Graphene / polyvinyl chloride composite material, preparation method and application thereof

Abstract

The application relates to a graphene / polyvinyl chloride composite material and a preparation method and application thereof, relates to the field of high polymer materials, and comprises polyvinyl chloride, modified graphene, a plasticizer, a lubricant, an antioxidant and a stabilizer; the modified graphene is obtained by sequentially performing oxygen-rich microwave plasma treatment and surface modifier coating treatment on graphite powder. On the basis of the prior art, the physical-chemical dual synergistic modification of the graphene is realized by adopting the synergistic effect of the oxygen-rich microwave plasma treatment and the composite surface modifier, the compatibility and dispersibility of the graphene in the polyvinyl chloride matrix and the toughening and reinforcing effect are improved, the stability of the obtained composite material in a high-humidity environment is remarkably improved, the service life of products such as pipe materials and cables can be effectively prolonged, and the graphene / polyvinyl chloride composite material is widely used.

Description

Technical Field

[0001] This invention relates to the field of polymer materials, and more particularly to a graphene / polyvinyl chloride composite material, its preparation method, and its application. Background Technology

[0002] Polyvinyl chloride (PVC), a common polymer material, is widely used in many fields due to its advantages such as low cost, good processing performance, and strong chemical corrosion resistance. In the pipe industry, PVC pipes are lightweight, corrosion-resistant, have low water flow resistance, and are easy to install, making them widely used in building water supply and drainage, municipal drainage, and agricultural irrigation systems. In the cable industry, PVC, due to its excellent insulation and flame-retardant properties, has become a common material for the outer sheath of wires and cables, providing protection for power transmission and communication lines.

[0003] However, PVC materials also exhibit some significant limitations in practical applications. Specifically, in high-humidity and high-heat environments, the mechanical properties of PVC materials are significantly affected, shortening the product's lifespan. Therefore, improving the stability of PVC materials in high-humidity and high-heat environments has become a crucial issue that urgently needs to be addressed in this field. Summary of the Invention

[0004] To address the above problems, this invention provides a graphene / polyvinyl chloride composite material, its preparation method, and its application.

[0005] In a first aspect, the present invention provides a graphene / polyvinyl chloride composite material, comprising polyvinyl chloride, modified graphene, plasticizer, lubricant, antioxidant and stabilizer; The modified graphene is obtained by sequentially treating graphite powder with oxygen-enriched microwave plasma and coating it with a surface modifier. The surface modifier comprises fish scale powder, fatty alcohol polyoxyethylene ether, and silane coupling agent in a weight ratio of (4-7):(1-2):(10-15), wherein the fatty alcohol polyoxyethylene ether has 8-12 polyoxyethylene chain units.

[0006] Furthermore, the graphene / polyvinyl chloride composite material comprises the following raw materials in parts by weight: 90-110 parts polyvinyl chloride, 1-3.5 parts modified graphene, 15-20 parts plasticizer, 1-3 parts lubricant, 0.3-0.8 parts antioxidant and 1-3 parts stabilizer.

[0007] Furthermore, the graphene / polyvinyl chloride composite material comprises the following raw materials in parts by weight: 100 parts polyvinyl chloride, 2 parts modified graphene, 18 parts plasticizer, 1.5 parts lubricant, 0.5 parts antioxidant and 2 parts stabilizer.

[0008] Furthermore, the preparation of the modified graphene includes the following process: Graphite powder with a particle size of 100-200 mesh was subjected to glow discharge treatment for 60-120s under microwave power of 410-500W and working medium of oxygen and nitrogen with a volume ratio of (5-8):1 to obtain graphene after oxygen-enriched microwave plasma treatment. Under ultrasonic power of 200-300W and temperature of 45-50℃, the graphene treated with oxygen-enriched microwave plasma, the surface modifier, and an ethanol-water mixture with pH of 4.2-4.5 and a volume ratio of (3-7):1 were heated and stirred for 60-90 minutes at a weight ratio of 100:(5-9):(400-500), filtered, and dried to obtain the modified graphene.

[0009] Furthermore, the weight ratio of the fish scale powder, the fatty alcohol polyoxyethylene ether, and the silane coupling agent is 5:1.5:13.

[0010] Furthermore, the particle size of the fish scale powder is 400-600 mesh; And / or, the fatty alcohol polyoxyethylene ether includes at least one of fatty alcohol polyoxyethylene ether-8, fatty alcohol polyoxyethylene ether-9, fatty alcohol polyoxyethylene ether-10, fatty alcohol polyoxyethylene ether-11 and fatty alcohol polyoxyethylene ether-12. And / or, the silane coupling agent includes at least one of γ-aminopropyltriethoxysilane and γ-(2,3-epoxypropoxy)propyltrimethoxysilane.

[0011] Furthermore, the plasticizer includes at least one of dioctyl terephthalate and di(2-propylheptyl) phthalate; And / or, the lubricant includes polyethylene wax; And / or, the antioxidant is composed of antioxidant 1010 and antioxidant 168 in a weight ratio of (2-3):1; And / or, the stabilizer includes a calcium-zinc composite stabilizer.

[0012] In a second aspect, the present invention provides a method for preparing the graphene / polyvinyl chloride composite material described in the first aspect, comprising the following steps: The raw materials are premixed and then kneaded to obtain a mixture; The mixture is melt-extruded to obtain the graphene / polyvinyl chloride composite material.

[0013] Furthermore, the working conditions for the internal mixing include: a temperature of 140-145℃ and a time of 10-20 minutes; And / or, the working conditions parameters for the melt extrusion include: using a twin-screw extruder, with a screw speed of 15-25 rpm, a zone 1 temperature of 140-145℃, a zone 2 temperature of 155-160℃, a zone 3 temperature of 165-170℃, a zone 4 temperature of 170-175℃, and a zone 5 temperature of 175-180℃.

[0014] Thirdly, the present invention provides the application of the graphene / polyvinyl chloride composite material described in the first aspect or the graphene / polyvinyl chloride composite material prepared by the preparation method described in the second aspect in the preparation of pipes and cable sheaths.

[0015] The technical solutions provided in the embodiments of the present invention have at least the following advantages compared with the prior art: This invention provides a graphene / polyvinyl chloride (PVC) composite material, its preparation method, and its applications. Based on existing technologies, this invention primarily achieves synergistic physical-chemical modification of graphene through the combined effects of oxygen-rich microwave plasma treatment and a composite surface modifier. This improves graphene's compatibility, dispersion, and toughening / reinforcing effects within the PVC matrix, significantly enhancing the stability of the resulting composite material under high humidity and heat conditions. This effectively extends the service life of products such as pipes and cables, making it suitable for a wide range of applications. Specifically: On the one hand, the present invention introduces oxygen-containing functional groups such as hydroxyl and carboxyl groups on the surface of graphite powder through oxygen-enriched microwave plasma technology, thereby improving its hydrophilicity and surface activity, while generating edge defects and active sites to enhance its chemical bonding ability with subsequent surface modifiers.

[0016] On the other hand, this invention selects fish scale powder, fatty alcohol polyoxyethylene ether, and silane coupling agent as a composite surface modifier. It utilizes the minerals and organic matter contained in fish scale powder and the long polyoxyethylene chains in fatty alcohol polyoxyethylene ether to undergo a condensation reaction with oxygen-containing functional groups on the surface of graphene through silane coupling agent, thereby constructing a stable three-dimensional network chemical interface layer of organic-inorganic hybrid on the surface of graphene. This achieves high dispersion and strong interfacial bonding of graphene in polyvinyl chloride and forms a hydrophobic barrier.

[0017] Therefore, this invention improves the compatibility, dispersion and toughening effect of graphene in polyvinyl chloride matrix through the synergistic effect of physical modification by oxygen-enriched microwave plasma and chemical modification by composite surface modifier, thereby significantly improving the stability of the obtained composite material in high humidity and heat environment and effectively extending the durability of the composite material in pipes, cables and other fields. Detailed Implementation

[0018] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0019] It should be noted that, unless otherwise specified, the raw materials involved in the graphene / polyvinyl chloride composite material provided by this invention can be self-made according to the preparation process disclosed in the prior art or directly use commercially available products, such as polyvinyl chloride, graphene, plasticizer, lubricant, antioxidant and stabilizer (the calcium-zinc composite stabilizer can be commercially available products such as WWP-R03, CZ757, etc.), fish scale powder (specifically, cleaned and dried fish scales can be ground and sieved to obtain fish scale powder of the preset particle size), etc.; at the same time, unless otherwise specified, the preparation process operation steps and parameters involved can be carried out according to the preparation process disclosed in the prior art or using existing equipment, and this invention document will not elaborate further.

[0020] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Experimental methods in the following embodiments, unless otherwise specified, are generally performed according to national standards. If no corresponding national standard exists, then generally accepted international standards, conventional conditions, or conditions recommended by the manufacturer are followed.

[0021] Example 1 This example provides a graphene / polyvinyl chloride composite material, which, by weight, comprises the following raw materials: 100 parts polyvinyl chloride, 2 parts modified graphene, 18 parts plasticizer, 1.5 parts lubricant, 0.5 parts antioxidant and 2 parts stabilizer; The modified graphene is obtained by sequentially treating graphite powder with oxygen-enriched microwave plasma and coating it with a surface modifier (specifically, a mixture of fish scale powder, fatty alcohol polyoxyethylene ether, and silane coupling agent in a weight ratio of 5:1.5:13, wherein the fish scale powder has a particle size of 500 mesh, the fatty alcohol polyoxyethylene ether is fatty alcohol polyoxyethylene ether-10, and the silane coupling agent is γ-(2,3-epoxypropoxy)propyltrimethoxysilane). The specific preparation process includes the following steps: 150-mesh graphite powder is subjected to microwave power... Graphene was obtained by glow discharge treatment for 90 s under working medium conditions of oxygen and nitrogen at 460 W and a volume ratio of 6:1. Then, under ultrasonic power of 250 W and temperature of 48 °C, the graphene treated with oxygen-enriched microwave plasma, the surface modifier, and a mixed solution of ethanol-water at pH 4.4 and a volume ratio of 4:1 were heated and stirred for 80 min at a weight ratio of 100:8:455. The mixture was then filtered and dried to obtain the modified graphene. The plasticizer is dioctyl terephthalate, the lubricant is polyethylene wax, the antioxidant is composed of antioxidant 1010 and antioxidant 168 in a weight ratio of 2.8:1, and the stabilizer is a calcium-zinc composite stabilizer.

[0022] The preparation method of the above graphene / polyvinyl chloride composite material includes the following steps: The raw materials are premixed and then kneaded to obtain a mixture; The mixture is melt-extruded to obtain the graphene / polyvinyl chloride composite material; The working conditions for the internal mixing include: a temperature of 142°C and a time of 15 min; the working conditions for the melt extrusion include: using a twin-screw extruder, a screw speed of 20 rpm, a zone 1 temperature of 142°C, a zone 2 temperature of 158°C, a zone 3 temperature of 167°C, a zone 4 temperature of 173°C, and a zone 5 temperature of 177°C.

[0023] Example 2 This example provides a graphene / polyvinyl chloride composite material, which, by weight, comprises the following raw materials: 90 parts polyvinyl chloride, 1 part modified graphene, 15 parts plasticizer, 1 part lubricant, 0.3 parts antioxidant and 1 part stabilizer; The modified graphene is obtained by sequentially treating graphite powder with oxygen-enriched microwave plasma and coating it with a surface modifier (specifically, fish scale powder, fatty alcohol polyoxyethylene ether, and silane coupling agent in a weight ratio of 4:1:10, wherein the fish scale powder has a particle size of 400 mesh, the fatty alcohol polyoxyethylene ether is fatty alcohol polyoxyethylene ether-8, and the silane coupling agent is γ-aminopropyltriethoxysilane). The specific preparation process includes the following steps: treating graphite powder with a particle size of 200 mesh with a microwave power of 500W... Graphene treated with oxygen-enriched microwave plasma was obtained by performing glow discharge treatment for 60 s under working medium conditions of oxygen and nitrogen in a volume ratio of 5:1. The graphene treated with oxygen-enriched microwave plasma, the surface modifier, and a mixed solution of ethanol-water with a pH of 4.2 and a volume ratio of 7:1 were heated and stirred for 90 min at a weight ratio of 100:5:400 under ultrasonic power of 200 W and temperature of 50 °C. The mixture was then filtered and dried to obtain the modified graphene. The plasticizer is di(2-propylheptyl) terephthalate, the lubricant is polyethylene wax, the antioxidant is composed of antioxidant 1010 and antioxidant 168 in a weight ratio of 2:1, and the stabilizer is a calcium-zinc composite stabilizer.

[0024] The preparation method of the above graphene / polyvinyl chloride composite material includes the following steps: The raw materials are premixed and then kneaded to obtain a mixture; The mixture is melt-extruded to obtain the graphene / polyvinyl chloride composite material; The working conditions for the internal mixing include: a temperature of 140℃ and a time of 20 min; the working conditions for the melt extrusion include: using a twin-screw extruder, a screw speed of 15 rpm, a zone 1 temperature of 140℃, a zone 2 temperature of 155℃, a zone 3 temperature of 165℃, a zone 4 temperature of 170℃, and a zone 5 temperature of 175℃.

[0025] Example 3 This example provides a graphene / polyvinyl chloride composite material, which, by weight, comprises the following raw materials: 110 parts polyvinyl chloride, 3.5 parts modified graphene, 20 parts plasticizer, 3 parts lubricant, 0.8 parts antioxidant and 3 parts stabilizer; The modified graphene is obtained by sequentially treating graphite powder with oxygen-enriched microwave plasma and coating it with a surface modifier (specifically, a mixture of fish scale powder, fatty alcohol polyoxyethylene ether, and silane coupling agent in a weight ratio of 7:2:15, wherein the fish scale powder has a particle size of 600 mesh, the fatty alcohol polyoxyethylene ether is fatty alcohol polyoxyethylene ether-12, and the silane coupling agent is γ-aminopropyltriethoxysilane). The specific preparation process includes the following steps: treating 200-mesh graphite powder with a microwave power of 410W... Graphene treated with oxygen-enriched microwave plasma was obtained by performing glow discharge treatment for 120 s under working medium conditions of oxygen and nitrogen in a volume ratio of 8:1. The graphene treated with oxygen-enriched microwave plasma, the surface modifier, and a mixed solution of ethanol-water with a pH of 4.5 and a volume ratio of 3:1 were heated and stirred for 60 min at a weight ratio of 100:9:500 under ultrasonic power of 300W and temperature of 45℃. The mixture was then filtered and dried to obtain the modified graphene. The plasticizer is di(2-propylheptyl) terephthalate, the lubricant is polyethylene wax, the antioxidant is composed of antioxidant 1010 and antioxidant 168 in a weight ratio of 3:1, and the stabilizer is a calcium-zinc composite stabilizer.

[0026] The preparation method of the above graphene / polyvinyl chloride composite material includes the following steps: The raw materials are premixed and then kneaded to obtain a mixture; The mixture is melt-extruded to obtain the graphene / polyvinyl chloride composite material; The working conditions for the internal mixing include: a temperature of 145°C and a time of 10 minutes; the working conditions for the melt extrusion include: using a twin-screw extruder, a screw speed of 25 rpm, a zone 1 temperature of 145°C, a zone 2 temperature of 160°C, a zone 3 temperature of 170°C, a zone 4 temperature of 175°C, and a zone 5 temperature of 180°C.

[0027] Comparative Example 1 This example provides a graphene / polyvinyl chloride composite material and its preparation method, which differs from Example 1 only in that: (1) The modified graphene was not subjected to oxygen-enriched microwave plasma treatment; the specific preparation process includes the following steps: graphite powder with a particle size of 150 mesh, the surface modifier in Example 1 and an ethanol-water mixture solution with pH 4.4 and a volume ratio of 4:1 were heated and stirred for 80 min at a weight ratio of 100:8:455, filtered and dried to obtain the modified graphene.

[0028] Comparative Example 2 This example provides a graphene / polyvinyl chloride composite material and its preparation method, which differs from Example 1 only in that: (1) No fish scale powder was added to the surface modifier, that is, the surface modifier was composed of fatty alcohol polyoxyethylene ether in Example 1 and silane coupling agent in Example 1 in a weight ratio of 6.5:13.

[0029] Comparative Example 3 This example provides a graphene / polyvinyl chloride composite material and its preparation method, which differs from Example 1 only in that: (1) No fatty alcohol polyoxyethylene ether was added to the surface modifier, that is, the surface modifier was composed of fish scale powder in Example 1 and silane coupling agent in Example 1 in a weight ratio of 6.5:13.

[0030] Comparative Example 4 This example provides a graphene / polyvinyl chloride composite material and its preparation method, which differs from Example 1 only in that: (1) The surface modifier is composed of fish scale powder in Example 1, fatty alcohol polyoxyethylene ether in Example 1 and silane coupling agent in Example 1 in a weight ratio of 1.5:5:13.

[0031] Test case The purpose of this test is to examine the stability of the graphene / polyvinyl chloride composite materials provided in the examples and comparative examples under high humidity and heat conditions. The test conditions include: measuring the tensile strength retention rate (%) of the samples obtained in the examples and comparative examples after one month in an environment with a temperature of 70±2℃ and a relative humidity of 95±5%, and using conventional polyvinyl chloride material (i.e., the material obtained in Example 1 without the addition of modified graphene) as a control. The test results are shown in Table 1.

[0032] Table 1 The test results above show that, compared with Comparative Examples 1-4 and conventional polyvinyl chloride materials, the graphene / polyvinyl chloride composite materials provided in Examples 1-3 of this invention exhibit a higher tensile strength retention rate under high humidity and heat conditions, maintaining above 90%. This indicates that the synergistic effect of physical modification of graphene using oxygen-enriched microwave plasma and chemical modification of the composite surface modifier significantly improves the stability of the resulting composite material under high humidity and heat conditions. Furthermore, the graphene / polyvinyl chloride composite materials provided in these embodiments possess both excellent mechanical properties (e.g., the tensile strength of Example 1 reaches 71.6 MPa) and thermal conductivity (e.g., the thermal conductivity of Example 1 reaches 0.6 W / mK), meeting the application requirements in fields such as pipes and cables.

[0033] In summary, the embodiments of the present invention provide a graphene / polyvinyl chloride composite material, its preparation method, and its application. Based on the prior art, the present invention mainly achieves physical-chemical dual synergistic modification of graphene by using the synergistic effect of oxygen-rich microwave plasma treatment and composite surface modifier, thereby improving its compatibility, dispersion, toughening, and reinforcing effects in polyvinyl chloride matrix. This significantly improves the stability of the resulting composite material in high humidity and heat environments, effectively extending the service life of products such as pipes and cables, and has a wide range of applications.

[0034] Various embodiments of the present invention may exist in the form of a range; it should be understood that the description in the form of a range is merely for convenience and brevity and should not be construed as a hard limitation on the scope of the invention; therefore, it should be considered that the range description has specifically disclosed all possible subranges and single numerical values ​​within that range. For example, it should be considered that the range description from 1 to 6 has specifically disclosed subranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., and single numbers within the range, such as 1, 2, 3, 4, 5, and 6, regardless of the range. Furthermore, whenever a numerical range is referred to herein, it means including any referenced number (fraction or integer) within the range referred to.

[0035] The above description is merely a specific embodiment of the present invention, enabling those skilled in the art to understand or implement the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the present invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features claimed herein.

Claims

1. A graphene / polyvinyl chloride composite material, characterized in that, Including polyvinyl chloride, modified graphene, plasticizers, lubricants, antioxidants, and stabilizers; The modified graphene is obtained by sequentially treating graphite powder with oxygen-enriched microwave plasma and coating it with a surface modifier. The surface modifier comprises fish scale powder, fatty alcohol polyoxyethylene ether, and silane coupling agent in a weight ratio of (4-7):(1-2):(10-15), wherein the fatty alcohol polyoxyethylene ether has 8-12 polyoxyethylene chain units.

2. The graphene / polyvinyl chloride composite material according to claim 1, characterized in that, The graphene / polyvinyl chloride composite material comprises the following raw materials in parts by weight: 90-110 parts polyvinyl chloride, 1-3.5 parts modified graphene, 15-20 parts plasticizer, 1-3 parts lubricant, 0.3-0.8 parts antioxidant and 1-3 parts stabilizer.

3. The graphene / polyvinyl chloride composite material according to claim 1, characterized in that, The graphene / polyvinyl chloride composite material comprises the following raw materials in parts by weight: 100 parts polyvinyl chloride, 2 parts modified graphene, 18 parts plasticizer, 1.5 parts lubricant, 0.5 parts antioxidant and 2 parts stabilizer.

4. The graphene / polyvinyl chloride composite material according to any one of claims 1-3, characterized in that, The preparation of the modified graphene includes the following process: Graphite powder with a particle size of 100-200 mesh was subjected to glow discharge treatment for 60-120s under microwave power of 410-500W and working medium of oxygen and nitrogen with a volume ratio of (5-8):1 to obtain graphene after oxygen-enriched microwave plasma treatment. Under ultrasonic power of 200-300W and temperature of 45-50℃, the graphene treated with oxygen-enriched microwave plasma, the surface modifier, and an ethanol-water mixture with pH of 4.2-4.5 and a volume ratio of (3-7):1 were heated and stirred for 60-90 minutes at a weight ratio of 100:(5-9):(400-500), filtered, and dried to obtain the modified graphene.

5. The graphene / polyvinyl chloride composite material according to any one of claims 1-3, characterized in that, The weight ratio of the fish scale powder, the fatty alcohol polyoxyethylene ether, and the silane coupling agent is 5:1.5:

13.

6. The graphene / polyvinyl chloride composite material according to any one of claims 1-3, characterized in that, The particle size of the fish scale powder is 400-600 mesh; And / or, the fatty alcohol polyoxyethylene ether includes at least one of fatty alcohol polyoxyethylene ether-8, fatty alcohol polyoxyethylene ether-9, fatty alcohol polyoxyethylene ether-10, fatty alcohol polyoxyethylene ether-11 and fatty alcohol polyoxyethylene ether-12. And / or, the silane coupling agent includes at least one of γ-aminopropyltriethoxysilane and γ-(2,3-epoxypropoxy)propyltrimethoxysilane.

7. The graphene / polyvinyl chloride composite material according to any one of claims 1-3, characterized in that, The plasticizer includes at least one of dioctyl terephthalate and di(2-propylheptyl) phthalate; And / or, the lubricant includes polyethylene wax; And / or, the antioxidant is composed of antioxidant 1010 and antioxidant 168 in a weight ratio of (2-3):1; And / or, the stabilizer includes a calcium-zinc composite stabilizer.

8. A method for preparing the graphene / polyvinyl chloride composite material according to any one of claims 1-7, characterized in that, Includes the following steps: The raw materials are premixed and then kneaded to obtain a mixture; The mixture is melt-extruded to obtain the graphene / polyvinyl chloride composite material.

9. The method for preparing the graphene / polyvinyl chloride composite material according to claim 8, characterized in that, The working conditions for the intensive mixing process include: a temperature of 140-145℃ and a time of 10-20 minutes. And / or, the working conditions parameters for the melt extrusion include: using a twin-screw extruder, with a screw speed of 15-25 rpm, a zone 1 temperature of 140-145℃, a zone 2 temperature of 155-160℃, a zone 3 temperature of 165-170℃, a zone 4 temperature of 170-175℃, and a zone 5 temperature of 175-180℃.

10. The application of a graphene / polyvinyl chloride composite material according to any one of claims 1-7 or a graphene / polyvinyl chloride composite material prepared by the preparation method according to any one of claims 8-9 in the preparation of pipes and cable sheaths.

Images