A method for preparing an ultra-high molecular weight polyethylene fiber cloth / polyolefin composite

Abstract

The application provides a preparation method of an ultrahigh molecular weight polyethylene fiber cloth / polyolefin composite material, and comprises the following steps: 1. Fiber / fiber cloth modification: ultrasonic cleaning of the ultrahigh molecular weight polyethylene fiber / fiber cloth, drying, low-temperature plasma surface treatment, electrophoretic deposition of a layer of functionalized dopa-based substance on the surface of the fiber / fiber cloth, drying, and obtaining modified ultrahigh molecular weight polyethylene fiber / fiber cloth; 2. Resin matrix modification: taking polyolefin resin matrix such as polyethylene, polypropylene, hydrocarbon resin, vacuum drying treatment, melting, adding a certain amount of ethylene-propylene-diene rubber (EPDM) and vulcanizing agent for blending, and then taking out and hot-pressing into a sheet-shaped resin matrix; and 3. Laminating the modified ultrahigh molecular weight polyethylene fiber / fiber cloth obtained in the step 1 and the sheet-shaped resin matrix obtained in the step 2, and hot-pressing into a shape.

Description

Technical Field

[0001] This invention belongs to the field of fiber-reinforced composite materials technology, specifically relating to a method for preparing an ultra-high molecular weight polyethylene fiber cloth / polyolefin composite material. Background Technology

[0002] Invention patent CN108819391A discloses a composite material of ultra-high molecular weight polyethylene fiber-reinforced polyolefin and its derivatives, which is formed by laminating and hot-pressing fiber cloth with polyolefin and its derivative powders. However, the preparation process does not employ measures to improve the fiber-resin matrix interface.

[0003] Invention patent CN110218382A discloses an ultra-high molecular weight polyethylene fiber reinforced composite material for antenna radomes. It is made by impregnating ultra-high molecular weight polyethylene fibers with organosilicon resin solution, then laminating them with a polyethylene film, and adding a polycarbonate protective film on the outermost layer to form a sandwich structure layout and hot-pressing composite.

[0004] Invention patent CN112009054A discloses a composite sheet with one or more layers, formed by hot pressing composite yarns together. The composite yarns contain multi-component fibers and high-strength fibers. The multi-component fibers are selected from core-sheath composite fibers with polypropylene as the core layer and ethylene copolymer as the sheath layer, and three-layer composite fibers with polypropylene as the core layer, ethylene copolymer as the intermediate layer, and polyethylene as the sheath layer. The high-strength fibers are selected from ultra-high molecular weight polyethylene fibers, glass fibers, carbon fibers, aramid fibers, and basalt fibers.

[0005] Existing technologies for improving the fiber-resin interface primarily involve modifying the fiber surface through methods such as liquid-phase oxidation, chemical surface functionalization, surface coating, corona treatment, and plasma surface treatment. Currently, there are no reports of modification of the resin matrix, or synergistic modification of the fiber surface and resin matrix. Known modification methods offer limited improvement in interfacial adhesion performance and cannot meet market demands.

[0006] Furthermore, ultra-high molecular weight polyethylene (UHMWPE) fibers have low dielectric parameters (dielectric constant and dielectric loss). When used as a reinforcing material in composites with polyolefins, they help maintain their dielectric properties. However, commonly used UHMWPE fiber surface modification methods can damage the fiber structure or introduce new substances, which is not conducive to their application in situations requiring low dielectric properties.

[0007] Therefore, it is necessary to develop new ultra-high molecular weight polyethylene fiber cloth / polyolefin composite materials and their preparation methods to overcome the shortcomings of existing technologies. Summary of the Invention

[0008] To overcome the shortcomings of existing technologies, this invention provides a method for preparing ultra-high molecular weight polyethylene fiber cloth / polyolefin composite materials. By integrating fiber surface modification and resin matrix modification, the interfacial bonding strength of the ultra-high molecular weight polyethylene fiber cloth / polyolefin composite materials is improved, and a lightweight composite material with low dielectric parameters that can be applied to automobiles, bicycles, bags, radomes, antenna covers and other fields is prepared.

[0009] The technical solution of the present invention is as follows: A method for preparing ultra-high molecular weight polyethylene fiber cloth / polyolefin composite material, comprising the following steps:

[0010] Step 1. Fiber / fiber cloth modification: Ultra-high molecular weight polyethylene fiber / fiber cloth is ultrasonically cleaned, dried, and then subjected to low-temperature plasma surface treatment. Electrophoretic deposition is then performed on the treated ultra-high molecular weight polyethylene fiber / fiber cloth to deposit a layer of functionalized auxiliary agent polydopamine on its surface. After drying, it is ready for use to obtain modified ultra-high molecular weight polyethylene fiber / fiber cloth.

[0011] Step 2. Resin matrix modification: Take a polyolefin resin matrix, such as polyethylene, polypropylene, hydrocarbon resin, etc., vacuum dry it, then melt it, add a certain amount of ethylene propylene diene monomer (EPDM) rubber and vulcanizing agent (sulfur vulcanizing agent, peroxide vulcanizing agent) and mix it evenly, then take it out and hot press it into sheet resin matrix.

[0012] Step 3. The modified ultra-high molecular weight polyethylene fiber / fiber cloth obtained in Step 1 is laminated with the sheet resin matrix obtained in Step 2 and hot-pressed.

[0013] The low-temperature plasma source used in the low-temperature plasma surface treatment is a linear cathode layer plasma source or a radio frequency inductively coupled plasma source.

[0014] The voltage for the low-temperature plasma surface treatment is 500-1000V, the current is 0.5-2A, the treatment time is 20-60min, and the gas source is nitrogen, argon, oxygen, acetylene, or a mixture thereof.

[0015] This invention modifies the polyolefin resin matrix with EPDM rubber and a vulcanizing agent, thereby improving the interfacial adhesion between the matrix and the fiber and enhancing the performance of the composite material. The EPDM rubber has a vinyl content greater than 50% by mass, and the third monomer is ethylidene norbornene or dicyclopentadiene, with a mass fraction of 1-5%. The amount of EPDM rubber added is 1-10 parts (relative to the resin matrix). The vulcanizing agent is a sulfur-based vulcanizing agent and / or a peroxide vulcanizing agent.

[0016] This invention improves the fiber-resin interface adhesion of composite materials through fiber surface modification and resin matrix modification, thereby enhancing the performance of the composite materials.

[0017] The fiber modification and resin modification methods used in this invention have virtually no impact on the dielectric parameters of the composite material, which is beneficial for its application in the field of high-frequency wave transmission. Attached image description:

[0018] Figure 1 This is a process flow diagram of the preparation method of an ultra-high molecular weight polyethylene fiber cloth / polyolefin composite material according to the present invention. Detailed Implementation

[0019] To make the objectives, technical solutions, and effects of this invention clearer, the invention will be further described below in conjunction with specific embodiments. It should be understood that the specific embodiments described herein are for illustrative purposes only and are not intended to limit the scope of the invention.

[0020] Example 1: A method for preparing an ultra-high molecular weight polyethylene fiber cloth / polyolefin composite material, comprising the following steps:

[0021] Step 1. Fiber / fiber cloth modification: Ultra-high molecular weight polyethylene fiber / fiber cloth is ultrasonically cleaned, dried, and then subjected to low-temperature plasma surface treatment. Electrophoretic deposition is then performed on the treated ultra-high molecular weight polyethylene fiber / fiber cloth to deposit a layer of functionalized auxiliary agent polydopamine on its surface. After drying, it is ready for use to obtain modified ultra-high molecular weight polyethylene fiber / fiber cloth.

[0022] Step 2. Resin matrix modification: Take polyethylene resin matrix, vacuum dry it, then melt it, add a certain amount of ethylene propylene diene monomer (EPDM) rubber and vulcanizing agent and mix them evenly, then take it out and hot press it into sheet resin matrix.

[0023] Step 3. The modified ultra-high molecular weight polyethylene fiber / fiber cloth obtained in Step 1 is laminated with the sheet resin matrix obtained in Step 2 and hot-pressed.

[0024] The low-temperature plasma source used in the low-temperature plasma surface treatment is a linear cathode layer plasma source.

[0025] The low-temperature plasma surface treatment uses a voltage of 500V, a current of 2A, a treatment time of 60min, and argon and oxygen as the gas sources.

[0026] The vulcanizing agent is a sulfur-based vulcanizing agent.

[0027] Example 2

[0028] A method for preparing an ultra-high molecular weight polyethylene fiber cloth / polyolefin composite material includes the following steps:

[0029] Step 1. Fiber / fiber cloth modification: Ultra-high molecular weight polyethylene fiber / fiber cloth is ultrasonically cleaned, dried, and then subjected to low-temperature plasma surface treatment. Electrophoretic deposition is then performed on the treated ultra-high molecular weight polyethylene fiber / fiber cloth to deposit a layer of functionalized auxiliary agent polydopamine on its surface. After drying, it is ready for use to obtain modified ultra-high molecular weight polyethylene fiber / fiber cloth.

[0030] Step 2. Resin matrix modification: Take polypropylene resin matrix, vacuum dry it, then melt it, add a certain amount of ethylene propylene diene monomer (EPDM) rubber and vulcanizing agent (sulfur vulcanizing agent, peroxide vulcanizing agent) and mix it evenly, then take it out and hot press it into sheet resin matrix.

[0031] Step 3. The modified ultra-high molecular weight polyethylene fiber / fiber cloth obtained in Step 1 is laminated with the sheet resin matrix obtained in Step 2 and hot-pressed.

[0032] The low-temperature plasma source used in the low-temperature plasma surface treatment is a radio frequency inductively coupled plasma source.

[0033] The low-temperature plasma surface treatment uses a voltage of 700V, a current of 1.5A, a treatment time of 45min, and argon and nitrogen as gas sources.

[0034] The vulcanizing agent is a sulfur-based vulcanizing agent or a peroxide vulcanizing agent.

[0035] Example 3

[0036] A method for preparing an ultra-high molecular weight polyethylene fiber cloth / polyolefin composite material includes the following steps:

[0037] Step 1. Fiber / fiber cloth modification: Ultra-high molecular weight polyethylene fiber / fiber cloth is ultrasonically cleaned, dried, and then subjected to low-temperature plasma surface treatment. Electrophoretic deposition is then performed on the treated ultra-high molecular weight polyethylene fiber / fiber cloth to deposit a layer of functionalized auxiliary agent polydopamine on its surface. After drying, it is ready for use to obtain modified ultra-high molecular weight polyethylene fiber / fiber cloth.

[0038] Step 2. Resin matrix modification: Take a hydrocarbon resin matrix, vacuum dry it, then melt it, add a certain amount of EPDM rubber and vulcanizing agent (sulfur vulcanizing agent, peroxide vulcanizing agent) and mix it evenly, then take it out and hot press it into sheet resin matrix.

[0039] Step 3. The modified ultra-high molecular weight polyethylene fiber / fiber cloth obtained in Step 1 is laminated with the sheet resin matrix obtained in Step 2 and hot-pressed.

[0040] The low-temperature plasma source used in the low-temperature plasma surface treatment is a linear cathode layer plasma source.

[0041] The low-temperature plasma surface treatment uses a voltage of 850V, a current of 1A, a treatment time of 30min, and a gas source of argon, nitrogen, and acetylene.

[0042] The vulcanizing agent is a peroxide vulcanizing agent.

[0043] Example 4

[0044] A method for preparing an ultra-high molecular weight polyethylene fiber cloth / polyolefin composite material includes the following steps:

[0045] Step 1. Fiber / fiber cloth modification: Ultra-high molecular weight polyethylene fiber / fiber cloth is ultrasonically cleaned, dried, and then subjected to low-temperature plasma surface treatment. Electrophoretic deposition is then performed on the treated ultra-high molecular weight polyethylene fiber / fiber cloth to deposit a layer of functionalized auxiliary agent polydopamine on its surface. After drying, it is ready for use to obtain modified ultra-high molecular weight polyethylene fiber / fiber cloth.

[0046] Step 2. Resin matrix modification: Take polyethylene hydrocarbon resin matrix, vacuum dry it, then melt it, add a certain amount of ethylene propylene diene monomer (EPDM) rubber and vulcanizing agent (sulfur vulcanizing agent, peroxide vulcanizing agent) and mix it evenly, then take it out and hot press it into sheet resin matrix.

[0047] Step 3. The modified ultra-high molecular weight polyethylene fiber / fiber cloth obtained in Step 1 is laminated with the sheet resin matrix obtained in Step 2 and hot-pressed.

[0048] The low-temperature plasma source used in the low-temperature plasma surface treatment is a radio frequency inductively coupled plasma source.

[0049] The low-temperature plasma surface treatment uses a voltage of 950V, a current of 0.5A, a treatment time of 20min, and a gas source of argon, nitrogen, and oxygen.

[0050] The vulcanizing agent is a sulfur-based vulcanizing agent.

[0051] Comparative example

[0052] A method for preparing an ultra-high molecular weight polyethylene fiber cloth / polyolefin composite material includes the following steps:

[0053] Step 1. Fiber / Fiber Cloth: Ultra-high molecular weight polyethylene fiber / fiber cloth is ultrasonically cleaned and dried for later use.

[0054] Step 2. Resin matrix: Take polyethylene resin matrix, vacuum dry it, then melt it and hot press it into sheet resin matrix.

[0055] Step 3. Lay the ultra-high molecular weight polyethylene fiber / fiber cloth obtained in Step 1 with the sheet resin matrix obtained in Step 2, and hot press them together.

[0056] To further verify the performance of the ultra-high molecular weight polyethylene fiber cloth / polyolefin composite material prepared in this invention, the inventors conducted tests on the ultra-high molecular weight polyethylene fiber cloth / polyolefin composite materials prepared in Examples 1-4 and Comparative Examples. The method or standard for testing the interfacial bond strength was (GB2792 or ASTM D3330), and the method or standard for testing the dielectric parameters was (ASTM D150).

[0057] The test data is shown in the table below.

[0058]

[0059] The above description, in conjunction with specific preferred embodiments, provides a further detailed explanation of the present invention and should not be construed as limiting the specific implementation of the invention to these descriptions. For those skilled in the art, the architectural form of this invention can be flexibly varied without departing from its conceptual framework, leading to the derivation of a series of products. Any simple deductions or substitutions should be considered as falling within the patent protection scope defined by the submitted claims.

Claims

1. A method for preparing an ultra-high molecular weight polyethylene fiber cloth / polyolefin composite material, characterized in that, Includes the following steps: Step 1. Fiber cloth modification: Ultra-high molecular weight polyethylene fiber cloth is ultrasonically cleaned, dried, and then subjected to low-temperature plasma surface treatment. Electrophoretic deposition is performed on the treated ultra-high molecular weight polyethylene fiber cloth to deposit a layer of functionalized additive polydopamine on its surface; then it is dried for later use to obtain modified ultra-high molecular weight polyethylene fiber cloth. Step 2. Resin matrix modification: Take a polyolefin resin matrix, vacuum dry it, then melt it, add ethylene propylene diene monomer (EPDM) rubber and vulcanizing agent and mix them evenly, then take it out and hot press it into a sheet resin matrix; Step 3. The modified ultra-high molecular weight polyethylene fiber cloth obtained in Step 1 is laminated with the sheet resin matrix obtained in Step 2 and hot-pressed. The polyolefin resin matrix is ​​selected from polyethylene, polypropylene, or mixtures thereof; The vulcanizing agent is a sulfur-based vulcanizing agent and / or a peroxide vulcanizing agent.

2. The method for preparing the ultra-high molecular weight polyethylene fiber cloth / polyolefin composite material according to claim 1, characterized in that, The low-temperature plasma source used in the low-temperature plasma surface treatment is a linear cathode layer plasma source or a radio frequency inductively coupled plasma source.

3. The method for preparing the ultra-high molecular weight polyethylene fiber cloth / polyolefin composite material according to claim 1, characterized in that, The voltage for the low-temperature plasma surface treatment is 500-1000V, the current is 0.5-2A, the treatment time is 20-60min, and the gas source is nitrogen, argon, oxygen, acetylene, or a mixture thereof.

4. The method for preparing the ultra-high molecular weight polyethylene fiber cloth / polyolefin composite material according to claim 1, characterized in that, The vinyl fraction of the EPDM rubber is greater than 50%, and the third monomer is ethylidene norbornene or dicyclopentadiene, with a mass fraction of 1-5%. The amount of EPDM rubber added is 1-10 parts of the polyolefin resin matrix.

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