WO2018045673A1 - 纳米石墨负载石墨烯纳米带改性聚乙烯薄膜的方法 - Google Patents

纳米石墨负载石墨烯纳米带改性聚乙烯薄膜的方法 Download PDF

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WO2018045673A1
WO2018045673A1 PCT/CN2016/111440 CN2016111440W WO2018045673A1 WO 2018045673 A1 WO2018045673 A1 WO 2018045673A1 CN 2016111440 W CN2016111440 W CN 2016111440W WO 2018045673 A1 WO2018045673 A1 WO 2018045673A1
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nanographite
polyethylene
graphene
masterbatch
nanocomposite
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郑玉婴
陈宇
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福州大学
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  • the invention belongs to the field of polymer materials, and in particular relates to a method for loading a graphene nano-belt modified polyethylene film with nano-graphite.
  • Polyethylene (PE) is a thermoplastic resin which has a simple structure and is widely used in composite packaging because of its good heat sealability, impact resistance, certain transparency and barrier properties.
  • PE Polyethylene
  • the traditional polyethylene film is prone to breakage due to the failure of mechanical properties; and due to the nature of the polymer, it is easy to accumulate static electricity and even cause serious accidents such as fire; these all limit the polyethylene film in the future.
  • the improvement of the mechanical properties and antistatic properties of polyethylene films has become the focus of research.
  • Modification of the polyethylene film can be achieved by adding a filler to the polymer, but conventional conventional filler modification effects are not significant. Therefore, the applicant tried to add a nano-scale filler because the physical properties of the material will only mutate when the filler particles are reduced to the nano-scale size.
  • graphene nanoribbons are stable to small molecules such as water due to their high aspect ratio, high specific surface area, low defects and adjustable morphology. And so on, it is easier to form a skeleton in the matrix, which is of great help to improve the mechanical properties of the matrix.
  • Nano-graphites have excellent high temperature resistance, good thermal conductivity, good electrical conductivity and high corrosion resistance, which can improve the wear resistance, pressure resistance or conductivity of materials. Due to its excellent adsorption, it can fill the edge defects of graphene nanoribbons on the one hand, and make the graphene nanoribbons more easily lap into 3D networks on the other hand. The synergistic effect of the two can improve the mechanical properties and resistance of the polymer films. Static performance.
  • the invention adopts longitudinal oxidation-cut multi-walled carbon nanotubes (MWNTs) method to prepare graphene oxide nanobelts (GONRs), and uses hydrazine hydrate to reduce GONRs to obtain graphene nanoribbons (GNRs); sodium dodecyl sulfate treatment of nanometer graphite (CNPs) improve the dispersibility, LDPE resin as the matrix, melt extrusion granulation in a twin-screw extruder, and finally use the flat vulcanizer to compress and cut the GNRs 75% -CNPs/LDPE composite film.
  • MWNTs longitudinal oxidation-cut multi-walled carbon nanotubes
  • the performance of the CNPs is not formed in the matrix because of the small particle size and large specific surface area, which can form a large agglomerate, can be uniformly dispersed and loaded onto the CNRs, and construct a 3D network with CNRs as the skeleton.
  • the unique effect of the nano-enhancement phase makes the prepared GNRs 75% -CNPs/LDPE composite film have excellent mechanical properties and antistatic properties.
  • the object of the present invention is to provide a method for high-nanometer graphite-loaded graphene nanoribbon modified polyethylene film in view of the deficiencies of the prior art.
  • the invention combines the high-dispersion nano-graphite onto the graphene nano-belt to form a 3D network structure, and the close combination with the polyethylene matrix makes the composite film have excellent antistatic property and mechanical property.
  • a method for nanometer graphite supported graphene nanobelt modified polyethylene film after treating nanographite with sodium dodecyl sulfate, loading on graphene nanobelt to form nanocomposite; then dispersing nanocomposite in In the polyethylene matrix, a nanocomposite-polyethylene masterbatch is prepared; the masterbatch and the polyethylene pellet are mixed and melted in a 1:1 mass ratio, and a composite film is obtained by tableting; in the nanocomposite, nanometer The mass ratio of the graphite and the graphene nanobelts is 1:4; in the composite film, the nanocomposite accounts for 0.2 to 1.5% of the mass of the polyethylene matrix.
  • the nanographite has a particle diameter of 30 to 100 nm.
  • the method for preparing the graphene nanoribbons comprises: preparing a graphene oxide nanobelt by longitudinal oxidation dicing of the multi-walled carbon nanotubes, and reducing the graphene oxide nanobelt by hydrazine hydrate to obtain a graphene nanobelt;
  • the diameter of the multi-walled carbon nanotubes is 40 to 80 nm, preferably 40 to 60 nm; the temperature at which hydrazine hydrate is reduced is 100 ° C, and the reaction time is 6 hours.
  • the polyethylene matrix has a melt index value of 1.0 to 3.0 g/10 min; preferably a range of 1.5 to 2.0 g/10 min.
  • the concentration of the nanocomposite in the nano solution in the step (2) is 0.002 mg ⁇ mL -1 ; the temperature at the temperature rising and stirring is 80 ° C; the mass ratio of the master batch to the pellet is 1:1, and the melting temperature is 140 ° C.
  • the composite film prepared by the invention has excellent antistatic property and mechanical property; and can be applied to film materials for precision electronic packaging and electronic equipment in actual production, especially for electronic products such as integrated circuit boards and mobile computers. In the middle, keep up with the pace of the development of modern high-tech technology.
  • nano-graphite has small particle size, large specific surface area, excellent structural stability and electrical conductivity, but its dispersion in the matrix.
  • the invention needs to be improved after the sodium dodecyl sulfate treatment, so that the nano graphite can be fully and uniformly supported on the graphene nanobelt, so that the two can fully overlap the 3D network, which is excellent antistatic property of the composite film and
  • the mechanical properties provide the basis;
  • the preparation method of the invention is scientific and reasonable, the process is simple, and the operability is strong, and the phenomenon that the nanometer graphite is easily agglomerated in the matrix is solved, and the two nano materials composite synergistically improve the performance of the polyethylene film, and the modification of the composite film in the future.
  • the prepared composite film has excellent antistatic properties and mechanical properties; it can be applied to precision electronic packaging and electronic equipment in practical production, especially for integrated circuit boards and mobile phones. In electronic products such as computers, we are keeping up with the pace of modern high-tech technology development.
  • Figure 1 is a dispersion diagram of nano-graphite in xylene before and after treatment with sodium lauryl sulfate (solution concentration is 0.5 mg ⁇ mL -1 , after standing for 15 days);
  • TEM 2 is a field emission transmission electron micrograph (TEM) of nanographite (A) and nanocomposite (B);
  • Figure 3 is a scanning electron microscope analysis (SEM) of the quenched section of the composite film sample prepared by the present invention
  • Figure 4 is a graph showing the volume resistivity of a polyethylene film and a polyethylene composite film with different contents of nano-filler
  • Figure 5 is the tensile strength of a pure polyethylene film and a polyethylene composite film with different content of nano-filler; pure LDPE (1), 0.2 wt% (2), 0.4 wt% (3), 0.5 wt% (4) , 0.6 wt% (5) and 0.8 wt% (6) GNRs 75% - Tens strength of the CNPs/LDPE composite film.
  • a method for nanometer graphite supported graphene nanobelt modified polyethylene film the specific steps are as follows:
  • GNRs graphene nanoribbons
  • GNRs 75% -CNPs composite nanomaterials 100mg nanographite (CNPs) was added to 70mL deionized water, 0.0237g sodium lauryl sulfate was slowly added, 100W ultrasonic for 1h to form a uniform dispersion; then 400mg GNRs were added The above dispersion, 100W ultrasonic 2h after formation of a stable dispersion, washed with anhydrous ethanol and deionized water multiple times, freeze-dried to obtain GNRs 75% -CNPs composite nanomaterials;
  • LDPE 1.7 g was placed in a round bottom flask, added to 30 mL of xylene, heated to 80 ° C and stirred until a paste, 0.05 g of GNRs 75% -CNPs was dissolved in 10 mL of xylene, and slowly poured into a round bottom flask. Stir well; slowly pour the mixture into a large amount of absolute ethanol, stir and flocculate, filter and dry to obtain GNRs 75% -CNPs/LDPE masterbatch, then the resulting GNRs 75% -CNPs/LDPE masterbatch and LDPE pellets The melt-extruded granulation was carried out at 140 ° C in a twin-screw extruder at 1:1. Finally, a 1.5 wt% GNRs 75% -CNPs/LDPE composite film was prepared by tableting using a flat vulcanizer.

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Abstract

一种纳米石墨负载石墨烯纳米带改性聚乙烯薄膜的方法。具体为：将纳米石墨经十二烷基硫酸钠处理后，负载到石墨烯纳米带上，形成纳米复合材料；然后将纳米复合材料分散于聚乙烯基体中，制得纳米复合材料-聚乙烯母料；母料与聚乙烯粒料按1:1质量比混合熔融，经压片切割制得复合薄膜。该复合薄膜可用于电子产业领域和精密电子包装领域。

Description

纳米石墨负载石墨烯纳米带改性聚乙烯薄膜的方法 技术领域
本发明属于高分子材料领域，具体涉及一种纳米石墨负载石墨烯纳米带改性聚乙烯薄膜的方法。
背景技术
聚乙烯(PE)是一种热塑性树脂，其结构简单，并且由于其具有良好的热封性、耐冲击性、一定的透明性和阻隔性，被广泛应用于复合包装。随着社会的不断进步，我们对聚乙烯薄膜的应用需求越来越大，范围越来越广。所以单纯的聚乙烯薄膜已经远远不能满足社会发展的需要。在一定的环境下传统聚乙烯薄膜因力学性能达不到要求易出现断裂破损的现象；而且由于聚合物本质的特点，容易积累静电甚至产生火灾等严重事故；这些都限制了聚乙烯薄膜在未来高科技产业中的应用，因此提高聚乙烯薄膜的力学性能和抗静电性能成为了研究重点。
对聚乙烯薄膜进行改性可以通过在聚合物中添加填料来达到目的，但是常规普通的填料改性效果不明显。所以申请人尝试添加纳米级的填料，因为只有当填料粒子减小至纳米级尺寸，材料的物性才会发生突变。石墨烯纳米带(GNRs)除了具有石墨烯优良的物理、化学以及机械性能外，由于自身较高的长径比，对水等小分子物质稳定，以及具有高比表面积、低缺陷、形态可调等特点，在基体中更易形成骨架，对于提高基体力学性能具有显著的帮助。纳米石墨(CNPs)具有优异的耐高温、导热性好、导电性好、耐腐蚀性极高等优点，可以提高材料的耐磨、抗压或传导性能。由于其优异的吸附性，一方面可以填补石墨烯纳米带的边缘缺陷，另一方面易使石墨烯纳米带更易搭接成3D网络，两者协同作用更能提升聚合物薄膜的力学性能和抗静电性能。
本发明采用纵向氧化切割多壁碳纳米管(MWNTs)法制得氧化石墨烯纳米带(GONRs)，并利用水合肼还原GONRs得到石墨烯纳米带(GNRs)；采用十二烷基硫酸钠处理纳米石墨(CNPs)改善其分散性，以LDPE树脂为基体，在双螺杆挤出机中熔融挤出造粒，最后利用平板硫化机经压片切割制备出GNRs75％-CNPs/LDPE复合材料薄膜，对其性能进行研究，经过处理的CNPs不会在基体中因为粒径小、比表面积大而形成较大的团聚体，可以均匀分散和负载到CNRs上，构建出以CNRs为骨架的3D网络，发挥纳米增强相的独特作用，使制备出的GNRs75％-CNPs/LDPE复合材料薄膜具有优异的力学性能和抗静电性能，
发明内容
本发明的目的在于针对现有技术的不足，提供一种高纳米石墨负载石墨烯纳米带改性聚乙烯薄膜的方法。本发明通过高分散性的纳米石墨负载到石墨烯纳米带上搭接成3D网络结构，与聚乙烯基体间的紧密结合使得复合材料薄膜具有优异的抗静电性能和力学性能。
为实现本发明的目的，采用如下技术方案：
一种纳米石墨负载石墨烯纳米带改性聚乙烯薄膜的方法：将纳米石墨经十二烷基硫酸钠处理后，负载到石墨烯纳米带上，形成纳米复合材料；然后将纳米复合材料分散于聚乙烯基体中，制得纳米复合材料-聚乙烯母料；母料与聚乙烯粒料按1:1质量比混合熔融，经压片切割制得复合薄膜；所述的纳米复合材料中，纳米石墨和石墨烯纳米带的质量比为1:4；所述的复合薄膜中，纳米复合材料占聚乙烯基体质量的0.2～1.5％。
所述的纳米石墨其粒径为30～100nm。
所述的石墨烯纳米带的制备方法为：将多壁碳纳米管经纵向氧化切割法制得氧化石墨烯纳米带，氧化石墨烯纳米带再经水合肼还原后得到石墨烯纳米带；所述的多壁碳纳米管的管径为40～80nm，优选范围为：40～60nm；水合肼还原的温度为100℃，反应时间为6h。
所述的聚乙烯基体的熔融指数值为1.0～3.0g/10min；优选范围为1.5～2.0g/10min。
所述的纳米石墨负载石墨烯纳米带改性聚乙烯薄膜的方法，具体步骤为：
(1)纳米复合材料的制备：将纳米石墨加入去离子水中，然后加入十二烷基硫酸钠，超声1h，形成均匀分散液；将石墨烯纳米带加入分散液中，超声2h形成稳定分散液，分散液经无水乙醇和去离子水洗涤、冷冻干燥后制得纳米复合材料；
(2)复合薄膜的制备：将纳米复合材料分散于二甲苯中形成分散液，超声形成均匀分散的纳米溶液；然后加入聚乙烯，升温搅拌至糊状液体，将糊状液体倒入无水乙醇中进行搅拌絮凝，过滤并干燥，得到母料；随后将母料与聚乙烯粒料混合，经熔融、挤出造粒，压片切割制得复合薄膜。
步骤(2)中纳米溶液中纳米复合材料的浓度为0.002mg·mL-1；升温搅拌的温度为80℃；母料与粒料的质量比为1:1，熔融温度为140℃。
经本发明制备出的复合材料薄膜有优异的抗静电性能、力学性能；在实际生产中可以应用于精密电子包装和电子器材方面薄膜材料，特别是适用于如集成电路板以及手机电脑等电子产品中，紧跟现代高科技技术发展的潮流步伐。
本发明的有益效果在于：
1)利用十二烷基硫酸钠处理纳米石墨，充分改善了纳米石墨的分散性，众所周知，纳米石墨粒径小、比表面积大、结构稳定性和导电性优异，但是其在基体中的分散性有待提高；本发明经过十二烷基硫酸钠处理后使纳米石墨可以充分均匀地负载在石墨烯纳米带上，使两者可以充分搭接出3D网络，为复合材料薄膜的优异抗静电性和力学性能提供了基础；
2)本发明制备方法科学合理、工序简单、操作性强，解决了纳米石墨在基体中容易团聚的现象，而且两种纳米材料复合协同改善聚乙烯薄膜的性能，为今后复合材料薄膜的改性提供了新的研究方向；制备出的复合材料薄膜具有优异的抗静电性能、力学性能；在实际生产中可以应用于精密电子包装和电子器材方面薄膜材料，特别是适用于如集成电路板以及手机电脑等电子产品中，紧跟现代高科技技术发展的潮流步伐。
附图说明
图1中经十二烷基硫酸钠处理前后的纳米石墨在二甲苯中的分散图(溶液浓度为0.5mg·mL-1，静置15d后)；
图2为纳米石墨(A)与纳米复合材料(B)的场发射透射电镜图(TEM)；
图3为本发明所制得的复合材料薄膜试样的淬断面喷金后的扫描电镜分析图(SEM)；
图4为纯聚乙烯薄膜以及添加不同含量纳米填料时聚乙烯复合材料薄膜的体积电阻变化曲线；
图5为纯聚乙烯薄膜以及添加不同含量纳米填料时聚乙烯复合材料薄膜的拉伸强度；纯LDPE(1)、0.2wt％(2)、0.4wt％(3)、0.5wt％(4)、0.6wt％(5)和0.8wt％(6)GNRs75％-CNPs/LDPE复合材料膜的拉伸强度。
具体实施方式
为进一步公开而不是限制本发明，以下结合实例对本发明作进一步的详细说明。
一种纳米石墨负载石墨烯纳米带改性聚乙烯薄膜的方法，具体步骤为：
(1)GONRs的制备：首先将180mL浓H2SO4缓慢地加入到圆底烧瓶中搅拌，再将20mL H3PO4慢慢滴入，在一定转速下混合均匀，将1g MWCNTs缓慢加入并搅拌30min至均匀，再将6g KMnO4缓慢加入到以上混合液中；将上述反应体系在50℃的油浴中搅拌反应24h后降温至室温，然后将其倒入含10mL H2O2的500mL去离子水中冰浴搅拌1h，此时溶液变成墨绿色说明反应充分，然后加入适量HCl离心至中性，最后在冷冻干燥机中干燥得到GONRs；
(2)石墨烯纳米带(GNRs)的制备：100mg GONRs溶于100mL去离子水中，100W超声1h形成均匀分散液，加入1g水合肼，于100℃下还原6h；得到的黑色糊状产物用无水乙 醇和去离子水洗涤多次以除去剩余的水合肼，最后在冷冻干燥机中干燥得到GNRs；
(3)GNRs75％-CNPs复合纳米材料的制备：将100mg纳米石墨(CNPs)加入70mL去离子水中，缓慢加入0.0237g十二烷基硫酸钠，100W超声1h形成均匀分散液；然后将400mgGNRs加入上述分散液，100W超声2h后形成稳定分散液，利用无水乙醇和去离子水洗涤多次，冷冻干燥得到GNRs75％-CNPs复合纳米材料；
(4)GNRs75％-CNPs/LDPE复合薄膜的制备：取5g LDPE置于圆底烧瓶中，加入30mL二甲苯，升温至80℃并搅拌至糊状；将0.05g GNRs75％-CNPs溶于10mL二甲苯后，缓慢倒入圆底烧瓶中，并在一定转速下搅拌均匀；将混合液缓慢的倒入大量的无水乙醇中搅拌絮凝，过滤并干燥，得到GNRs75％-CNPs/LDPE母料；
(5)随后将所得GNRs75％-CNPs/LDPE母料与LDPE粒料按1:1加入双螺杆挤出机中在140℃下融熔挤出造粒，最后利用平板硫化机经压片切割制备出厚度为0.5mm不同含量的GNRs75％-CNPs/LDPE复合材料薄膜。
对比例1
取5g LDPE加入30mL二甲苯并搅拌至糊状液体，将混合液缓慢的倒入大量的无水乙醇中搅拌絮凝，过滤并干燥，得到母料，随后将所得母料与LDPE粒料按1:1比例加入双螺杆挤出机中在140℃下融熔挤出造粒，最后利用平板硫化机经压片切割制备出厚度为0.5mmLDPE薄膜。
实施例1
取5g LDPE置于圆底烧瓶中，加入30mL二甲苯，升温至80℃并搅拌至糊状；将0.05g GNRs75％-CNPs溶于10mL二甲苯中，缓慢倒入圆底烧瓶中，搅拌均匀；将混合液缓慢的倒入大量的无水乙醇中搅拌絮凝，过滤并干燥，得到GNRs75％-CNPs/LDPE母料，随后将所得GNRs75％-CNPs/LDPE母料与LDPE粒料按1:1加入双螺杆挤出机中在140℃下融熔挤出造粒，最后利用平板硫化机经压片切割制备出0.5wt％GNRs75％-CNPs/LDPE复合材料薄膜。
实施例2
取12.5g LDPE置于圆底烧瓶中，加入60mL二甲苯，升温至80℃并搅拌至糊状；将0.05g GNRs75％-CNPs溶于10mL二甲苯中，缓慢倒入圆底烧瓶中，搅拌均匀；将混合液缓慢的倒入大量的无水乙醇中搅拌絮凝，过滤并干燥，得到GNRs75％-CNPs/LDPE母料，随后将所得GNRs75％-CNPs/LDPE母料与LDPE粒料按1:1加入双螺杆挤出机中在140℃下融熔挤出造粒，最后利用平板硫化机经压片切割制备出0.2wt％GNRs75％-CNPs/LDPE复合材料薄膜。
实施例3
取6.25g LDPE置于圆底烧瓶中，加入40mL二甲苯中，升温至80℃并搅拌至糊状，将0.05g GNRs75％-CNPs溶于10mL二甲苯中，缓慢倒入圆底烧瓶中，搅拌均匀；将混合液缓慢的倒入大量的无水乙醇中搅拌絮凝，过滤并干燥，得到GNRs75％-CNPs/LDPE母料，随后将所得GNRs75％-CNPs/LDPE母料与LDPE粒料按1:1加入双螺杆挤出机中在140℃下融熔挤出造粒，最后利用平板硫化机经压片切割制备出0.4wt％GNRs75％-CNPs/LDPE复合材料薄膜。
实施例4
取4.17g LDPE置于圆底烧瓶中，加入30mL二甲苯中，升温至80℃并搅拌至糊状，将0.05g GNRs75％-CNPs溶于10mL二甲苯中，缓慢倒入圆底烧瓶中，搅拌均匀；将混合液缓慢的倒入大量的无水乙醇中搅拌絮凝，过滤并干燥，得到GNRs75％-CNPs/LDPE母料，随后将所得GNRs75％-CNPs/LDPE母料与LDPE粒料按1:1加入双螺杆挤出机中在140℃下融熔挤出造粒，最后利用平板硫化机经压片切割制备出0.6wt％GNRs75％-CNPs/LDPE复合材料薄膜。
实施例5
取3.125g LDPE置于圆底烧瓶中，加入30mL二甲苯中，升温至80℃并搅拌至糊状，将0.05g GNRs75％-CNPs溶于10mL二甲苯中，缓慢倒入圆底烧瓶中，搅拌均匀；将混合液缓慢的倒入大量的无水乙醇中搅拌絮凝，过滤并干燥，得到GNRs75％-CNPs/LDPE母料，随后将所得GNRs75％-CNPs/LDPE母料与LDPE粒料按1:1加入双螺杆挤出机中在140℃下融熔挤出造粒，最后利用平板硫化机经压片切割制备出0.8wt％GNRs75％-CNPs/LDPE复合材料薄膜。
实施例6
取2.5g LDPE置于圆底烧瓶中，加入30mL二甲苯中，升温至80℃并搅拌至糊状，将0.05g GNRs75％-CNPs溶于10mL二甲苯中，缓慢倒入圆底烧瓶中，搅拌均匀；将混合液缓慢的倒入大量的无水乙醇中搅拌絮凝，过滤并干燥，得到GNRs75％-CNPs/LDPE母料，随后将所得GNRs75％-CNPs/LDPE母料与LDPE粒料按1:1加入双螺杆挤出机中在140℃下融熔挤出造粒，最后利用平板硫化机经压片切割制备出1.0wt％GNRs75％-CNPs/LDPE复合材料薄膜。
实施例7
取1.7g LDPE置于圆底烧瓶中，加入30mL二甲苯中，升温至80℃并搅拌至糊状，将0.05g GNRs75％-CNPs溶于10mL二甲苯中，缓慢倒入圆底烧瓶中，搅拌均匀；将混合液缓慢的倒入大量的无水乙醇中搅拌絮凝，过滤并干燥，得到GNRs75％-CNPs/LDPE母料，随后将所得GNRs75％-CNPs/LDPE母料与LDPE粒料按1:1加入双螺杆挤出机中在140℃下融熔挤出造粒，最后利用平板硫化机经压片切割制备出1.5wt％GNRs75％-CNPs/LDPE复合材料薄膜。

Claims (9)

  1. 一种纳米石墨负载石墨烯纳米带改性聚乙烯薄膜的方法，其特征在于：将纳米石墨经十二烷基硫酸钠处理后，负载到石墨烯纳米带上，形成纳米复合材料；然后将纳米复合材料分散于聚乙烯基体中，制得纳米复合材料-聚乙烯母料；母料与聚乙烯粒料按1:1质量比混合熔融，经压片切割制得复合薄膜；所述的纳米复合材料中，纳米石墨和石墨烯纳米带的质量比为1:4；所述的复合薄膜中，纳米复合材料占聚乙烯基体质量的0.2～1.5％。
  2. 根据权利要求1所述的纳米石墨负载石墨烯纳米带改性聚乙烯薄膜的方法，其特征在于：所述的纳米石墨其粒径为30～100nm。
  3. 根据权利要求1所述的纳米石墨负载石墨烯纳米带改性聚乙烯薄膜的方法，其特征在于：所述的石墨烯纳米带的制备方法为：将多壁碳纳米管经纵向氧化切割法制得氧化石墨烯纳米带，氧化石墨烯纳米带再经水合肼还原后得到石墨烯纳米带。
  4. 根据权利要求3所述的纳米石墨负载石墨烯纳米带改性聚乙烯薄膜的方法，其特征在于：所述的多壁碳纳米管的管径为40～80nm。
  5. 根据权利要求3所述的纳米石墨负载石墨烯纳米带改性聚乙烯薄膜的方法，其特征在于：水合肼还原的温度为100℃，反应时间为6h。
  6. 根据权利要求1所述的纳米石墨负载石墨烯纳米带改性聚乙烯薄膜的方法，其特征在于：所述的聚乙烯基体的熔融指数值为1.0～3.0g/10min。
  7. 根据权利要求1所述的纳米石墨负载石墨烯纳米带改性聚乙烯薄膜的方法，其特征在于：具体步骤为：
    (1)纳米复合材料的制备：将纳米石墨加入去离子水中，然后加入十二烷基硫酸钠，超声1h，形成均匀分散液；将石墨烯纳米带加入分散液中，超声2h形成稳定分散液，分散液经无水乙醇和去离子水洗涤、冷冻干燥后制得纳米复合材料；
    (2)复合薄膜的制备：将纳米复合材料分散于二甲苯中形成分散液，超声形成均匀分散的纳米溶液；然后加入聚乙烯，升温搅拌至糊状液体，将糊状液体倒入无水乙醇中进行搅拌絮凝，过滤并干燥，得到母料；随后将母料与聚乙烯粒料混合，经熔融、挤出造粒，压片切割制得复合薄膜。
  8. 根据权利要求7所述的纳米石墨负载石墨烯纳米带改性聚乙烯薄膜的方法，其特征在于：步骤(2)中纳米溶液中纳米复合材料的浓度为0.002mg·mL-1；升温搅拌的温度为80℃；母料与粒料的质量比为1:1，熔融温度为140℃。
  9. 一种如权利要求1-8任一项所述的方法制得的纳米石墨负载石墨烯纳米带改性聚乙烯薄膜。
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CN114989467A (zh) * 2022-07-22 2022-09-02 中山大学 一种超高分子量聚乙烯/石墨复合材料及其制备方法
CN115960410A (zh) * 2022-12-30 2023-04-14 广东创阳新材料科技有限公司 一种改性母粒及其所制备的聚乙烯保护膜

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