阅读说明：本技术 托辊用石墨烯导电高分子复合材料、制备方法及应用 (Graphene conductive polymer composite material for carrier roller, preparation method and application ) 是由 宗旭 田振宇 吴昊 谢卫宏 刘中车 郑雅轩 瞿研 于 2021-08-30 设计创作，主要内容包括：本发明公开了托辊用石墨烯导电高分子复合材料,各组分按照重量份数计,包括：50～70份高密度聚乙烯、10～30份无碱玻璃纤维、1～10份导电剂、1～5份接枝剂、0.1～1份石墨烯、0.1～0.5份抗氧剂、0.1～0.5份抗紫外剂和0.1～1份润滑剂。本发明还公开了制备方法及应用。本发明在提升材料导电性能的同时提升力学性能,并且加工工艺简单、制造成本低廉、具有较高的性价比。(The invention discloses a graphene conductive polymer composite material for a carrier roller, which comprises the following components in parts by weight: 50-70 parts of high-density polyethylene, 10-30 parts of alkali-free glass fiber, 1-10 parts of a conductive agent, 1-5 parts of a grafting agent, 0.1-1 part of graphene, 0.1-0.5 part of an antioxidant, 0.1-0.5 part of an anti-ultraviolet agent and 0.1-1 part of a lubricant. The invention also discloses a preparation method and application. The invention improves the mechanical property while improving the electrical conductivity of the material, and has the advantages of simple processing technology, low manufacturing cost and higher cost performance.)

1. The graphene conductive polymer composite material for the carrier roller is characterized by comprising the following components in parts by weight:

2. the graphene conductive polymer composite material for a carrier roller according to claim 1, wherein the graphene conductive polymer composite material comprises the following components in parts by weight:

3. a graphene conductive polymer composite material for a carrier roller according to claim 1 or 2, wherein the sum of the parts by weight of the components is 100.

4. A graphene conductive polymer composite material for a carrier roller according to claim 1 or 2, wherein the high density polyethylene is 100-grade polyethylene and has a molecular weight of 4-30 ten thousand.

5. The graphene conductive polymer composite material for the carrier roller according to claim 1 or 2, wherein the alkali-free glass fiber has a diameter of 8-14 micrometers, preferably 13-14 micrometers.

6. The graphene conductive polymer composite material for the carrier roller according to claim 1 or 2, wherein the conductive agent is conductive carbon black or/and carbon nanotubes; or/and

the grafting agent is PE grafted maleic anhydride; or/and

the antioxidant is 1010 or/and 168; or/and

the anti-ultraviolet agent is UV531 or/and UV 770.

7. The graphene conductive polymer composite material for the carrier roller according to claim 1 or 2, wherein the parameter of the graphene is BET (BET) not less than 180m²G, D50 is less than or equal to 27 mu m, and the mass fraction of oxygen<1％。

8. A graphene conductive polymer composite material for a carrier roller as claimed in claim 1 or 2, wherein the lubricant is one or more of erucamide, zinc stearate or calcium stearate.

9. A preparation method of the graphene conductive polymer composite material for the carrier roller as claimed in any one of claims 1 to 8, characterized by comprising:

weighing high-density polyethylene, graphene, a grafting agent, a conductive agent, an antioxidant, an anti-ultraviolet agent and a lubricant, and putting the materials into a high-speed stirrer to be mixed and stirred to be used as a mixed material, wherein the stirring time is preferably 10-30 min;

and simultaneously adding the mixed material into a double-screw extruder through a hopper by a weightless scale for extrusion, simultaneously weighing alkali-free glass fibers, adding the alkali-free glass fibers into a fiber adding port in the operation process of the double-screw extruder, mixing and extruding the mixed material and the weighed alkali-free glass fibers to obtain the graphene conductive polymer composite material for the carrier roller, wherein preferably, the feeding speed of the double-screw extruder is 30-50rpm, and the rotating speed of a host is 300 plus 500 rpm.

10. An application of the graphene conductive polymer composite material for the carrier roller according to any one of claims 1 to 8 in the carrier roller.

Technical Field

The invention relates to the technical field of polymer processing, in particular to a graphene conductive polymer composite material for a carrier roller, a preparation method and application.

Background

The carrier roller is used as an important component of the belt conveyor and is used for supporting the weight of the conveying belt and materials, and the carrier roller has the characteristics of multiple types and large using amount. Research studies have shown that conventional idlers on the market account for 35% of the total cost of a belt conveyor, but at the same time offer 70% resistance to the transport of material during the conveying process, and therefore the quality of the idler has a critical effect on the overall performance of the belt conveyor. The existing carrier roller on the market is divided into steel and plastic, the steel carrier roller is a main product on the market all the time due to excellent performance, but with the industrial modernization development, the steel carrier roller has the defects of heavy weight, high cost and the like; therefore, the plastic carrier roller gradually becomes a new generation product with light weight and low cost for replacing a steel carrier roller.

CN104292699A discloses an antistatic flame-retardant composite material for coal mine and a preparation method thereof, wherein a conductive filler/PVC composite powder material is prepared by mixing a mixture of carbon nanotubes and graphene with a part of polyvinyl chloride (PVC) resin according to a proportion; the obtained conductive filler/PVC composite powder material, the rest of PVC resin, ABS, a compatibilizer, a heat stabilizer, a lubricant and a processing aid are mixed at a high speed to obtain a compound, and the mixed compound is placed in a conical double-screw extruder to be extruded and granulated at a sectional temperature, so that the antistatic flame-retardant composite material for the coal mine is obtained. CN107418045B discloses a "graphene modified polypropylene machine with high strength and high rigidity" and a preparation method thereof, in which various additives such as graphene, alkali-free glass fiber, enzymatic lignin, compatilizer, etc. are dispersed in matrix resin by a twin screw; the invention patent uses modified homo-polypropylene as matrix resin, and the addition amount of graphene is very high (15-20 parts), so that the cost is very high on one hand, and the processing is very difficult on the other hand.

In order to make the material reach the conductive level, namely the surface resistance (less than or equal to 10)⁶Ω), a large amount of conductive agent such as conductive carbon black, carbon nanotubes, etc. is required, which easily causes an increase in the cost of the material and a decrease in mechanical properties, and is not suitable for mass production and use for a long period of time. Under the condition of a low addition amount (0.1-1%), the graphene can not only improve the conductivity of the material, but also improve the mechanical property of the material, so that the material can meet the use requirement under a conductive environment, and has excellent mechanical property.

Disclosure of Invention

Aiming at one or more problems in the prior art, the invention provides a graphene conductive polymer composite material for a carrier roller, which comprises the following components in parts by weight:

optionally, the components comprise, by weight:

optionally, the sum of the parts by weight of the components is 100.

Optionally, the high-density polyethylene is 100-grade polyethylene, the molecular weight is 4-30 ten thousand, and the high-density polyethylene has the advantages of high hardness, high density, high mechanical strength of the material and the like compared with conventional low-density polyethylene, and compared with polyvinyl chloride, the high-density polyethylene belongs to an environment-friendly material, and compared with polypropylene, the high-density polyethylene has better toughness.

Optionally, the diameter of the alkali-free glass fiber is 8-14 microns, and preferably, the diameter of the alkali-free glass fiber is 13-14 microns.

Optionally, the conductive agent is conductive carbon black or/and carbon nanotubes.

Optionally, the grafting agent is PE grafted maleic anhydride. The grafting agent has the function of increasing the interface compatibility between the matrix resin and the inorganic filler (such as glass fiber), and has great help to improve the mechanical property of the material within a certain range (such as 5 parts of grafting agent can improve the mechanical property of more than or equal to 20%). If the addition amount is too high, the redundant components do not play a role of interface bonding, and the mechanical property of the material is negatively affected.

Optionally, the parameter of the graphene is BET ≥ 180m²G, D50 is less than or equal to 27 mu m, and the mass fraction of oxygen<1%, the larger the BET is, the smaller the oxygen mass fraction is, and the better the corresponding graphene conductivity is. The conductivity of the material can reach the standard by independently adding the conductive energy, but the mechanical reduction of the material is serious, the conventional use of the material after forming is not facilitated, and the addition of the graphene can improve the conductivity of the material (for example, 0.5 percent of the graphene can ensure that the original surface resistance of the material is 10⁸The omega HDPE composite material is lifted to be less than or equal to 10⁶Ω), mechanical properties can also be improved (example: 0.5 percent of graphene can improve the tensile strength of the HDPE composite material by more than or equal to 10 percent). The graphene can improve the conductivity of the material and the mechanical property of the material under the condition of low addition (0.1-1%), so that the material can meet the use requirement under a conductive environment, and has excellent mechanical property.

Optionally, the antioxidant is antioxidant 1010 or/and antioxidant 168.

Optionally, the anti-ultraviolet agent is UV531 or/and UV 770.

Optionally, the lubricant is one or more of erucamide, zinc stearate or calcium stearate.

According to another aspect of the invention, a preparation method of the graphene conductive polymer composite material for the carrier roller is provided, which includes:

weighing high-density polyethylene, graphene, a grafting agent, a conductive agent, an antioxidant, an anti-ultraviolet agent and a lubricant, and putting the materials into a high-speed stirrer to be mixed and stirred to be used as a mixed material (powder material), preferably, the stirring time is 10-30 min;

adding the mixed materials (granules and powder) into a double-screw extruder through a hopper for extrusion by a weightless scale, simultaneously weighing alkali-free glass fibers, adding the alkali-free glass fibers into a fiber adding port in the operation process of the double-screw extruder, mixing and extruding the mixed materials and the weighed alkali-free glass fibers to obtain the graphene conductive polymer composite material for the carrier roller, preferably, the feeding speed of the double-screw extruder is 30-50rpm, the rotating speed of a host is 300 plus 500rpm, the glass fibers are added from the fiber adding port, the fiber adding port is directly connected with the screw, and the higher the rotating speed of the host is and the higher the content of the glass fibers is at the same feeding speed.

According to a third aspect of the invention, an application of the graphene conductive polymer composite material for the carrier roller in the carrier roller is provided.

According to the graphene conductive polymer composite material for the carrier roller and the preparation method thereof, graphene is added, so that the mechanical property is improved while the conductive property of the material is improved, and the graphene conductive polymer composite material is simple in processing technology, low in manufacturing cost and high in cost performance.

The graphene conductive polymer composite material has good comprehensive performance, and has better advantages and application prospects compared with the traditional steel carrier roller in the market. The carrier roller made of the graphene conductive polymer composite material has the advantages of high strength, low manufacturing cost, light weight, low requirement on an extruder and the like.

The carrier roller in the current market is mostly made of steel, the cost of raw materials is high, the weight is heavy, and in the invention, the carrier roller special material with the conductive performance prepared by taking the general-purpose plastic high-density polyethylene as the matrix material has the advantages of lower cost, low requirement on equipment, simple processing and forming process and obvious advantages.

The carrier roller produced by the graphene conductive polymer composite material has the advantages of light weight, easiness in replacement and maintenance and the like, and can replace a conventional steel carrier roller to be used in the scenes such as mines, chemical engineering, wharfs, salt yards and the like.

Detailed Description

The technical solutions of the present invention will be described clearly and completely in the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

The conductive polymer composite material for the carrier roller of the embodiment comprises the following raw material components in parts by weight:

67 parts of high-density polyethylene, 25 parts of alkali-free glass fiber, 3 parts of conductive agent, 0.1 part of graphene, 4 parts of grafting agent, 0.1 part of antioxidant, 0.5 part of anti-ultraviolet agent and 0.3 part of lubricant, wherein the total is 100 parts.

Wherein the specification of the high-density polyethylene is as follows: 100 grade polyethylene, molecular weight 10 ten thousand;

the diameter of the alkali-free glass fiber is 14 micrometers;

the conductive agent is: conductive carbon black

The grafting agent is: grafting maleic anhydride on PE;

BET of graphene is 260m²The preparation method comprises the following steps of (1) selecting an enhanced graphene product (product model: SE1430) produced by Heizhou sixth-element material science and technology limited company, wherein D50 is 27 mu m, and the mass fraction of oxygen is 0.8%;

the antioxidant is as follows: an antioxidant 1010;

the uvioresistant agent is: UV 531;

the lubricant is: and (3) zinc stearate.

The preparation method of the conductive polymer composite material for the carrier roller of the embodiment comprises the following steps:

accurately weighing the resin, the graphene and other fillers (grafting agent, conductive agent, antioxidant, uvioresistant agent and lubricant) in the formula, putting the materials into a high-speed stirrer, mixing and stirring the materials to obtain powder for 10-30min, then accurately adding the granules and the powder into a double-screw extruder through a hopper by weight loss scale for extrusion, simultaneously adding a certain number of alkali-free glass fibers into a fiber adding port according to the formula amount in the operation process of the double-screw extruder, adjusting the feeding speed to 30-50rpm and the rotating speed of a main machine to 300-500rpm, and enabling the content of the alkali-free glass fibers in the final particles to meet the addition amount in the formula. Finally, preparing the graphene conductive polymer composite material for the carrier roller.

Wherein the parameters of the twin-screw extrusion are set as follows: the temperatures of the first stage to the tenth stage were 180 ℃, 190 ℃, 210 ℃, 220 ℃, 240 ℃ for the head temperature, 400rpm for the main machine, and 40rpm for the feeding rate, respectively. The pellets were pelletized by twin screw extrusion and the resulting pellets were sampled to test performance.

Example 2

The conductive polymer composite material for the carrier roller of the embodiment comprises the following raw material components in parts by weight:

70 parts of high-density polyethylene, 20 parts of alkali-free glass fiber, 6 parts of conductive agent, 0.5 part of graphene, 2 parts of grafting agent, 0.3 part of antioxidant, 0.2 part of anti-ultraviolet agent and 1 part of lubricant, wherein the total is 100 parts.

Wherein the specification of the high-density polyethylene is as follows: 100 grade polyethylene, molecular weight 10 ten thousand;

the diameter of the alkali-free glass fiber is 13 micrometers;

the conductive agent is: conductive carbon black

The grafting agent is: grafting maleic anhydride on PE;

BET of graphene is 220m²The preparation method comprises the following steps of (1) selecting an enhanced graphene product (product model: SE1430) produced by Heizhou sixth-element material science and technology limited company, wherein D50 is 27 mu m, and the mass fraction of oxygen is 0.8%;

the antioxidant is as follows: an antioxidant 168;

the uvioresistant agent is: UV 770;

the lubricant is: calcium stearate.

The preparation method of the conductive polymer composite material for the carrier roller in the embodiment is the same as that in the embodiment 1.

The pellets were pelletized by twin screw extrusion and the resulting pellets were sampled to test performance.

Example 3

The conductive polymer composite material for the carrier roller of the embodiment comprises the following raw material components in parts by weight:

67 parts of high-density polyethylene, 25 parts of alkali-free glass fiber, 6 parts of conductive agent, 0.5 part of graphene, 1 part of grafting agent, 0.2 part of antioxidant, 0.2 part of anti-ultraviolet agent and 0.1 part of lubricant, wherein the total is 100 parts.

Wherein the specification of the high-density polyethylene is as follows: 100 grade polyethylene, molecular weight 10 ten thousand;

the diameter of the alkali-free glass fiber is 13 micrometers;

the conductive agent is: conductive carbon black

The grafting agent is: grafting maleic anhydride on PE;

BET of graphene is 260m²The preparation method comprises the following steps of (1) selecting an enhanced graphene product (product model: SE1430) produced by Heizhou sixth-element material science and technology limited company, wherein D50 is 27 mu m, and the mass fraction of oxygen is 0.8%;

the antioxidant is as follows: an antioxidant 1010;

the uvioresistant agent is: UV 770;

the lubricant is: erucamide.

The preparation method of the conductive polymer composite material for the carrier roller in the embodiment is the same as that in the embodiment 1.

The pellets were pelletized by twin screw extrusion and the resulting pellets were sampled to test performance.

Example 4

The conductive polymer composite material for the carrier roller of the embodiment comprises the following raw material components in parts by weight:

60 parts of high-density polyethylene, 24 parts of alkali-free glass fiber, 10 parts of conductive agent, 0.1 part of graphene, 5 parts of grafting agent, 0.3 part of antioxidant, 0.3 part of anti-ultraviolet agent and 0.3 part of lubricant, wherein the total is 100 parts.

Wherein the specification of the high-density polyethylene is as follows: 100 grade polyethylene, molecular weight 10 ten thousand;

the diameter of the alkali-free glass fiber is 14 micrometers;

the conductive agent is: conductive carbon black

The grafting agent is: grafting maleic anhydride on PE;

BET of graphene is 260m²The preparation method comprises the following steps of (1) selecting an enhanced graphene product (product model: SE1430) produced by Heizhou sixth-element material science and technology limited company, wherein D50 is 27 mu m, and the mass fraction of oxygen is 0.8%;

the antioxidant is as follows: an antioxidant 168;

the uvioresistant agent is: UV 531;

the lubricant is: calcium stearate.

The preparation method of the conductive polymer composite material for the carrier roller in the embodiment is the same as that in the embodiment 1.

The pellets were pelletized by twin screw extrusion and the resulting pellets were sampled to test performance.

Example 5

The conductive polymer composite material for the carrier roller of the embodiment comprises the following raw material components in parts by weight:

66 parts of high-density polyethylene, 30 parts of alkali-free glass fiber, 1 part of conductive agent, 1 part of graphene, 1 part of grafting agent, 0.5 part of antioxidant, 0.1 part of anti-ultraviolet agent and 0.4 part of lubricant, wherein the total is 100 parts.

Wherein the specification of the high-density polyethylene is as follows: 100 grade polyethylene, molecular weight 10 ten thousand;

the diameter of the alkali-free glass fiber is 13 micrometers;

the conductive agent is: carbon nanotube

The grafting agent is: grafting maleic anhydride on PE;

BET of graphene is 260m²The preparation method comprises the following steps of (1) selecting an enhanced graphene product (product model: SE1430) produced by Heizhou sixth-element material science and technology limited company, wherein D50 is 27 mu m, and the mass fraction of oxygen is 0.8%;

the antioxidant is as follows: an antioxidant 1010;

the uvioresistant agent is: UV 770;

the lubricant is: erucamide.

The preparation method of the conductive polymer composite material for the carrier roller in the embodiment is the same as that in the embodiment 1.

The pellets were pelletized by twin screw extrusion and the resulting pellets were sampled to test performance.

Comparative example 1

The conductive polymer composite material for the carrier roller of the comparative example comprises the following raw material components in parts by weight:

65 parts of high-density polyethylene, 25 parts of alkali-free glass fiber, 5 parts of conductive agent, 4 parts of grafting agent, 0.3 part of antioxidant, 0.3 part of anti-ultraviolet agent and 0.4 part of lubricant, wherein the total is 100 parts.

Wherein the specification of the high-density polyethylene is as follows: 100 grade polyethylene, molecular weight 10 ten thousand;

the diameter of the alkali-free glass fiber is 13 micrometers;

the conductive agent is: carbon nanotube

The grafting agent is: grafting maleic anhydride on PE;

the antioxidant is as follows: an antioxidant 1010;

the uvioresistant agent is: UV 531;

the lubricant is: erucamide.

The preparation method of the conductive polymer composite material for the carrier roller in the comparative example is the same as that of the embodiment 1.

The pellets were pelletized by twin screw extrusion and the resulting pellets were sampled to test performance.

Comparative example 2

The conductive polymer composite material for the carrier roller of the comparative example comprises the following raw material components in parts by weight:

68 parts of high-density polyethylene, 25 parts of alkali-free glass fiber, 6 parts of conductive agent, 0.5 part of graphene, 0.1 part of antioxidant, 0.2 part of anti-ultraviolet agent and 0.2 part of lubricant, wherein the total is 100 parts.

Wherein the specification of the high-density polyethylene is as follows: 100 grade polyethylene, molecular weight 10 ten thousand;

the diameter of the alkali-free glass fiber is 13 micrometers;

the conductive agent is: conductive carbon black

BET of graphene is 260m²G, D50 is 27 μm, mass fraction of oxygen0.8 percent, and selecting an enhanced graphene product (product model: SE1430) produced by Heizhou sixth element material science and technology Limited;

the antioxidant is as follows: an antioxidant 168;

the uvioresistant agent is: UV 531;

the lubricant is: erucamide.

The preparation method of the conductive polymer composite material for the carrier roller in the comparative example is the same as that of the embodiment 1.

The pellets were pelletized by twin screw extrusion and the resulting pellets were sampled to test performance.

Comparative example 3

The conductive polymer composite material for the carrier roller of the comparative example comprises the following raw material components in parts by weight:

63 parts of high-density polyethylene, 25 parts of alkali-free glass fiber, 5 parts of conductive agent, 0.2 part of graphene, 6 parts of grafting agent, 0.1 part of antioxidant, 0.3 part of anti-ultraviolet agent and 0.4 part of lubricant, wherein the total is 100 parts.

Wherein the specification of the high-density polyethylene is as follows: 100 grade polyethylene, molecular weight 10 ten thousand;

the diameter of the alkali-free glass fiber is 13 micrometers;

the conductive agent is: carbon nanotube

The grafting agent is: grafting maleic anhydride on PE;

the antioxidant is as follows: an antioxidant 1010;

the uvioresistant agent is: UV 531;

the lubricant is: erucamide.

The preparation method of the conductive polymer composite material for the carrier roller in the comparative example is the same as that of the embodiment 1.

Comparative example 4

The conductive polymer composite material for the carrier roller of the comparative example comprises the following raw material components in parts by weight:

64 parts of high-density polyethylene, 24 parts of alkali-free glass fiber, 8 parts of conductive agent, 0.8 part of graphene, 2.5 parts of grafting agent, 0.2 part of antioxidant, 0.2 part of anti-ultraviolet agent and 0.3 part of lubricant, wherein the total is 100 parts.

Wherein the specification of the high-density polyethylene is as follows: 100 grade polyethylene, molecular weight 10 ten thousand;

the diameter of the alkali-free glass fiber is 14 micrometers;

the conductive agent is: conductive carbon black

The grafting agent is: grafting maleic anhydride on PE;

BET of graphene is 170m²(iv)/g, D50 is 30 μm, the mass fraction of oxygen is 1.05%, provided by Changzhou Xiancheng nano;

the antioxidant is as follows: an antioxidant 1010;

the uvioresistant agent is: UV 770;

the lubricant is: erucamide.

The preparation method of the conductive polymer composite material for the carrier roller in the embodiment is the same as that in the embodiment 1.

The pellets were pelletized by twin screw extrusion and the resulting pellets were sampled to test performance.

Wherein the raw materials used in examples 1-5 and comparative examples 1-3 are commercially available except for graphene.

The performances of the conductive polymer composite materials for the carrier rollers prepared in examples 1 to 5 and comparative examples 1 to 3 were tested by the following test methods and test standards, respectively:

conducting electricity: GB/T1410-2006.

Tensile strength: GB/T1040.1-2006.

Bending strength: GB/T9341-2008.

Flexural modulus: GB/T9341-2008.

Density: GB/T1033.1-2008.

Shore hardness: GB/T2411-2008.

The results are shown in table 1 (the values in table 1 are the average values obtained by testing three samples of the same batch):

TABLE 1

As can be seen from the above table, the main performance data of the graphene conductive polymer composite material of the present invention are as follows: conductivity, i.e. surface resistance, less than or equal to 10⁶Omega, tensile strength is more than or equal to 50MPa, bending strength is more than or equal to 60MPa, bending modulus is more than or equal to 2500MPa, density is less than or equal to 1.25g/cm³Hardness (Shore Hardness) is not less than 60D. Wherein the surface resistance of the material reaches less than or equal to 10⁴Omega, meet the requirement of making bearing seat products of the carrier roller.

Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.