WO2019237489A1 - 一种石墨烯增强聚乙烯管材及其制备方法 - Google Patents

一种石墨烯增强聚乙烯管材及其制备方法 Download PDF

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WO2019237489A1
WO2019237489A1 PCT/CN2018/100232 CN2018100232W WO2019237489A1 WO 2019237489 A1 WO2019237489 A1 WO 2019237489A1 CN 2018100232 W CN2018100232 W CN 2018100232W WO 2019237489 A1 WO2019237489 A1 WO 2019237489A1
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graphene
polyethylene
parts
reinforced
polyethylene pipe
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PCT/CN2018/100232
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English (en)
French (fr)
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李茂东
黄国家
杨波
翟伟
辛明亮
尹香槟
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广州特种承压设备检测研究院
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/2224—Magnesium hydroxide
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/04—Antistatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/18—Applications used for pipes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Definitions

  • the invention relates to the field of plastic pipes, in particular to a graphene-reinforced polyethylene pipe and a preparation method thereof.
  • PE Polyethylene
  • Pipe is a very important one. Compared with other materials, PE pipe has the following characteristics: odorless, non-toxic, and excellent low temperature resistance Performance, chemical stability, resistance to most acids and alkalis (not resistant to acids with oxidizing properties), insoluble in general solvents at room temperature, low water absorption, and no swelling and other properties, is widely used in pipe systems.
  • PE pipes Due to the characteristics of PE materials, PE pipes also have certain weaknesses, such as low strength, bumping against solid stones and metals, which can cause pits until they perforate; no flame retardancy; there is a limit to the maximum operating pressure, and low temperature resistance Poor performance. Therefore, to maintain the original excellent performance of PE pipes, improve its lack of toughness, improve its flame retardant properties, abrasion resistance, impact resistance, crack resistance, anti-scaling performance, corrosion resistance and prolong the service life of the system.
  • One of the topics of innovative development of PE pipeline One of the topics of innovative development of PE pipeline.
  • Reinforced polyethylene pipes are an important direction to improve the performance of polyethylene pipes.
  • large-scale applications are mainly steel tape or steel pipe reinforced polyethylene pipes.
  • reinforcement due to the large and uneven internal stress between steel and polyethylene, reinforcement The effect is not obvious, and there are also problems such as the connection, butt and capping between the tubes.
  • the inner wall of the traditional high-density polyethylene pipe is rough, which easily causes problems such as scaling of the conveyed material, and the recycled pipe has poor recyclability.
  • the object of the present invention is to provide a graphene-reinforced polyethylene pipe, which has good flexibility, mechanical strength, anti-aging performance and antistatic performance.
  • a graphene reinforced polyethylene pipe comprising the following components by weight: 75 to 100 parts of polyethylene, 0.1 to 5 parts of graphene, and 3 to 8 parts of lubricant, 2 to 4 parts of antistatic agent and 3 to 5 parts of flame retardant.
  • the present invention uses graphene as the reinforcing phase of the polyethylene pipe.
  • Graphene has a lamellar structure, has great flexibility, and has a large contact surface with polyethylene. Compared to other materials, it can be obtained with a small amount of graphene. Enhance the effect, and avoid the high content to hinder the arrangement of polyethylene molecular chains.
  • the graphene-reinforced polyethylene pipe obtained by optimizing the distribution ratio of each group of the present invention has the following advantages: 1. it has excellent flexibility and formability; 2. the graphene is uniformly distributed in the polyethylene matrix and the orientation is basically consistent with the matrix The combination is firm, does not escape and lose due to friction, and has good durability; 3. Graphene and polyethylene have no conflict with other additives and cooperate well, and the antistatic performance, mechanical strength and thermal aging performance of the composite material are improved.
  • the graphene-reinforced polyethylene pipe includes the following components by weight: 85 to 100 parts of polyethylene, 0.5 to 1 part of graphene, 3 to 8 parts of lubricant, 2 to 4 parts of antistatic agent, and flame retardancy 3 to 5 servings.
  • the lubricant is a compound of one or more of stearic acid, paraffin wax, or polyethylene wax, preferably polyethylene wax;
  • the antistatic agent is carbon black, and white carbon black or conductive acetylene may be selected.
  • Carbon black is preferably conductive acetylene carbon black;
  • the flame retardant is a mixture of magnesium hydroxide and aluminum hydroxide, and the mass ratio of magnesium hydroxide and aluminum hydroxide is preferably (1 to 2): 1.
  • the invention also provides a method for preparing a graphene-reinforced polyethylene pipe, including the following steps:
  • step S2 mixing the organically modified graphene obtained in step S1 with polyethylene in xylene, stirring at 125-135 ° C, and then removing the xylene to obtain a graphene / polyethylene modified master batch;
  • step S3 mixing and extruding the graphene / polyethylene modified masterbatch obtained in step S2 with polyethylene to obtain a graphene and polyethylene composite;
  • step S4 Melt mixing and extruding the graphene and polyethylene composite obtained in step S3 with a lubricant, an antistatic agent, and a flame retardant to obtain a graphene-reinforced polyethylene pipe.
  • the present invention organically modifies graphene to generate active functional groups such as carboxyl and hydroxyl groups, and uses these active functional groups to introduce a coupling agent molecular chain on the surface of graphene, greatly improving graphite.
  • the lipophilicity of the ene surface improves the compatibility of graphene with the polyethylene matrix, which can increase the interfacial bonding force between graphene and polyethylene and improve the mechanical strength of the composite pipe.
  • the compounding of graphene and polyethylene in the present invention is performed in two steps: the first step is to prepare graphene / polyethylene modified masterbatch in a liquid phase solvent, and the liquid phase is mixed to fully extend the graphene and polyethylene molecular chains.
  • the second step is to use physical and mechanical mixing, which is suitable for the operation of a large number of materials.
  • the two-step method for preparing graphene and polyethylene composites improves the dispersibility of graphene in polyethylene and enhances the effect better. It avoids the disadvantages of graphene agglomerates and low dispersion caused by one-step mixing method. , While meeting the needs of industrial mass production.
  • the mass ratio of the coupling agent to the graphene is (0.1 to 3): 100.
  • the mass ratio of the coupling agent to the graphene is (0.5 to 1.5): 100.
  • Coupling agent is covalently connected to epoxy groups on graphene.
  • Graphene has a lamellar structure with a large specific surface area.
  • An appropriate amount of coupling agent is beneficial to enhance the contact and adhesion between graphene and polyethylene. Too much coupling agent will cause As a result, the original performance of graphene is reduced; too little coupling agent is not conducive to the adhesion of graphene to polyethylene.
  • the mass concentration of graphene is 0.1 to 10 mg / ml.
  • the mass concentration of graphene is 0.5 to 2 mg / ml.
  • Graphene has a lamellar structure, which is conducive to the full development of the lamellar layer, and is not easy to agglomerate; the graphene concentration is too high, it is easy to agglomerate; the graphene concentration is too low, and the large amount of solvent causes waste.
  • the coupling agent is an aluminum-titanium composite coupling agent or a titanate coupling agent;
  • the organic solvent is an alcoholic organic solvent, preferably methanol, ethanol, or isopropanol.
  • the coupling agent is an aluminum-titanium composite coupling agent or a titanate coupling agent;
  • the organic solvent is an alcoholic organic solvent, preferably methanol, ethanol, or isopropanol.
  • the mass ratio of the organically modified graphene to polyethylene is (0.1 to 1): 10. At a temperature of 125 to 135 ° C, polyethylene is in a molten state. In xylene solvents, this mass ratio is more conducive to full contact and mixing of graphene and polyethylene, thereby producing high uniformity, good dispersibility, and graphene content. High graphene / polyethylene modified masterbatch, ready for next blending with polyethylene.
  • the polyethylene is preferably a high-density polyethylene having a density of 0.930 to 0.950 g / cm 3 and a melt index of 0.15 to 1.4 g / 10 min.
  • the mass ratio of the graphene / polyethylene modified masterbatch to polyethylene is 1: (8-10). Under this mass ratio, rapid mixing of graphene / polyethylene modified masterbatch and polyethylene can be realized, which is suitable for industrial mass production.
  • the temperature during the extrusion is 180 to 210 ° C
  • the rotation speed is 55 to 110 rad / min
  • the traction speed is 340 to 750 cm / min. Under these conditions, it is favorable for the orientation crystallization of polyethylene, thereby improving the mechanical strength.
  • the temperature during the extrusion process is set in sections: the length of the barrel area of the extruder is divided into 4 sections, and the temperature of each section is: the first section is 180 ⁇ 3 ° C, and the The second stage is 185 ⁇ 3 ° C, the third stage is 190 ⁇ 3 ° C, and the fourth stage is 195 ⁇ 3 ° C; the die length in the die area of the extruder is divided into 7 stages, and the temperature of each stage is: the first stage It is 195 ⁇ 5 °C, the second stage is 185 ⁇ 5 °C, the third stage is 190 ⁇ 5 °C, the fourth stage is 195 ⁇ 5 °C, the fifth stage is 200 ⁇ 5 °C, and the sixth stage is 205 ⁇ 5 °C
  • the 7th paragraph is 210 ⁇ 5 °C.
  • the graphene-reinforced polyethylene pipe of this embodiment includes the following components by weight: 80 parts of high-density polyethylene, 0.2 parts of graphene, 3 parts of lubricant, 2 parts of antistatic agent, and 5 parts of flame retardant.
  • the density of high-density polyethylene is 0.93g / cm 3 and the melt index is 1.4g / 10min
  • the lubricant is stearic acid, paraffin or polyethylene wax
  • the antistatic agent is conductive acetylene carbon black
  • the flame retardant is mass ratio A 2: 1 mixture of magnesium hydroxide and aluminum hydroxide.
  • the raw materials are prepared according to the foregoing mass parts, and then the graphene-reinforced polyethylene pipe is prepared according to the following steps:
  • the graphene-reinforced polyethylene pipe of this embodiment includes the following components by weight: 90 parts of high-density polyethylene, 0.6 parts of graphene, 5 parts of lubricant, 3 parts of antistatic agent, and 5 parts of flame retardant.
  • the density of high-density polyethylene is 0.93g / cm 3 and the melt index is 1.4g / 10min;
  • the lubricant is paraffin;
  • the antistatic agent is conductive acetylene carbon black;
  • the flame retardant is magnesium hydroxide with a mass ratio of 1: 1 And aluminum hydroxide.
  • the raw materials are prepared according to the foregoing mass parts, and then the graphene-reinforced polyethylene pipe is prepared according to the following steps:
  • the graphene-reinforced polyethylene pipe of this embodiment includes the following components by weight: 100 parts of high-density polyethylene, 1 part of graphene, 8 parts of lubricant, 4 parts of antistatic agent, and 3 parts of flame retardant.
  • the density of high-density polyethylene is 0.93g / cm 3 and the melt index is 1.4g / 10min;
  • the lubricant is paraffin;
  • the antistatic agent is conductive acetylene carbon black;
  • the flame retardant is magnesium hydroxide with a mass ratio of 2: 1 And aluminum hydroxide.
  • the raw materials are prepared according to the foregoing mass parts, and then the graphene-reinforced polyethylene pipe is prepared according to the following steps:
  • Example 1 Example 2
  • Example 3 Oxidation induction time (200 ° C, min) 65 70 93 90 Elongation at break (%) 453 490 650 553 Surface resistance ( ⁇ ) 6.7E + 09 4.8E + 09 5.1E + 08 6.0E + 08
  • Tensile strength (MPa) 41.2 43.1 47.3 44.6 Bending strength (kJ / m 2 ) 31.3 33.4 35.1 36.9
  • the graphene-reinforced polyethylene pipes of Examples 1 to 3 took longer to start the autocatalytic oxidation reaction under high temperature (200 ° C) and oxygen conditions than the existing polyethylene pipes, indicating that the graphite of the present invention
  • the polyethylene-reinforced polyethylene pipe has good anti-aging performance
  • the graphene-reinforced polyethylene pipe of Examples 1 to 3 has a larger elongation at break than the existing polyethylene pipe, indicating that the graphene-reinforced polyethylene pipe of the present invention has good Good flexibility and tear resistance
  • the surface resistance of the graphene-reinforced polyethylene pipes of Examples 1 to 3 is greater than the existing polyethylene pipes, indicating that the graphene-reinforced polyethylene pipes of the present invention have good antistatic properties
  • the tensile strength and flexural strength of the graphene-reinforced polyethylene pipes of Examples 1 to 3 are greater than those of the existing polyethylene pipes, indicating that the graphene-reinforced poly
  • the graphene-reinforced polyethylene pipe of the present invention has better flexibility, mechanical strength, anti-aging performance, and antistatic performance, and has excellent comprehensive performance. It can be used for wire and cable, gas drainage, water supply and drainage, and positive Negative pressure ventilation, spraying and other uses.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Rigid Pipes And Flexible Pipes (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

一种石墨烯增强聚乙烯管材及其制备方法。所述石墨烯增强聚乙烯管材包括以下重量份的组分：聚乙烯75～100份，石墨烯0.1～5份，润滑剂3～8份，抗静电剂2～4份，阻燃剂3～5份。所述制备方法包括先对石墨烯进行有机化改性、然后通过液相溶剂混合和物理机械混合两步法制备石墨烯与聚乙烯复合材料，再与其它组分混合挤出。获得的石墨烯增强聚乙烯管材具有良好的柔韧性、力学强度、抗老化性能和抗静电性能。

Description

一种石墨烯增强聚乙烯管材及其制备方法 技术领域
本发明涉及塑料管道领域，尤其涉及一种石墨烯增强聚乙烯管材及其制备方法。
背景技术
聚乙烯(PE)是结构最简单的高分子有机化合物，当今世界应用最广泛的高分子材料之一。聚乙烯由乙烯聚合而成，可制成各种应用材料，管材是其中非常重要的一种，与其他材质的管材相比，PE管具有以下特点：无臭，无毒，具有优良的耐低温性能，化学稳定性好，能耐大多数酸碱的侵蚀(不耐具有氧化性质的酸)，常温下不溶于一般溶剂，吸水性小，且不发生溶胀等性质，被广泛用于管材系统。
由于PE材料本身的特点，PE管也有一定的弱点，如强度低，碰到坚石、金属碰撞挤压，易引起凹坑，直至穿孔；没有阻燃性；对最高使用压力有限制，耐低温性能差等。因此保持PE管道原有的优良性能，改善其韧性不足，提高其阻燃性能、耐磨性能、抗冲击性、抗开裂性、防结垢性能、耐腐蚀性能、延长系统使用寿命，就成了PE管道创新发展的课题之一。
增强聚乙烯管是改进聚乙烯管道性能的重要方向，目前大规模应用的主要是钢带或钢管增强聚乙烯管，但由于钢与聚乙烯之间存在较大的和不均匀的内应力，增强效果不明显，而且还存在管管之间的连接、对接和封端等问题。此外，传统的高密度聚乙烯管材的内壁毛糙，极易引起被输送材料结垢等问题，报废后的管材的再生利用性差。
石墨烯的出现给这个难题的破解带来了希望。石墨烯是目前世界上已知的力学强度最高(断裂强度130GPa，杨氏模量1.0TPa)、最薄(厚度0.3nm)、最导电(电阻率10 -6Ω·cm，略低于最导电的金属银)、最导热(室温下热导率达到5000W/m·k，超过目前已知导热率最高的金刚石)等性能。石墨烯的这些优异性能，使得石墨烯极有可能成为提高塑料管道综合性能的材料。石墨烯不溶于水和有机溶剂，具有优异的力学性能和导电性能及其独特的一维纳米结构所特有的纳米效应，但由于其表面原子具有较高的表面能和表面结合能，分散性差且易于形成大的团聚体，在作为聚乙烯基体的增强材料时极易发生团聚，从而导致石墨烯在聚乙烯基体中分散程度低，进而影响复合材料的应用性能。将石墨烯与聚乙烯基材直接复合的工艺步骤简单，但由于石墨烯的表面与聚乙烯的结合较差，不易得到稳定、老化性能好的聚乙烯管材。
发明内容
基于此，本发明的目的在于，提供一种石墨烯增强聚乙烯管材，其具有良好的柔韧性、力学强度、抗老化性能和抗静电性能。
本发明的目的是通过以下技术方案实现的：一种石墨烯增强聚乙烯管材，包括以下重量份的组分：聚乙烯75～100份，石墨烯0.1～5份，润滑剂3～8份，抗静电剂2～4份，阻燃剂3～5份。
相对于现有技术，本发明采用石墨烯作为聚乙烯管的增强相，石墨烯为片层结构，柔性大，与聚乙烯接触面大，相对于其它的材料，用少量的石墨烯就可以获得增强效果，且可避免高含量对聚乙烯分子链的排列产生阻碍作用。本发明通过优化各组分配比获得的石墨烯增强聚乙烯管材，具有以下优点：1、具有优异的柔韧性、成型性；2、石墨烯在聚乙烯基体中分布均匀且取向基本一致，与基体结合牢固，不因摩擦而逸散和丧失，耐久性好；3、石墨烯和聚乙烯与其他助剂无冲突，协同配合好，复合材料的抗静电性能、力学强度和热老化性能得到提高。
进一步地，所述石墨烯增强聚乙烯管材包括以下重量份的组分：聚乙烯85～100份，石墨烯0.5～1份，润滑剂3～8份，抗静电剂2～4份，阻燃剂3～5份。
进一步地，所述润滑剂为硬脂酸、石蜡或聚乙烯蜡中的一种或多种的复合，优选为聚乙烯蜡；所述抗静电剂为炭黑，可选用白炭黑或导电乙炔炭黑，优选为导电乙炔炭黑；所述阻燃剂为氢氧化镁和氢氧化铝的混合物，氢氧化镁和氢氧化铝的质量比优选为(1～2):1。
本发明还提供了一种石墨烯增强聚乙烯管材的制备方法，包括以下步骤：
S1：将石墨烯与偶联剂置于有机溶剂中回流80～120min，然后除去有机溶剂，获得有机化改性后的石墨烯；
S2：将步骤S1获得的有机化改性后的石墨烯与聚乙烯置于二甲苯中混合，在125～135℃下搅拌，然后除去二甲苯，获得石墨烯/聚乙烯改性母粒；
S3：将步骤S2获得的石墨烯/聚乙烯改性母粒与聚乙烯混合挤出造粒，获得石墨烯与聚乙烯复合物；
S4：将步骤S3获得的石墨烯与聚乙烯复合物与润滑剂、抗静电剂、阻燃剂熔融混合挤出，获得石墨烯增强聚乙烯管材。
相对于现有技术，首先，本发明对石墨烯进行有机化改性，使其产生羧基和羟基等活性功能基团，利用这些活性官能团在石墨烯表面引入偶联剂分子链，大大改善了石墨烯表面的亲油性，提高石墨烯与聚乙烯基体的相容性，从而可以增加石墨烯与聚乙烯的界面结合力，提升复合管材的力学强度。然后，本发明中石墨烯与聚乙烯的复合分两步进行：第一步在液 相溶剂中制备石墨烯/聚乙烯改性母粒，液相混合，使石墨烯和聚乙烯分子链充分伸展、分散、结合，促进石墨烯在聚乙烯中均匀分布与接触结合；第二步再采用物理机械混合，适于大量物料的操作。采用两步法制备石墨烯与聚乙烯复合材料，提高了石墨烯在聚乙烯中的分散性，增强效果更佳，避免了一步混合法产生的石墨烯聚集成团、分散性程度不高的缺点，同时又符合工业批量生产的需求。
进一步地，所述步骤S1中，偶联剂与石墨烯的质量比为(0.1～3):100。优选的，偶联剂与石墨烯的质量比为(0.5～1.5):100。偶联剂与石墨烯上环氧基团共价连接，石墨烯为片层结构，比表面积大，适量偶联剂有利于增强石墨烯和聚乙烯的接触粘接；偶联剂过多，会导致石墨烯原本性能下降；偶联剂过少，不利于石墨烯与聚乙烯的粘接。
进一步地，所述步骤S1中，石墨烯的质量浓度为0.1～10mg/ml。优选的，石墨烯的质量浓度为0.5～2mg/ml。石墨烯为片层结构，该浓度下有利于片层的充分展开，而不易发生团聚；石墨烯浓度过高，易发生团聚；石墨烯浓度过低，溶剂用量大造成浪费。
进一步地，所述步骤S1中，所述偶联剂为铝钛复合偶联剂或钛酸酯偶联剂；所述有机溶剂为醇类有机溶剂，优选为甲醇、乙醇、异丙醇中的一种或多种的复合。
进一步地，所述步骤S2中，有机化改性后的石墨烯与聚乙烯的质量比为(0.1～1):10。温度125～135℃下，聚乙烯为熔融状态，在二甲苯溶剂中，该质量比下，更有利于石墨烯与聚乙烯充分接触混合，从而制得均匀性高、分散性好、石墨烯含量高的石墨烯/聚乙烯改性母粒，为下一步与聚乙烯混合做准备。所述聚乙烯优选为高密度聚乙烯，其密度为0.930～0.950g/cm 3，熔融指数为0.15～1.4g/10min。
进一步地，所述步骤S3中，石墨烯/聚乙烯改性母粒与聚乙烯的质量比为1:(8～10)。该质量比下，能实现石墨烯/聚乙烯改性母粒与聚乙烯的快速混合，适用于工业批量生产。
进一步地，所述步骤S4中，挤出过程中的温度为180～210℃、转速为55～110rad/min、牵引速度为340～750cm/min。该条件下，有利于聚乙烯的取向结晶，从而提升力学强度。
进一步地，所述步骤S4中，对挤出过程中的温度进行分段设置：挤出机的机筒区长度均分为4段，每段温度为：第1段为180±3℃，第2段为185±3℃，第3段为190±3℃，第4段为195±3℃；挤出机模头区的模头长度均分为7段，每段温度为：第1段为195±5℃，第2段为185±5℃，第3段为190±5℃，第4段为195±5℃，第5段为200±5℃，第6段为205±5℃，第7段为210±5℃。
为了更好地理解和实施，下面结合实施例说明本发明。
具体实施方式
实施例1
本实施例的石墨烯增强聚乙烯管材，包括以下重量份的组分：高密度聚乙烯80份，石墨烯0.2份，润滑剂3份，抗静电剂2份，阻燃剂5份。其中，高密度聚乙烯的密度为0.93g/cm 3熔融指数为1.4g/10min；润滑剂为硬脂酸、石蜡或聚乙烯蜡；抗静电剂为导电乙炔炭黑；阻燃剂为质量比为2:1的氢氧化镁和氢氧化铝的混合物。
本实施例先按照上述质量份准备原料，然后按照下述步骤制备石墨烯增强聚乙烯管材：
(1)石墨烯的预处理：将石墨烯与铝钛复合偶联剂置于乙醇中回流120min，其中，铝钛复合偶联剂与石墨烯质量比为0.6:100，石墨烯的质量浓度为0.2mg/ml；然后除去乙醇，干燥，获得有机化改性后的石墨烯。
(2)将有机化改性后的石墨烯与聚乙烯按质量比0.2:10加入到二甲苯中，升温至130℃，搅拌混合30min，然后除去二甲苯，干燥，获得石墨烯/聚乙烯改性母粒。
(3)将石墨烯/聚乙烯改性母粒与聚乙烯按质量比1:8混合，挤出并造粒，获得石墨烯与聚乙烯复合物。
(4)用喷雾器添加润滑剂、抗静电剂和阻燃剂，搅拌30min后与石墨烯与聚乙烯复合物熔融混合挤出，挤出机的温度为180～210℃，挤出机转速为55～110rad/min，牵引速度为340～750cm/min，获得石墨烯增强聚乙烯管材。
(5)挤出后的管材在水温25℃下定型后，再置于18℃的水箱中进行二次冷却。
实施例2
本实施例的石墨烯增强聚乙烯管材，包括以下重量份的组分：高密度聚乙烯90份，石墨烯0.6份，润滑剂5份，抗静电剂3份，阻燃剂5份。其中，高密度聚乙烯的密度为0.93g/cm 3熔融指数为1.4g/10min；润滑剂为石蜡；抗静电剂为导电乙炔炭黑；阻燃剂为质量比为1:1的氢氧化镁和氢氧化铝的混合物。
本实施例先按照上述质量份准备原料，然后按照下述步骤制备石墨烯增强聚乙烯管材：
(1)石墨烯的预处理：将石墨烯与铝钛复合偶联剂置于乙醇中回流100min，其中，铝钛复合偶联剂与石墨烯质量比为0.5:100，石墨烯的质量浓度为0.6mg/ml；然后除去乙醇，干燥，获得有机化改性后的石墨烯。
(2)将有机化改性后的石墨烯与聚乙烯按质量比0.6:10加入到二甲苯中，升温至130℃，搅拌混合30min，然后除去二甲苯，干燥，获得石墨烯/聚乙烯改性母粒。
(3)将石墨烯/聚乙烯改性母粒与聚乙烯按质量比1:10混合，挤出并造粒，获得石墨烯 与聚乙烯复合物。
(4)用喷雾器添加润滑剂、抗静电剂和阻燃剂，搅拌30min后与石墨烯与聚乙烯复合物熔融混合挤出，挤出机的温度为180～210℃，挤出机转速为55～110rad/min，牵引速度为340～750cm/min，获得石墨烯增强聚乙烯管材。
(5)挤出后的管材在水温25℃下定型后，再置于18℃的水箱中进行二次冷却。
实施例3
本实施例的石墨烯增强聚乙烯管材，包括以下重量份的组分：高密度聚乙烯100份，石墨烯1份，润滑剂8份，抗静电剂4份，阻燃剂3份。其中，高密度聚乙烯的密度为0.93g/cm 3熔融指数为1.4g/10min；润滑剂为石蜡；抗静电剂为导电乙炔炭黑；阻燃剂为质量比为2:1的氢氧化镁和氢氧化铝的混合物。
本实施例先按照上述质量份准备原料，然后按照下述步骤制备石墨烯增强聚乙烯管材：
(1)石墨烯的预处理：将石墨烯与铝钛复合偶联剂置于乙醇中回流100min，其中，铝钛复合偶联剂与石墨烯质量比为2:100，石墨烯的质量浓度为0.1mg/ml；然后除去乙醇，干燥，获得有机化改性后的石墨烯。
(2)将有机化改性后的石墨烯与聚乙烯按质量比1:10加入到二甲苯中，升温至130℃，搅拌混合30min，然后除去二甲苯，干燥，获得石墨烯/聚乙烯改性母粒。
(3)将石墨烯/聚乙烯改性母粒与聚乙烯按质量比1:10混合，挤出并造粒，获得石墨烯与聚乙烯复合物。
(4)用喷雾器添加润滑剂、抗静电剂和阻燃剂，搅拌30min后与石墨烯与聚乙烯复合物熔融混合挤出，挤出机的温度为180～210℃，挤出机转速为55～110rad/min，牵引速度为340～750cm/min，获得石墨烯增强聚乙烯管材。
(5)挤出后的管材在水温25℃下定型后，再置于18℃的水箱中进行二次冷却。
对实施例1～3的石墨烯增强聚乙烯管材进行性能测试，并与现有聚乙烯管材的性能进行对比，结果如下表1：
表1实施例1～3的石墨烯增强聚乙烯管材性能测试结果
性能 现有聚乙烯管材 实施例1 实施例2 实施例3
氧化诱导时间(200℃，min) 65 70 93 90
断裂伸长率(％) 453 490 650 553
表面电阻(Ω) 6.7E+09 4.8E+09 5.1E+08 6.0E+08
拉伸强度(MPa) 41.2 43.1 47.3 44.6
弯曲强度(kJ/m 2) 31.3 33.4 35.1 36.9
从表中可以看出，实施例1～3的石墨烯增强聚乙烯管材在高温(200℃)和氧气条件下开始发生自动催化氧化反应的时间比现有聚乙烯管材长，说明本发明的石墨烯增强聚乙烯管材具有良好的抗老化性能；实施例1～3的石墨烯增强聚乙烯管材的断裂伸长率比现有聚乙烯管材大，说明本发明的石墨烯增强聚乙烯管材具有良好的柔韧性好和抗撕裂性；实施例1～3的石墨烯增强聚乙烯管材的表面电阻比现有聚乙烯管材大，说明本发明的石墨烯增强聚乙烯管材具有良好的抗静电性能；实施例1～3的石墨烯增强聚乙烯管材的拉伸强度和弯曲强度比现有聚乙烯管材大，说明本发明的石墨烯增强聚乙烯管材具有良好的力学性能。
相对于现有技术，本发明的石墨烯增强聚乙烯管材具有更好的柔韧性、力学强度、抗老化性能和抗静电性能，综合性能优异，可用于电线电缆、抽放瓦斯、供水排水、正负压通风、喷浆等用途。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。

Claims (10)

  1. 一种石墨烯增强聚乙烯管材，其特征在于：包括以下重量份的组分：聚乙烯75～100份，石墨烯0.1～5份，润滑剂3～8份，抗静电剂2～4份，阻燃剂3～5份。
  2. 根据权利要求1所述的石墨烯增强聚乙烯管材，其特征在于：包括以下重量份的组分：聚乙烯85～100份，石墨烯0.5～1份，润滑剂3～8份，抗静电剂2～4份，阻燃剂3～5份。
  3. 根据权利要求1所述的石墨烯增强聚乙烯管材，其特征在于：所述润滑剂为硬脂酸、石蜡或聚乙烯蜡中的一种或多种的复合；所述抗静电剂为白炭黑或导电乙炔炭黑；所述阻燃剂为氢氧化镁和氢氧化铝的混合物，氢氧化镁和氢氧化铝的质量比为(1～2):1。
  4. 一种石墨烯增强聚乙烯管材的制备方法，其特征在于：包括以下步骤：
    S1：将石墨烯与偶联剂置于有机溶剂中回流80～120min，然后除去有机溶剂，获得有机化改性后的石墨烯；
    S2：将步骤S1获得的有机化改性后的石墨烯与聚乙烯置于二甲苯中混合，在125～135℃下搅拌，然后除去二甲苯，获得石墨烯/聚乙烯改性母粒；
    S3：将步骤S2获得的石墨烯/聚乙烯改性母粒与聚乙烯混合挤出造粒，获得石墨烯与聚乙烯复合物；
    S4：将步骤S3获得的石墨烯与聚乙烯复合物与润滑剂、抗静电剂、阻燃剂熔融混合挤出，获得石墨烯增强聚乙烯管材。
  5. 根据权利要求4所述的石墨烯增强聚乙烯管材的制备方法，其特征在于：所述步骤S1中，偶联剂与石墨烯的质量比为(0.1～3):100。
  6. 根据权利要求4或5所述的石墨烯增强聚乙烯管材的制备方法，其特征在于：所述步骤S1中，石墨烯的质量浓度为0.1～10mg/ml。
  7. 根据权利要求6所述的石墨烯增强聚乙烯管材的制备方法，其特征在于：所述步骤S1中，所述偶联剂为铝钛复合偶联剂或钛酸酯偶联剂，所述有机溶剂为甲醇、乙醇、异丙醇中的一种或多种的复合。
  8. 根据权利要求6所述的石墨烯增强聚乙烯管材的制备方法，其特征在于：所述步骤S2中，有机化改性后的石墨烯与聚乙烯的质量比为(0.1～1):10。
  9. 根据权利要求8所述的石墨烯增强聚乙烯管材的制备方法，其特征在于：所述步骤S3中，石墨烯/聚乙烯改性母粒与聚乙烯的质量比为1:(8～10)。
  10. 根据权利要求9所述的石墨烯增强聚乙烯管材的制备方法，其特征在于：所述步骤S4中，挤出过程中的温度为180～210℃、转速为55～110rad/min、牵引速度为340～750cm/min。
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