to water is 1:1), vacuum-drying to obtain a white blocky solid, dissolving the solid with tetrahydrofuran, adjusting the pH value to about 5 with hydrochloric acid, then pouring into methanol for precipitation, and vacuum-drying to obtain 220g of white powder; adding the obtained white powder, 44g of plasticizer DOP and 110g of maleic anhydride into a high-speed mixer, uniformly mixing, mixing at 160 ℃ for 3min, adding 22g of kaolin, and continuously mixing for 5min to obtain modified PVC resin;
the preparation method comprises the following steps:
s1, treating a flame retardant: weighing the components of the flame retardant, drying, grinding and uniformly mixing, wherein the drying temperature is 50 ℃, and the drying time is 2 hours for later use;
s2, mixing: drying the modified PVC resin at the drying temperature of 50 ℃ for 2h, adding an ultraviolet absorbent UV-9, an antioxidant 168, hydroxybenzoate, light calcium carbonate, graphene and turpentine, heating to 50 ℃, stirring and mixing uniformly, adding the treated flame retardant, and carrying out mixing extrusion granulation in a mixing extruder to obtain the modified PVC cable material.
Example 2
The raw materials comprise the following components in parts by weight: 500 parts of modified PVC resin, 5 parts of ultraviolet absorbent UV-P, 10766 parts of antioxidant, 7 parts of flame retardant, 3 parts of sodium diacetate, 20 parts of light calcium carbonate, 10 parts of graphene and 25 parts of turpentine.
The flame retardant is prepared from the following raw materials in parts by weight: 15 parts of melamine, 400010 parts of polyethylene glycol, 5 parts of ammonium polyphosphate, 2 parts of red phosphorus and 5 parts of aluminum hydroxide.
The modified PVC resin is prepared by the following method: dissolving 100g of PVC resin in an organic solvent, adding 200g of potassium carbonate and 150g of thiosalicylic acid, reacting for 15h at 60 ℃ under the protection of nitrogen, pouring into a methanol/water mixed solution (the volume ratio of methanol to water is 1:1), vacuum-drying to obtain a white blocky solid, dissolving the solid with tetrahydrofuran, adjusting the pH value to about 5 with hydrochloric acid, then pouring into methanol for precipitation, and vacuum-drying to obtain 210g of white powder; adding the obtained white powder, 42g of plasticizer DOP and 105g of maleic anhydride into a high-speed mixer, uniformly mixing, mixing at 160 ℃ for 3min, then adding 21g of kaolin, and continuously mixing for 5min to obtain modified PVC resin;
the preparation method comprises the following steps:
s1, treating a flame retardant: weighing the components of the flame retardant, drying, grinding and uniformly mixing, wherein the drying temperature is 50 ℃, and the drying time is 5 hours for later use;
s2, mixing: drying the modified PVC resin at the drying temperature of 50 ℃ for 5h, adding an ultraviolet absorbent UV-P, an antioxidant 1076, sodium diacetate, light calcium carbonate, graphene and turpentine, heating to 50 ℃, stirring and mixing uniformly, adding the treated flame retardant, and mixing, extruding and granulating in a mixing extruder to obtain the modified PVC cable material.
Example 3
The raw materials comprise the following components in parts by weight: 350 parts of modified PVC resin, 3263 parts of ultraviolet absorbent, 10104 parts of antioxidant, 4 parts of flame retardant, 1 part of calcium propionate, 12 parts of light calcium carbonate, 7 parts of graphene and 20 parts of turpentine.
The flame retardant is prepared from the following raw materials in parts by weight: 11 parts of melamine, 40006 parts of polyethylene glycol, 3 parts of ammonium polyphosphate, 1.2 parts of red phosphorus and 2.2 parts of aluminum hydroxide.
The modified PVC resin is prepared by the following method: dissolving 100g of PVC resin in an organic solvent, adding 200g of potassium carbonate and 150g of thiosalicylic acid, reacting for 11h at 60 ℃ under the protection of nitrogen, pouring into a methanol/water mixed solution (the volume ratio of methanol to water is 1:1), vacuum-drying to obtain a white blocky solid, dissolving the solid with tetrahydrofuran, adjusting the pH value to about 5 with hydrochloric acid, then pouring into methanol for precipitation, and vacuum-drying to obtain 225g of white powder; adding the obtained white powder, 45g of plasticizer DOP and 112.5g of maleic anhydride into a high-speed mixer, uniformly mixing, mixing for 3min at 160 ℃, then adding 22.5g of kaolin, and continuously mixing for 5min to obtain modified PVC resin;
the preparation method comprises the following steps:
s1, treating a flame retardant: weighing the components of the flame retardant, drying, grinding and uniformly mixing, wherein the drying temperature is 50 ℃, and the drying time is 3 hours for later use;
s2, mixing: drying the modified PVC resin at the drying temperature of 50 ℃ for 3h, adding an ultraviolet absorbent 326, an antioxidant 1010, calcium propionate, light calcium carbonate, graphene and turpentine, heating to 50 ℃, uniformly stirring and mixing, adding the treated flame retardant, and mixing and extruding in a mixing extruder for granulation to obtain the modified PVC cable material.
Example 4
The raw materials comprise the following components in parts by weight: 450 parts of modified PVC resin, 6 parts of ultraviolet absorbent UV-11305 parts, 6 parts of antioxidant BHT, 6 parts of flame retardant, 2 parts of dehydroacetic acid, 17 parts of light calcium carbonate, 9 parts of graphene and 24 parts of turpentine.
The flame retardant is prepared from the following raw materials in parts by weight: 14 parts of melamine, 40008 parts of polyethylene glycol, 4 parts of ammonium polyphosphate, 1.8 parts of red phosphorus and 4 parts of aluminum hydroxide.
The modified PVC resin is prepared by the following method: dissolving 100g of PVC resin in an organic solvent, adding 200g of potassium carbonate and 150g of thiosalicylic acid, reacting for 14h at 60 ℃ under the protection of nitrogen, pouring into a methanol/water mixed solution (the volume ratio of methanol to water is 1:1), vacuum-drying to obtain a white blocky solid, dissolving the solid with tetrahydrofuran, adjusting the pH value to about 5 with hydrochloric acid, then pouring into methanol for precipitation, and vacuum-drying to obtain 230g of white powder; adding the obtained white powder, 46g of plasticizer DOP and 115g of maleic anhydride into a high-speed mixer, uniformly mixing, mixing at 160 ℃ for 3min, then adding 23g of kaolin, and continuously mixing for 5min to obtain modified PVC resin;
the preparation method comprises the following steps:
s1, treating a flame retardant: weighing the components of the flame retardant, drying, grinding and uniformly mixing, wherein the drying temperature is 50 ℃, and the drying time is 4 hours for later use;
s2, mixing: drying the modified PVC resin at the drying temperature of 50 ℃ for 4h, adding an ultraviolet absorbent UV-1130, an antioxidant BHT, dehydroacetic acid, light calcium carbonate, graphene and turpentine, heating to 50 ℃, stirring and mixing uniformly, adding the treated flame retardant, and mixing, extruding and granulating in a mixing extruder to obtain the modified PVC cable material.
Example 5
The raw materials comprise the following components in parts by weight: 400 parts of modified PVC resin, 5314 parts of ultraviolet absorber UV, 5 parts of antioxidant BHT, 5 parts of flame retardant, 1.5 parts of sodium lactate, 16 parts of light calcium carbonate, 8 parts of graphene and 22 parts of turpentine.
The flame retardant is prepared from the following raw materials in parts by weight: 13 parts of melamine, 40007 parts of polyethylene glycol, 3 parts of ammonium polyphosphate, 1.5 parts of red phosphorus and 3 parts of aluminum hydroxide.
The modified PVC resin is prepared by the following method: dissolving 100g of PVC resin in an organic solvent, adding 200g of potassium carbonate and 150g of thiosalicylic acid, reacting for 10-15h at 60 ℃ under the protection of nitrogen, pouring into a methanol/water mixed solution (the volume ratio of methanol to water is 1:1), drying in vacuum to obtain a white blocky solid, dissolving the solid with tetrahydrofuran, adjusting the pH value to about 5 with hydrochloric acid, then pouring into methanol for precipitation, and drying in vacuum to obtain 220g of white powder; adding the obtained white powder, 44g of plasticizer DOP and 110g of maleic anhydride into a high-speed mixer, uniformly mixing, mixing at 160 ℃ for 3min, adding 22g of kaolin, and continuously mixing for 5min to obtain modified PVC resin;
the volume ratio of methanol to water in the methanol/water mixed solution is 1:1, the mass ratio of the PVC resin, the potassium carbonate and the thiosalicylic acid is 1:1.5:2, and the mass ratio of the white powder, the plasticizer DOP, the maleic anhydride and the kaolin is 10:2:5:1
The preparation method comprises the following steps:
s1, treating a flame retardant: weighing the components of the flame retardant, drying, grinding and uniformly mixing, wherein the drying temperature is 50 ℃, and the drying time is 3 hours for later use;
s2, mixing: drying the modified PVC resin at 50 ℃ for 3h, adding an ultraviolet absorber UV531, an antioxidant BHT, sodium lactate, light calcium carbonate, graphene and turpentine, heating to 50 ℃, stirring and mixing uniformly, adding the treated flame retardant, and mixing and extruding in a mixing extruder for granulation to obtain the modified PVC cable material.
Test example 1
The modified PVC cable material prepared in example 5 of the invention and the commercial common PVC cable material were subjected to performance tests, and the results are shown in Table 1.
TABLE 1
Compared with the prior art, the modified PVC resin has good plasticizing performance, can effectively reduce the glass transition temperature of the PVC resin, and effectively improves the service life, mechanical property and heat-resistant stability of the PVC resin;
the added flame retardant is small in addition amount and good in flame retardant effect, and does not affect the mechanical property of a cable material, ammonium polyphosphate and red phosphorus generate phosphoric acid and polymetaphosphoric acid with a dehydration effect at high temperature, aluminum hydroxide generates a compact aluminum oxide film under the high temperature and dehydration effects and coats the surface of a cable, meanwhile, melamine and polyethylene glycol 4000 generate ammonia and water vapor, the water vapor generated by reaction and the ammonia gas form a porous carbon layer and are attached to the surface of the oxide film to play a heat insulation effect, and therefore high-efficiency flame retardance is achieved;
according to the invention, the graphene is added, so that the cable material has good conductivity; by adding the ultraviolet absorber, the antioxidant and the preservative, the cable material has good performances of oxidation resistance, aging resistance, corrosion resistance and the like;
the cable material has the advantages of wide raw material source, simple preparation method and lower cost, and the prepared cable material has good mechanical property, high temperature resistance, aging resistance and flame retardant property, is safe and environment-friendly, and has wide application prospect.
Various modifications may be made to the above without departing from the spirit and scope of the invention as defined by the appended claims. The scope of the invention is therefore intended to be limited not by the above description, but rather by the scope of the appended claims.
Claims (10)
1. The modified PVC cable material is characterized by being prepared from the following raw materials: modified PVC resin, an ultraviolet absorbent, an antioxidant, a flame retardant, a preservative, light calcium carbonate, graphene and turpentine oil;
the modified PVC resin is prepared by the following method: dissolving PVC resin in an organic solvent, adding potassium carbonate and thiosalicylic acid, reacting at 60 ℃ for 10-15h under the protection of nitrogen, pouring into a methanol/water mixed solution, drying in vacuum to obtain a white massive solid, dissolving the solid with tetrahydrofuran, adjusting the pH value to about 5 with hydrochloric acid, then pouring into methanol for precipitation, and drying in vacuum to obtain white powder; adding the obtained white powder, plasticizer DOP and maleic anhydride into a high-speed mixer, uniformly mixing, mixing for 3min at 160 ℃, then adding kaolin, and continuously mixing for 5min to obtain modified PVC resin;
the volume ratio of methanol to water in the methanol/water mixed solution is 1:1, the mass ratio of the PVC resin, the potassium carbonate and the thiosalicylic acid is 1:1.5:2, and the mass ratio of the white powder, the plasticizer DOP, the maleic anhydride and the kaolin is 10:2:5: 1.
2. The modified PVC cable material of claim 1, which is prepared from the following raw materials in parts by weight: 300 parts of modified PVC resin, 2-5 parts of ultraviolet absorbent, 3-6 parts of antioxidant, 2-7 parts of flame retardant, 1-3 parts of preservative, 10-20 parts of light calcium carbonate, 5-10 parts of graphene and 18-25 parts of turpentine.
3. The modified PVC cable material of claim 2, which is prepared from the following raw materials in parts by weight: 450 parts of modified PVC resin 350-5 parts of ultraviolet absorbent, 4-6 parts of antioxidant, 4-6 parts of flame retardant, 1-2 parts of preservative, 12-17 parts of light calcium carbonate, 7-9 parts of graphene and 20-24 parts of turpentine.
4. The modified PVC cable material according to claim 3, which is prepared from the following raw materials in parts by weight: 400 parts of modified PVC resin, 4 parts of ultraviolet absorber, 5 parts of antioxidant, 5 parts of flame retardant, 1.5 parts of preservative, 16 parts of light calcium carbonate, 8 parts of graphene and 22 parts of turpentine.
5. The modified PVC cable material of claim 1, wherein the flame retardant is prepared from the following raw materials in parts by weight: 10-15 parts of melamine, 40005-10 parts of polyethylene glycol, 2-5 parts of ammonium polyphosphate, 1-2 parts of red phosphorus and 2-5 parts of aluminum hydroxide.
6. The modified PVC cable material of claim 1, wherein the UV absorber is selected from one or more of UV absorber 326, UV absorber UV-P, UV absorber UV-R, UV absorber UV-1130, UV absorber UV-9 and UV absorber UV 531.
7. The modified PVC cable material of claim 1, wherein the antioxidant is selected from one or more of antioxidant 1076, antioxidant 1010, antioxidant BHT, antioxidant 168, antioxidant 264 and antioxidant T501.
8. The modified PVC cable material of claim 1, wherein the preservative is selected from one or more of dehydroacetic acid, sodium dehydroacetate, hydroxybenzoate, sodium diacetate, sodium lactate and calcium propionate.
9. A process for the preparation of a modified PVC cable material according to any one of claims 1 to 8, characterized in that it comprises the following steps:
s1, treating a flame retardant: weighing the components of the flame retardant, drying, grinding and uniformly mixing for later use;
s2, mixing: drying the modified PVC resin, adding an ultraviolet absorbent, an antioxidant, a preservative, light calcium carbonate, graphene and turpentine, heating to 50 ℃, uniformly stirring and mixing, adding the treated flame retardant, and mixing, extruding and granulating in a mixing extruder to obtain the modified PVC cable material.
10. The method for preparing the modified PVC cable material according to claim 9, wherein the drying temperature is 50 ℃ and the drying time is 2-5 h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112063076A (en) * | 2020-09-16 | 2020-12-11 | 博罗县东明新材料研究所 | Graphene polyvinyl chloride composite material and preparation method thereof |
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| KR20170017141A (en) * | 2015-08-05 | 2017-02-15 | (주)다이나믹 | An eco-friendly master batch for expanded cross-linked polyolefin having the flame retardancy and the foam composition by using the same |
| CN105837930A (en) * | 2015-12-31 | 2016-08-10 | 宁波能之光新材料科技有限公司 | Soft PP flame retardant with ultrahigh fluidity |
| CN108384143A (en) * | 2018-02-26 | 2018-08-10 | 合肥尚强电气科技有限公司 | Anti-freezing flame-retardant cable material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112063076A (en) * | 2020-09-16 | 2020-12-11 | 博罗县东明新材料研究所 | Graphene polyvinyl chloride composite material and preparation method thereof |
| CN112063076B (en) * | 2020-09-16 | 2023-03-28 | 博罗县东明新材料研究所 | Graphene polyvinyl chloride composite material and preparation method thereof |
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