High-performance graphene carrier roller pipe body material and preparation method thereof

Abstract

The invention relates to the field of carrier roller pipe body material preparation, and particularly discloses a high-performance graphene carrier roller pipe body material and a preparation method thereof.The carrier roller pipe body material is prepared from, by weight, 60-100 parts of ultra-high molecular weight polyethylene and 32-70 parts of master batch; the master batch comprises the following raw materials in parts by weight: 2-6 parts of graphene, 5-10 parts of an antistatic agent, 14-20 parts of a flame retardant, 2-8 parts of a filler, 2-7 parts of a first coupling agent, 0.5-2 parts of an antioxidant A, 0.5-1 part of a nucleating agent, 2-6 parts of a charring agent and 4-10 parts of an ethylene-acrylic acid copolymer. The carrier roller pipe body material provided by the invention has excellent permanent antistatic property and flame retardance, and is excellent in mechanical property and high in performance stability.

Description

Technical Field

[0001] The invention belongs to the field of roller tube material preparation, and in particular relates to a high-performance graphene roller tube material and a preparation method thereof. Background Art

[0002] In recent years, in the field of coal mine belt conveyors, due to the increasingly high requirements for energy saving, consumption reduction, environmental protection and noise reduction, traditional steel rollers can no longer meet the requirements of use. Their defects such as corrosion resistance and easy mixing of foreign matter often cause "axis sticking" phenomenon, and the belts are prone to heat due to long-term friction and accidents. These shortcomings can no longer make up for their price advantages, and non-metallic polymer roller materials are widely recognized.

[0003] In order to improve the applicability of non-metallic polymer roller materials, existing technologies have begun to use graphene as a nano-enhanced component to compound with polymer materials. When a small amount of graphene is added, the physical properties of the polymer can be greatly improved. However, when adding graphene, conductive carbon black masterbatch and flame retardant masterbatch are often directly added for modification to obtain non-metallic polymer dual-resistance materials with antistatic and flame retardancy, but this will obviously affect the mechanical properties of the non-metallic polymer dual-resistance materials themselves.

[0004] The invention patent with application number 201811629133.X discloses an environmentally friendly anti-static flame retardant graphene-modified high-density polyethylene mining pipe, which is composed of the following raw materials by weight ratio: 100 parts of high-density polyethylene; 1-10 parts of graphene; 5-25 parts of toughening modifier; 3-10 parts of compatibilizer; 2-7 parts of conductive filler; 5-35 parts of halogen-free flame retardant; 1-5 parts of flame retardant synergist; 2-10 parts of magnesium hydroxide; 0.5-5 parts of zinc borate; 0.5-3 parts of lubricant; 0.3-2 parts of antioxidant; 0.1-1.5 parts of coupling agent. The invention has excellent electrical conductivity, good flame retardant properties, and high mechanical properties, and solves the problems of high filler addition, serious loss of mechanical properties, and poor processability of HDPE anti-static flame retardant materials.

[0005] It can be found that the flame retardant and antistatic properties of the pipe material obtained after the flame retardant and antistatic modification of the polymer are greatly improved. However, when used as a mining roller material, it is easily affected by the temperature and humidity environment, resulting in insufficient long-term antistatic effect of the pipe material. In addition, the mechanical properties of the above-mentioned pipe materials are easily affected by the poor compatibility of the flame retardant and antistatic modifiers in the system, which limits the practical application of the pipe material.

[0006] In view of this, it is particularly important to disclose a high-performance graphene roller tube material in the present invention. Summary of the invention

[0007] In view of the defects of the prior art, the present invention provides a high-performance graphene roller tube material and a preparation method thereof. The graphene roller tube material provided by the present invention has excellent permanent antistatic and flame retardancy, excellent mechanical properties, and high performance stability.

[0008] In order to achieve the above object, the technical solution adopted by the present invention is as follows:

[0009] On the one hand, the present invention provides a high-performance graphene roller tube material, which comprises the following raw materials in parts by weight: 60 to 100 parts of ultra-high molecular weight polyethylene and 32 to 70 parts of masterbatch; the masterbatch comprises the following raw materials in parts by weight: 2 to 6 parts of graphene, 5 to 10 parts of antistatic agent, 14 to 20 parts of flame retardant, 2 to 8 parts of filler, 2 to 7 parts of first coupling agent, 0.5 to 2 parts of antioxidant A, 0.5 to 1 part of nucleating agent, 2 to 6 parts of carbonizing agent and 4 to 10 parts of ethylene-acrylic acid copolymer.

[0010] Preferably, the graphene is flake graphene with a particle size of 700 to 1500 meshes.

[0011] Graphene has excellent conductivity and unique two-dimensional network structure. The present invention preferably uses flaky graphene with a particle size of 700 to 1500 meshes, which can cooperate with antistatic agents to make the permanent antistatic property of the roller tube material stronger; at the same time, when flaky graphene with a specific particle size is added to the system, it is beneficial to further improve the uniformity and stability of each component and improve the long-term performance of the graphene roller tube material. The possible reason is that the presence of modified montmorillonite in the system further enhances the slip between the flaky graphene, promotes the synergy and interaction between the components of the system, and forms a good and uniform three-dimensional conductive network and stable structure in the matrix system.

[0012] In some embodiments of the present invention, the viscosity average molecular weight of the ultra-high molecular weight polyethylene is ≥ 3.5 million. Preferably, the viscosity average molecular weight of the ultra-high molecular weight polyethylene is 3.5 million.

[0013] In some embodiments of the present invention, the antistatic agent is a mixture of nano superconductive carbon black, micro powder graphite and modified low density polyethylene.

[0014] Preferably, the mass ratio of the nano superconductive carbon black, micro powder graphite and modified low density polyethylene is (0.8-1.3):1:(0.2-0.6).

[0015] Further preferably, the mass ratio of the nano superconductive carbon black, micro powder graphite and modified low density polyethylene is 1.1:1:0.4.

[0016] In some embodiments of the present invention, the preparation steps of the modified low-density polyethylene are as follows: add an organic solvent and low-density polyethylene into a reactor, then add an initiator and a modified monomer in sequence, heat to 40-70°C, stir evenly, introduce an inert atmosphere, treat with an ultraviolet lamp for 0.5-1h, rinse with an organic solvent, dry, add antioxidant B, melt-knead at 180-220°C and a rotation speed of 50-150r / min for 20-40min, and extrude and granulate to obtain the modified low-density polyethylene.

[0017] Preferably, the preparation steps of the modified low-density polyethylene are as follows:

[0018] Add an organic solvent and low-density polyethylene into a reactor, then add an initiator and a modified monomer in sequence, heat to 55°C, stir evenly, introduce a nitrogen atmosphere, treat with a 1000W ultraviolet lamp for 0.75h, rinse with an organic solvent, dry, add an antioxidant B, melt-knead at 200°C and a rotation speed of 100r / min for 30min, and extrude and granulate to obtain the modified low-density polyethylene.

[0019] In some embodiments of the present invention, the modified monomer is maleic anhydride or acrylic acid; the mass ratio of the modified monomer to low-density polyethylene is (0.2-0.5):1.

[0020] Preferably, the modified monomer is maleic anhydride; and the mass ratio of the modified monomer to low-density polyethylene is 0.35:1.

[0021] Preferably, the organic solvent is acetone or xylene.

[0022] Preferably, the amount of the organic solvent added is 2 to 6 times the total mass of the low-density polyethylene and the modified monomer.

[0023] Further preferably, the amount of the organic solvent added is 4 times the total mass of the low-density polyethylene and the modified monomer.

[0024] Preferably, the initiator is dibenzoyl peroxide.

[0025] Preferably, the added amount of the initiator is 0.1-1% of the total mass of the low-density polyethylene and the modified monomer.

[0026] Further preferably, the added amount of the initiator is 0.6% of the total mass of the low-density polyethylene and the modified monomer.

[0027] Preferably, the antioxidant B is antioxidant 264.

[0028] Preferably, the added amount of the antioxidant B is 0.05-0.5% of the total mass of the low-density polyethylene and the modified monomer.

[0029] Further preferably, the added amount of the antioxidant B is 0.3% of the total mass of the low-density polyethylene and the modified monomer.

[0030] Preferably, the particle size of the modified low-density polyethylene is 30-40 meshes.

[0031] The applicant has carried out a grafting reaction between low-density polyethylene and modified monomers. The introduction of low-density polyethylene makes the viscosity of the masterbatch containing the modified low-density polyethylene antistatic agent and the ultra-high molecular weight polyethylene approach matching, thereby improving the processing fluidity of the pipe material and weakening the phase separation phenomenon between the ultra-high molecular weight polyethylene and the masterbatch. At this time, the intermolecular diffusion of each component at the interface between the two phases is good, which is conducive to the construction of strong intermolecular interactions, promotes the uniformity and stability of each component, and improves the long-term performance.

[0032] In some embodiments of the present invention, the flame retardant is two or three of microcapsule red phosphorus flame retardant, nano magnesium hydroxide and ammonium polyphosphate.

[0033] Preferably, the flame retardant is a mixture of microcapsule red phosphorus flame retardant and nano magnesium hydroxide.

[0034] Preferably, the mass ratio of the microcapsule red phosphorus flame retardant to nano magnesium hydroxide is (0.4-0.8):1.

[0035] Further preferably, the mass ratio of the microcapsule red phosphorus flame retardant to nano magnesium hydroxide is 0.6:1.

[0036] Preferably, the microcapsule red phosphorus flame retardant is microcapsule red phosphorus flame retardant ZP-H01.

[0037] In some embodiments of the present invention, the filler is a mixture of modified montmorillonite and white carbon black.

[0038] In some embodiments of the present invention, the preparation steps of the modified montmorillonite are as follows:

[0039] Add montmorillonite and deionized water into a reactor, stir and mix at a speed of 500 to 1200 r / min for 15 to 30 minutes, heat to 50 to 70° C., add a dispersant and a second coupling agent, stir and mix at a speed of 500 to 1200 r / min for 10 to 20 minutes, add linear low-density polyethylene, stir and mix for 2 to 8 minutes, cool to room temperature, and dry to obtain the modified montmorillonite.

[0040] Preferably, the preparation steps of the modified montmorillonite are as follows:

[0041] Montmorillonite and deionized water were added to the reactor, stirred and mixed at a speed of 800 r / min for 20 minutes, heated to 60° C., and then a dispersant and a second coupling agent were added, stirred and mixed at a speed of 800 r / min for 15 minutes, and then linear low-density polyethylene was added, mixed and stirred for 5 minutes, cooled to room temperature, and dried to obtain the modified montmorillonite.

[0042] In some embodiments of the present invention, the mass ratio of the montmorillonite, the dispersant, the second coupling agent and the linear low-density polyethylene is 10: (0.6-1): (0.2-0.8): (2-2.5).

[0043] Preferably, the mass ratio of the montmorillonite, the dispersant, the second coupling agent and the linear low-density polyethylene is 10:0.8:0.5:2.3.

[0044] Preferably, the dispersant is ethylene bisstearamide.

[0045] Preferably, the second coupling agent is a titanate coupling agent.

[0046] Further preferably, the second coupling agent is titanate coupling agent NXH-501.

[0047] Preferably, the amount of deionized water added is 60 to 90 times the mass of montmorillonite.

[0048] Further preferably, the amount of deionized water added is 75 times the mass of montmorillonite.

[0049] Preferably, the mass ratio of the modified montmorillonite to white carbon black is 1:(0.2-1).

[0050] Preferably, the mass ratio of the modified montmorillonite to white carbon black is 1:0.6.

[0051] In the prior art, montmorillonite is an extremely important reinforcing filler for many polymer systems. To address its poor dispersibility, it is often modified by quaternary ammonium ions or silane coupling agents and prepared by ion exchange of cations in the interlayer of montmorillonite. However, in order to compensate for the loss of mechanical properties caused by ultra-high molecular weight polyethylene, a large amount of organic modified montmorillonite is often required. Even if the system has excellent compatibility, it is very easy to have unstable phenomena such as desorption, which affects the performance of the pipe material. Based on this, the present invention introduces linear low-density polyethylene and a dispersant combined with a coupling agent as a composite modifier to modify montmorillonite. At this time, the composite modifier is embedded in the montmorillonite layer to increase its interlayer spacing, reduce the attraction between adjacent sheets, increase the dispersibility and polarity of the modified montmorillonite, further increase the interaction between the modified montmorillonite and the system, especially improve the fit between the main component of the montmorillonite and the ultra-high molecular weight polyethylene, and further improve the mechanical properties of the pipe material; on the other hand, the introduction of the -CO-NH- group in the montmorillonite modified by the composite modifier cooperates with the main component of the antistatic agent, giving the system a better antistatic effect.

[0052] Preferably, the first coupling agent is a silane coupling agent.

[0053] Further preferably, the first coupling agent is silane coupling agent KH-560.

[0054] Preferably, the antioxidant A is antioxidant 1010.

[0055] Preferably, the nucleating agent is zinc stearate.

[0056] Preferably, the char-forming agent is glycerol.

[0057] Another aspect of the present invention further provides a method for preparing a high-performance graphene roller tube material, comprising the following steps:

[0058] (1) mixing an antistatic agent, graphene and a filler, adding a first coupling agent, heating to 100 to 110° C., stirring at a speed of 500 to 700 r / min for 10 to 30 min, and cooling to room temperature to obtain a mixture;

[0059] (2) adding a flame retardant, an antioxidant A, a nucleating agent, a carbonizing agent, an ethylene-acrylic acid copolymer and the mixture of step (1) into a reactor, and stirring at a speed of 400 to 600 r / min for 10 to 30 min to obtain a masterbatch;

[0060] (3) adding ultra-high molecular weight polyethylene to the masterbatch of step (2), stirring at a speed of 900 to 1100 r / min for 20 to 40 min, and obtaining the high-performance graphene roller tube material.

[0061] Preferably, the method for preparing the high-performance graphene roller tube material comprises the following steps:

[0062] (1) mixing an antistatic agent, graphene and a filler, adding a first coupling agent, heating to 105° C., stirring at a speed of 600 r / min for 20 min, and cooling to room temperature to obtain a mixture;

[0063] (2) adding a flame retardant, an antioxidant A, a nucleating agent, a carbonizing agent, an ethylene-acrylic acid copolymer and the mixture of step (1) into a reactor, and stirring at a speed of 500 r / min for 20 min to obtain a masterbatch;

[0064] (3) adding ultra-high molecular weight polyethylene to the masterbatch of step (2), stirring at a speed of 1000 r / min for 30 min, and obtaining the high-performance graphene roller tube material.

[0065] Compared with the prior art, the present invention has the following beneficial effects:

[0066] (1) The present invention provides a high-performance graphene roller tube material and a preparation method thereof. Specific graphene is added to the roller tube material system, and is coordinated with an antistatic agent containing modified low-density polyethylene, a filler containing modified montmorillonite, and other preferred components to enable the material to have excellent permanent antistatic and flame retardancy, as well as excellent mechanical properties and high performance stability.

[0067] (2) The applicant grafted low-density polyethylene with modified monomers. The introduction of low-density polyethylene made the viscosity of the masterbatch containing the modified low-density polyethylene antistatic agent and the ultra-high molecular weight polyethylene close to matching, thereby improving the processing fluidity of the pipe material and weakening the phase separation phenomenon between the ultra-high molecular weight polyethylene and the masterbatch. At this time, the intermolecular diffusion of each component at the interface between the two phases is good, which is conducive to the construction of strong intermolecular interactions, promotes the uniformity and stability of each component, and improves the long-term performance.

[0068] (3) The present invention modifies montmorillonite by introducing linear low-density polyethylene and a dispersant in combination with a coupling agent as a composite modifier. At this time, the composite modifier is embedded in the montmorillonite layer to increase its interlayer spacing, reduce the attraction between adjacent sheets, increase the dispersibility and polarity of the modified montmorillonite, further increase the interaction between the modified montmorillonite and the system, and especially improve the fit between the main component of montmorillonite and ultra-high molecular weight polyethylene, further improving the mechanical properties of the pipe material; on the other hand, the introduction of the -CO-NH- group in the montmorillonite modified by the composite modifier cooperates with the main component of the antistatic agent to give the system a better antistatic effect. DETAILED DESCRIPTION

[0069] The present invention will be described below in conjunction with specific embodiments. It should be noted that the following embodiments are examples of the present invention and are only used to illustrate the present invention, but not to limit the present invention. Other combinations and various modifications within the concept of the present invention may be performed without departing from the spirit or scope of the present invention.

[0070] If not otherwise specified, the reagents used below can be easily obtained from commercial companies, among which ultra-high molecular weight polyethylene (viscosity average molecular weight of 3.5 million) was purchased from Zhejiang Jiuding Chemical Materials Co., Ltd.; low-density polyethylene was purchased from Herun Plastics (Shenzhen) Co., Ltd.; ethylene-acrylic acid copolymer was purchased from Suzhou Shuangjing Plastic Technology Co., Ltd.; montmorillonite was purchased from Sishui Yitong Bentonite Co., Ltd.; linear low-density polyethylene was purchased from Dongguan Hualixing Plastic Raw Materials Co., Ltd.; and flake graphene (particle size of 1000 mesh) was purchased from Nangong Jiuxin New Material Technology Co., Ltd.

[0071] Preparation Example 1

[0072] The preparation steps of modified low-density polyethylene are as follows:

[0073] Add 40 mL of acetone and 10 g of low-density polyethylene into a reactor, then add 0.08 g of dibenzoyl peroxide and 3.5 g of maleic anhydride in sequence, heat to 55° C., stir evenly, introduce nitrogen atmosphere, treat with a 1000 W ultraviolet lamp for 0.75 h, rinse with acetone three times, dry, add 0.04 g of antioxidant 264, melt-mix at 200° C. and a rotation speed of 100 r / min for 30 min, and extrude and granulate to obtain the modified low-density polyethylene.

[0074] Preparation Example 2

[0075] The preparation steps of the modified low-density polyethylene are the same as those of Preparation Example 1, except that 1 g of maleic anhydride is added.

[0076] Preparation Example 3

[0077] The preparation steps of the modified low-density polyethylene are the same as those of Preparation Example 1, except that 6 g of maleic anhydride is added.

[0078] Preparation Example 4

[0079] The preparation steps of modified montmorillonite are as follows:

[0080] 10 g of montmorillonite and 750 mL of deionized water were added to the reactor, stirred and mixed at a speed of 800 r / min for 20 min, heated to 60° C., 0.8 g of ethylene bisstearamide and 0.5 g of titanate coupling agent NXH-501 were added, stirred and mixed at a speed of 800 r / min for 15 min, 2.3 g of linear low-density polyethylene was added, mixed and stirred for 5 min, cooled to room temperature, and dried to obtain the modified montmorillonite.

[0081] Preparation Example 5

[0082] The preparation steps of modified montmorillonite are the same as those of Preparation Example 4, except that 0.5 g of ethylene bisstearamide is added.

[0083] Preparation Example 6

[0084] The preparation steps of modified montmorillonite are the same as those of Preparation Example 4, except that 1.1 g of ethylene bisstearamide is added.

[0085] Preparation Example 7

[0086] The preparation steps of modified montmorillonite are the same as those of Preparation Example 4, except that 1.5 g of linear low-density polyethylene is added.

[0087] Preparation Example 8

[0088] The preparation steps of modified montmorillonite are the same as those of Preparation Example 4, except that 2.6 g of linear low-density polyethylene is added.

[0089] Preparation Example 9

[0090] The preparation steps of modified montmorillonite are as follows:

[0091] 10 g of montmorillonite and 750 mL of deionized water were added to the reactor, stirred and mixed at a speed of 800 r / min for 20 min, heated to 60° C., and then 0.8 g of ethylene bisstearamide and 0.5 g of titanate coupling agent NXH-501 were added, stirred and mixed at a speed of 800 r / min for 15 min, and then centrifuged and dehydrated, washed with deionized water 3 times, and dried to obtain the modified montmorillonite.

[0092] Unless otherwise specified, the graphene used in the following embodiments is all flake graphene, and the preferred particle size is 1000 mesh.

[0093] Example 1

[0094] A high-performance graphene roller tube material, the roller tube material comprising the following raw materials in parts by weight: 80 parts of ultra-high molecular weight polyethylene and 51 parts of masterbatch;

[0095] The masterbatch comprises the following raw materials in parts by weight: 3.3 parts of nano superconductive carbon black, 3 parts of micro powder graphite and 0.4 parts of modified low density polyethylene, 6.4 parts of microcapsule red phosphorus flame retardant ZP-H01, 10.6 parts of nano magnesium hydroxide, 3.1 parts of modified montmorillonite, 1.9 parts of white carbon black, 4.5 parts of silane coupling agent KH-560, 1.25 parts of antioxidant 1010, 0.75 parts of zinc stearate, 4 parts of propylene glycol, 4 parts of graphene and 7 parts of ethylene-acrylic acid copolymer.

[0096] The method for preparing the high-performance graphene roller tube material of this embodiment comprises the following steps:

[0097] (1) mixing nano superconductive carbon black, micro powder graphite, modified low density polyethylene, graphene, modified montmorillonite and white carbon black, adding silane coupling agent KH-560, heating to 105° C., stirring at a speed of 600 r / min for 20 min, and cooling to room temperature to obtain a mixture;

[0098] (2) adding microcapsule red phosphorus flame retardant ZP-H01, nano magnesium hydroxide, antioxidant 1010, zinc stearate, glycerol, ethylene-acrylic acid copolymer and the mixture of step (1) into a reactor, stirring at a speed of 500 r / min for 20 min to obtain a masterbatch;

[0099] (3) adding ultra-high molecular weight polyethylene to the masterbatch of step (2), stirring at a speed of 1000 r / min for 30 min, and obtaining the high-performance graphene roller tube material.

[0100] The modified low-density polyethylene used was obtained from Preparation Example 1, and the modified montmorillonite was obtained from Preparation Example 4.

[0101] Example 2

[0102] A high-performance graphene roller tube material, the roller tube material comprising the following raw materials in parts by weight: 60 parts of ultra-high molecular weight polyethylene and 32 parts of masterbatch;

[0103] The masterbatch comprises the following raw materials in parts by weight: 2.2 parts of nano superconductive carbon black, 2 parts of micro powder graphite and 0.8 parts of modified low density polyethylene, 5.25 parts of microcapsule red phosphorus flame retardant ZP-H01, 8.75 parts of nano magnesium hydroxide, 1.25 parts of modified montmorillonite, 0.75 parts of white carbon black, 2 parts of silane coupling agent KH-560, 0.5 parts of antioxidant 1010, 0.5 parts of zinc stearate, 2 parts of propylene glycol, 2 parts of graphene and 4 parts of ethylene-acrylic acid copolymer.

[0104] The method for preparing the high-performance graphene roller tube material of this embodiment comprises the following steps:

[0105] (1) mixing nano superconductive carbon black, micro powder graphite, modified low density polyethylene, graphene, modified montmorillonite and white carbon black, adding silane coupling agent KH-560, heating to 100° C., stirring at a speed of 500 r / min for 30 min, and cooling to room temperature to obtain a mixture;

[0106] (2) adding microcapsule red phosphorus flame retardant ZP-H01, nano magnesium hydroxide, antioxidant 1010, zinc stearate, glycerol, ethylene-acrylic acid copolymer and the mixture of step (1) into a reactor, stirring at a speed of 600 r / min for 10 min to obtain a masterbatch;

[0107] (3) adding ultra-high molecular weight polyethylene to the masterbatch of step (2), stirring at a speed of 900 r / min for 40 min, and obtaining the high-performance graphene roller tube material.

[0108] The modified low-density polyethylene used was obtained from Preparation Example 1, and the modified montmorillonite was obtained from Preparation Example 4.

[0109] Example 3

[0110] A high-performance graphene roller tube material, the roller tube material comprising the following raw materials in parts by weight: 100 parts of ultra-high molecular weight polyethylene and 70 parts of masterbatch;

[0111] The masterbatch comprises the following raw materials in parts by weight: 4.4 parts of nano superconductive carbon black, 4 parts of micro powder graphite and 1.6 parts of modified low density polyethylene, 7.5 parts of microcapsule red phosphorus flame retardant ZP-H01, 12.5 parts of nano magnesium hydroxide, 5 parts of modified montmorillonite, 3 parts of white carbon black, 7 parts of silane coupling agent KH-560, 2 parts of antioxidant 1010, 1 part of zinc stearate, 6 parts of propylene glycol, 6 parts of graphene and 10 parts of ethylene-acrylic acid copolymer.

[0112] The method for preparing the high-performance graphene roller tube material of this embodiment comprises the following steps:

[0113] (1) mixing nano superconductive carbon black, micro powder graphite, modified low density polyethylene, graphene, modified montmorillonite and white carbon black, adding silane coupling agent KH-560, heating to 110° C., stirring at a speed of 700 r / min for 10 min, and cooling to room temperature to obtain a mixture;

[0114] (2) adding microcapsule red phosphorus flame retardant ZP-H01, nano magnesium hydroxide, antioxidant 1010, zinc stearate, glycerol, ethylene-acrylic acid copolymer and the mixture of step (1) into a reactor, stirring at a speed of 400 r / min for 30 min to obtain a masterbatch;

[0115] (3) adding ultra-high molecular weight polyethylene to the masterbatch of step (2), stirring at a speed of 1100 r / min for 20 min, and obtaining the high-performance graphene roller tube material.

[0116] The modified low-density polyethylene used was obtained from Preparation Example 1, and the modified montmorillonite was obtained from Preparation Example 4.

[0117] Example 4

[0118] A high-performance graphene roller tube material and a preparation method thereof. The specific implementation method is the same as that of Example 1, except that the modified low-density polyethylene used is obtained from Preparation Example 2.

[0119] Example 5

[0120] A high-performance graphene roller tube material and a preparation method thereof. The specific implementation method is the same as that of Example 1, except that the modified low-density polyethylene used is obtained from Preparation Example 3.

[0121] Example 6

[0122] A high-performance graphene roller tube material and a preparation method thereof. The specific implementation method is the same as that of Example 1, except that the modified montmorillonite used is obtained from Preparation Example 5.

[0123] Example 7

[0124] A high-performance graphene roller tube material and a preparation method thereof, wherein the specific implementation manner is the same as that of Example 1, except that the modified montmorillonite used is obtained from Preparation Example 6.

[0125] Example 8

[0126] A high-performance graphene roller tube material and a preparation method thereof. The specific implementation method is the same as that of Example 1, except that the modified montmorillonite used is obtained from Preparation Example 7.

[0127] Example 9

[0128] A high-performance graphene roller tube material and a preparation method thereof, wherein the specific implementation manner is the same as that of Example 1, except that the modified montmorillonite used is obtained from Preparation Example 8.

[0129] Example 10

[0130] A high-performance graphene roller tube material and a preparation method thereof, wherein the specific implementation manner is the same as that of Example 1, except that the modified montmorillonite used is obtained from Preparation Example 9.

[0131] Embodiment 11

[0132] A high-performance graphene roller tube material and a preparation method thereof, wherein the specific implementation manner is the same as that of Example 1, except that the antistatic agent is a mixture of 3.5 parts of nano superconductive carbon black and 3.2 parts of micro powder graphite.

[0133] Example 12

[0134] A high-performance graphene roller tube material and a preparation method thereof, wherein the specific implementation manner is the same as that of Example 1, except that an equal amount of montmorillonite is used to replace modified montmorillonite.

[0135] Embodiment 13

[0136] A high-performance graphene roller tube material and a preparation method thereof, wherein the specific implementation manner is the same as that of Example 1, except that the modified low-density polyethylene is replaced by an equal amount of low-density polyethylene.

[0137] Performance Testing

[0138] The roller tube material prepared in the above examples 1-13 was extruded into a tube on a single screw extruder, and the extrusion melt temperature was controlled at 225-230° C. to obtain a roller tube. The following performance tests were performed. The specific test results are shown in Table 1:

[0139] (1) Mechanical properties test: The tensile strength and elongation at break of the above roller tube body are tested in accordance with standard GB / T1040-2006. The greater the tensile strength and elongation at break, the better the mechanical properties;

[0140] (2) Antistatic performance test: The antistatic performance test of the above roller tube body is carried out according to the standard MT / T1019-2006. The smaller the surface resistance, the better the antistatic performance;

[0141] (3) Flame retardant performance test: The flame retardant performance test of the roller tube body is carried out according to the standard MT113-1995. The shorter the flame burning time, the better the flame retardant performance.

[0142] Table 1

[0143]

[0144]

[0145] It can be seen from Table 1 that the roller tube material provided by Examples 1 to 3 of the present invention has both excellent permanent antistatic properties and flame retardancy, and has excellent mechanical properties and high performance stability.

[0146] By comparing Examples 4 to 5 with Example 1, it can be seen that when the amount of monomer grafting for preparing modified low-density polyethylene is changed, the tensile strength and elongation at break of the roller tube material will deteriorate; the antistatic agent added in Example 11 does not contain modified low-density polyethylene, and the mechanical properties and antistatic properties deteriorate, and the flame retardant properties are also affected to a certain extent; Example 13 adds unmodified low-density polyethylene, and its interaction with the components in the system is weakened, resulting in a significant impact on the mechanical properties and antistatic properties of the roller tube material; all of which illustrate that the viscosity between the masterbatch of the roller tube material containing the antistatic agent prepared under specific conditions and the ultra-high molecular weight polyethylene of the present invention is matched, the phase separation phenomenon is improved, the strong interaction between the molecules of each component is good, and it is uniform and stable, with excellent comprehensive performance.

[0147] Compared with Example 1, Examples 6 and 7 can illustrate that changing the amount of ethylene bisstearic acid amide added in the modified montmorillonite will lead to a deterioration in the tensile strength and elongation at break of the roller tube material, while the antistatic performance of Example 7 is better than that of Example 6, which may be due to the enrichment of -CO-NH- groups and the synergistic antistatic agent main component giving the system a better antistatic effect; Examples 8 and 9 can illustrate that changing the amount of low-density polyethylene added in the modified montmorillonite will lead to a deterioration in the tensile strength and elongation at break of the roller tube material; Example 10 has an effect on the antistatic performance of montmorillonite. Failure to add linear low-density polyethylene during the modification process will lead to deterioration in the mechanical properties, antistatic properties and flame retardant properties of the roller tube material. This may be due to the deterioration in the interaction between the modified montmorillonite and the system, especially the greater impact on the fit between the main component of montmorillonite and the ultra-high molecular weight polyethylene, and the deterioration in the system stability leading to deterioration in the overall performance. Example 12 adds unmodified montmorillonite and white carbon black as filler. At this time, the mechanical properties defects of the tube material are not effectively compensated, and the tensile strength and elongation at break both decrease to a certain extent.

[0148] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. Although the present invention has been disclosed as a preferred embodiment as above, it is not used to limit the present invention. Any technician familiar with this profession can make some changes or modifications to equivalent embodiments of equivalent changes using the technical contents disclosed above without departing from the scope of the technical solution of the present invention. However, any simple modification, equivalent change and modification made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention still fall within the scope of the technical solution of the present invention.

Claims

1. A high-performance graphene roller tube material, characterized in that: The roller tube material comprises the following raw materials in parts by weight: 60 to 100 parts of ultra-high molecular weight polyethylene and 32 to 70 parts of masterbatch; The masterbatch comprises the following raw materials in parts by weight: 2 to 6 parts of graphene, 5 to 10 parts of antistatic agent, 14 to 20 parts of flame retardant, 2 to 8 parts of filler, 2 to 7 parts of first coupling agent, 0.5 to 2 parts of antioxidant A, 0.5 to 1 part of nucleating agent, 2 to 6 parts of carbonizing agent and 4 to 10 parts of ethylene-acrylic acid copolymer.

2. A high-performance graphene roller tube material according to claim 1, characterized in that: The viscosity average molecular weight of the ultra-high molecular weight polyethylene is ≥3.5 million.

3. A high-performance graphene roller tube material according to claim 1, characterized in that: The antistatic agent is a mixture of nano superconductive carbon black, micro powder graphite and modified low density polyethylene.

4. A high-performance graphene roller tube material according to claim 3, characterized in that: The preparation steps of the modified low-density polyethylene are as follows: Add an organic solvent and low-density polyethylene into a reactor, then add an initiator and a modified monomer in sequence, raise the temperature to 40-70°C, stir evenly, introduce an inert atmosphere, treat with an ultraviolet lamp for 0.5-1h, rinse with an organic solvent, dry, add an antioxidant B, melt-knead for 20-40min at a temperature of 180-220°C and a rotation speed of 50-150r / min, and extrude and granulate to obtain the modified low-density polyethylene.

5. A high-performance graphene roller tube material according to claim 4, characterized in that: The modified monomer is maleic anhydride or acrylic acid; the mass ratio of the modified monomer to low-density polyethylene is (0.2-0.5):

1.

6. The high-performance graphene roller tube material according to claim 1, characterized in that: The flame retardant is two or three of microcapsule red phosphorus flame retardant, nano magnesium hydroxide and ammonium polyphosphate.

7. The high-performance graphene roller tube material according to claim 1, characterized in that: The filler is a mixture of modified montmorillonite and white carbon black.

8. The high-performance graphene roller tube material according to claim 7, characterized in that: The preparation steps of the modified montmorillonite are as follows: Add montmorillonite and deionized water into a reactor, stir and mix at a speed of 500 to 1200 r / min for 15 to 30 minutes, heat to 50 to 70° C., add a dispersant and a second coupling agent, stir and mix at a speed of 500 to 1200 r / min for 10 to 20 minutes, add linear low-density polyethylene, stir and mix for 2 to 8 minutes, cool to room temperature, and dry to obtain the modified montmorillonite.

9. A high-performance graphene roller tube material according to claim 8, characterized in that: The mass ratio of the montmorillonite, the dispersant, the second coupling agent and the linear low-density polyethylene is 10: (0.6-1): (0.2-0.8): (2-2.5).

10. A method for preparing the high-performance graphene roller tube material according to any one of claims 1 to 9, characterized in that: The following steps are involved: (1) mixing an antistatic agent, graphene and a filler, adding a first coupling agent, heating to 100 to 110° C., stirring at a speed of 500 to 700 r / min for 10 to 30 min, and cooling to room temperature to obtain a mixture; (2) adding a flame retardant, an antioxidant A, a nucleating agent, a carbonizing agent, an ethylene-acrylic acid copolymer and the mixture of step (1) into a reactor, and stirring at a speed of 400 to 600 r / min for 10 to 30 min to obtain a masterbatch; (3) adding ultra-high molecular weight polyethylene to the masterbatch of step (2), stirring at a speed of 900 to 1100 r / min for 20 to 40 min, and obtaining the high-performance graphene roller tube material.

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