CN107189122B - A kind of carbon fiber-based puncture resistant rubber composite material and preparation method thereof - Google Patents

Abstract

The invention discloses a carbon fiber-based puncture-resistant rubber composite material and a preparation method thereof, and relates to the technical field of rubber/carbon fiber composite materials. Including the following raw materials in parts by weight: rubber 100, 2,2'-diallyl bisphenol A 5-10, liquid nitrile rubber 8-15, chopped carbon fiber 0.5-2.0, vulcanization active agent 3-5, surface active Agent 0.5-2.0, cross-linking agent 0.5-2.5, vulcanization accelerator 0.5-3.5, anti-aging agent 0.5-3.0, reinforcing agent 15-30. Preparation method: chopped carbon fiber is dispersed in 2,2'-diallyl bisphenol A and liquid nitrile rubber at 110-140°C to form rubberized carbon fiber, and then mixed with rubber, vulcanized and cross-linked to obtain the product . The rubber is composed of natural rubber and synthetic rubber, and the synthetic rubber is nitrile rubber and styrene-butadiene rubber, or nitrile rubber and butadiene rubber, or nitrile rubber, styrene-butadiene rubber and butadiene rubber. The composite material has stable performance, simple preparation process, high efficiency, low cost and good dispersion effect of carbon fiber in rubber.

Description

A carbon fiber-based puncture-resistant rubber composite material and its preparation method

technical field

The invention relates to the technical field of rubber/carbon fiber composite materials, in particular to a carbon fiber-based puncture-resistant rubber composite material and a preparation method thereof.

Background technique

Short fiber reinforced rubber composite (SFRC) is a reinforced composite material similar to polymer blends made by dispersing short fibers in a rubber matrix and compounding them with rubber. SFRC not only has the elasticity of rubber, but also maintains the strength and stiffness of fibers. The products made of it have excellent properties such as high strength, high modulus, tear resistance, and swelling resistance. The performance of the product can be designed by controlling the orientation of the short fiber in the product. This material combines the flexibility of rubber with the rigidity of short fibers, resulting in high modulus, high puncture resistance, high tear strength, and high stress and anisotropy at low elongation Features.

At present, carbon fiber has attracted widespread attention at home and abroad because of its high modulus, high strength, low density, low thermal expansion coefficient, and high dimensional stability. become a hotspot in this field. Carrying out research work on chopped carbon fiber and rubber composite materials is of great significance for improving the overall level of my country's rubber industry. However, in the actual production and processing process, it is difficult for carbon fiber to disperse evenly into the rubber matrix, and due to self-aggregation, the interfacial bonding force between rubber and carbon fiber is very low, and it is easy to phase separate, so that the performance of the composite material Greatly discounted, far less than expected performance indicators.

In order to overcome this problem, scientists from various countries have used various methods to chemically modify and modify the surface of carbon fibers, such as electrochemical oxidation, coupling agent coating, sol-gel modification, chemical grafting modification, etc. However, the above-mentioned methods all have problems such as low efficiency, high cost, and difficulty in large-scale industrialization, and some methods also have problems such as solvent recovery and environmental pollution due to the use of a large amount of solvent. Therefore, the development of new methods for the preparation of green and environmentally friendly carbon fiber-based puncture-resistant rubber composites has become an urgent problem to be solved in the field of special engineering rubber composites.

Contents of the invention

The technical problem to be solved by the present invention is to provide a carbon fiber-based puncture-resistant rubber composite material and its preparation method. The performance of the composite material product is stable, the preparation process is simple, easy to implement, high in efficiency, low in cost, and the dispersion effect of carbon fiber in rubber Well, the production process is pollution-free.

In order to solve the above technical problems, the technical solution adopted by the present invention is: a carbon fiber-based puncture-resistant rubber composite material, including the following raw materials in parts by weight: 100 parts of rubber, 2,2'-diallyl bisphenol A 5 ～10 parts, 8～15 parts of liquid nitrile rubber, 0.5～2.0 parts of chopped carbon fiber, 3～5 parts of vulcanization activator, 0.5～2.0 parts of surfactant, 0.5～2.5 parts of crosslinking agent, 0.5～2.0 parts of vulcanization accelerator 3.5 parts, 0.5-3.0 parts of anti-aging agent, 15-30 parts of reinforcing agent; the rubber is composed of natural rubber and synthetic rubber, wherein the synthetic rubber is a mixture of nitrile rubber and styrene-butadiene rubber, or the synthetic rubber is nitrile rubber and butadiene rubber, or synthetic rubber is a mixture of nitrile rubber, styrene-butadiene rubber and butadiene rubber.

The structural formula of 2,2'-diallyl bisphenol A is as follows:

Preferably, the number average molecular weight of the liquid nitrile rubber is 3000-3500.

Preferably, the length of the chopped carbon fiber is 2-10 mm.

Preferably, the vulcanization active agent is zinc oxide, the surfactant is stearic acid, the crosslinking agent is sulfur, and the reinforcing agent is carbon black.

Preferably, the vulcanization accelerator is zinc dimethyl dithiocarbamate, N-cyclohexyl-2-benzothiazole sulfenamide, tetramethylthiuram disulfide, zinc diethyldithiocarbamate , 4,4'-dithiodimorpholine, dibenzothiazole disulfide, bispentamethylenethiuram hexasulfide, and bispentamethylenethiuram tetrasulfide.

Preferably, the anti-aging agent is N-isopropyl-N'-phenyl-p-phenylenediamine, N,N'-di(2-naphthyl)-p-phenylenediamine, nickel dibutyldithiocarbamate, 2 , any one or more of 2,4-trimethyl-1,2-dihydroquinoline polymer, N-phenyl-2-naphthylamine.

The preparation method of the above-mentioned carbon fiber-based puncture-resistant rubber composite material comprises the following steps:

(1) Chopped carbon fibers are dispersed in a mixture of 2,2'-diallyl bisphenol A and liquid nitrile rubber at 110-140°C to form rubberized carbon fibers;

(2) Rubberized carbon fiber and rubber are mixed, vulcanized and cross-linked under the action of vulcanization active agent, surfactant, crosslinking agent, vulcanization accelerator, anti-aging agent and reinforcing agent to obtain carbon fiber-based puncture-resistant rubber composite material.

Preferably, the preparation method of carbon fiber-based puncture-resistant rubber composite material comprises the following steps:

(1) Rubberized carbon fiber: first heat the mixture of 2,2'-diallyl bisphenol A and liquid nitrile rubber to 110-140°C, stir for 10-30 minutes, gradually add chopped carbon fiber, and stir for 2 ~6 hours to obtain rubberized carbon fiber;

(2) Compounding of rubberized carbon fiber and rubber: firstly, the natural rubber is masticated on the open mixer, and the masticated natural rubber and synthetic rubber are put into the internal mixer together, and mixed for 0.5 to 2 minutes, and then mixed to the internal mixer. Add surfactant, vulcanization active agent, anti-aging agent, reinforcing agent and rubberized carbon fiber into the machine and banbury for 2 to 5 minutes, put the banburyed rubber into the open mixer, add vulcanization accelerator and crosslinking agent, After 6 to 10 times of thinning, the film is removed; the mixed rubber film obtained after the film is placed in a flat vulcanizer and vulcanized at 140 to 160°C for 10 to 20 minutes to obtain a carbon fiber-based puncture-resistant rubber composite material.

Since the rubberized carbon fiber contains a large amount of cyano group (-CN), which is the same as the functional group of the rubber used, according to the principle of similar compatibility, the rubberized carbon fiber can be uniformly dispersed in the rubber matrix. It can be seen that the mixture of 2,2'-diallyl bisphenol A and liquid nitrile rubber is not only used as a dispersant for chopped carbon fibers, but also as a compatibilizer for rubber and carbon fibers, so that chopped carbon fibers are well dispersed in rubber In the substrate, the ultimate goal of the present invention is thus achieved.

The beneficial effects produced by adopting the above-mentioned technical solution are: the present invention organically combines chopped carbon fibers and rubber through the rubberization of carbon fibers, and solves the problems of poor dispersion of carbon fibers in the rubber matrix, easy self-aggregation and phase separation, The synergistic effect between the various components in the composite material can be fully exerted, and technical support is provided for the preparation of high-performance rubber/carbon fiber composite materials. In addition, the preparation method is simple in operation, high in efficiency and low in cost. Since no solvent is used, the preparation process is safer, more environmentally friendly, and easier to implement. The dispersion effect of carbon fibers in rubber is good, and the product performance is stable.

Detailed ways

Explanation: Various raw materials used in the examples of the present invention, internal mixer, double-roll mill, flat vulcanizer, rotorless vulcanizer, and universal tensile testing machine are all commercially available products.

Example 1

A carbon fiber-based puncture-resistant rubber composite material, comprising the following raw materials in parts by weight: 45 parts of natural rubber, 45 parts of nitrile rubber, 10 parts of styrene-butadiene rubber, 5 parts of 2,2'-diallyl bisphenol A, 8 parts of liquid nitrile rubber, 0.5 parts of chopped carbon fiber, 3.0 parts of zinc oxide vulcanization activator, 0.5 parts of surfactant stearic acid, 0.5 parts of crosslinking agent sulfur, 1.0 part of vulcanization accelerator tetramethylthiuram disulfide , 0.5 parts of vulcanization accelerator 4,4'-dithiodimorpholine, 1.2 parts of vulcanization accelerator N-cyclohexyl-2-benzothiazole sulfenamide, anti-aging agent N-isopropyl-N'-benzene 1.0 parts of p-phenylenediamine, 1.0 parts of antioxidant 2,2,4-trimethyl-1,2-dihydroquinoline polymer, and 15 parts of reinforcing agent carbon black. The number average molecular weight of liquid nitrile rubber is 3000-3500; the length of chopped carbon fiber is 2-10mm.

The preparation method of the above-mentioned carbon fiber-based puncture-resistant rubber composite material comprises the following steps:

(1) Rubberized carbon fiber: in parts by weight, first heat 5 parts of 2,2'-diallyl bisphenol A and 8 parts of liquid nitrile rubber in an oil bath to 120°C, stir for 20 minutes, and gradually add short Cut 0.5 parts of carbon fibers, and react with high-speed stirring for 4 hours to obtain rubberized carbon fibers.

(2) Compounding of rubberized carbon fiber and rubber: First, add natural rubber on the open mill for masticating, put 45 parts of natural rubber masticated, 45 parts of nitrile rubber and 10 parts of styrene-butadiene rubber into the internal mixer together, Mix for 1 minute, then add 0.5 parts of stearic acid, 3.0 parts of zinc oxide, 1.0 parts of N-isopropyl-N'-phenyl-p-phenylenediamine, 2,2,4-trimethyl - 1.0 parts of 1,2-dihydroquinoline polymer, 15 parts of carbon black and the rubberized carbon fiber of step (1), banburying for 3 minutes, putting the rubber material of banburying on the open mixer, adding tetrasulfide 1.0 parts of methyl thiuram, 0.5 parts of 4,4'-dithiodimorpholine, 1.2 parts of N-cyclohexyl-2-benzothiazole sulfenamide, 0.5 parts of sulfur, thin the film after 7 times ; Put the mixed rubber film obtained after the next film into a flat vulcanizer and vulcanize at 155°C for 15 minutes to obtain the final product.

Example 2

A carbon fiber-based puncture-resistant rubber composite material, comprising the following raw materials in parts by weight: 40 parts of natural rubber, 50 parts of nitrile rubber, 10 parts of styrene-butadiene rubber, 5 parts of 2,2'-diallyl bisphenol A, 10 parts of liquid nitrile rubber, 0.8 parts of chopped carbon fiber, 3.5 parts of zinc oxide vulcanization activator, 0.8 parts of surfactant stearic acid, 0.8 parts of crosslinking agent sulfur, 1.2 parts of zinc diethyldithiocarbamate vulcanization accelerator Parts, 1.2 parts of vulcanization accelerator bispentamethylenethiuram hexasulfide, 1.1 parts of anti-aging agent N,N'-di(2-naphthyl)-p-phenylenediamine, anti-aging agent 2,2,4-trimethyl- 0.9 parts of 1,2-dihydroquinoline polymer, 20 parts of reinforcing agent carbon black. The number average molecular weight of liquid nitrile rubber is 3000-3500; the length of chopped carbon fiber is 2-10mm.

The preparation method of the above-mentioned carbon fiber-based puncture-resistant rubber composite material comprises the following steps:

(1) Rubberized carbon fiber: in parts by weight, first heat 5 parts of 2,2'-diallyl bisphenol A and 10 parts of liquid nitrile rubber in an oil bath to 130°C, stir for 25 minutes, and gradually add short Cut 0.8 parts of carbon fiber and react with high-speed stirring for 5 hours to obtain rubberized carbon fiber.

(2) Compounding of rubberized carbon fiber and rubber: first, add natural rubber on the open mill for masticating, put 40 parts of natural rubber masticated, 50 parts of nitrile rubber and 10 parts of styrene-butadiene rubber into the internal mixer together, Mix for 1 minute, then add 0.8 parts of stearic acid, 3.5 parts of zinc oxide, 1.1 parts of N,N'-di(2-naphthyl)-p-phenylenediamine, 2,2,4-trimethyl 0.9 parts of base-1,2-dihydroquinoline polymer, 20 parts of carbon black and the rubberized carbon fiber of step (1), banburying for 3.5 minutes, put the banburying good rubber on the open mixer, add diethyl ether 1.2 parts of zinc dithiocarbamate, 1.2 parts of bispentamethylene thiuram hexasulfide, and 0.8 parts of sulfur, after 8 times of thinning, the film is removed; the mixed rubber film obtained after the film is placed in a flat vulcanizer Vulcanized at 160°C for 12 minutes to obtain the final product.

Example 3

A carbon fiber-based puncture-resistant rubber composite material, comprising the following raw materials in parts by weight: 40 parts of natural rubber, 50 parts of nitrile rubber, 10 parts of butadiene rubber, 6 parts of 2,2'-diallyl bisphenol A, 12 parts of liquid nitrile rubber, 1.2 parts of chopped carbon fiber, 4.0 parts of zinc oxide vulcanization activator, 0.8 parts of surfactant stearic acid, 1.0 parts of crosslinking agent sulfur, 1.2 parts of vulcanization accelerator tetramethylthiuram disulfide , 1.3 parts of vulcanization accelerator dibenzothiazole disulfide, 0.5 parts of anti-aging agent N-isopropyl-N'-phenyl-p-phenylenediamine, 0.8 parts of anti-aging agent nickel dibutyl dithiocarbamate, anti-aging agent N - 1.0 parts of phenyl-2-naphthylamine, 24 parts of reinforcing agent carbon black. The number average molecular weight of liquid nitrile rubber is 3000-3500; the length of chopped carbon fiber is 2-10mm.

The preparation method of the above-mentioned carbon fiber-based puncture-resistant rubber composite material comprises the following steps:

(1) Rubberized carbon fiber: in parts by weight, first heat 6 parts of 2,2'-diallyl bisphenol A and 12 parts of liquid nitrile rubber in an oil bath to 135°C, stir for 25 minutes, and gradually add short Cut 1.2 parts of carbon fiber and react with high-speed stirring for 4.5 hours to obtain rubberized carbon fiber.

(2) Compounding of rubberized carbon fiber and rubber: First, add natural rubber on the open mill for masticating, put 40 parts of natural rubber masticated, 50 parts of nitrile rubber and 10 parts of butadiene rubber into the internal mixer together, Mix for 1.5 minutes, then add 0.8 parts of stearic acid, 4.0 parts of zinc oxide, 0.5 parts of N-isopropyl-N'-phenyl-p-phenylenediamine, nickel dibutyldithiocarbamate to the mixer 0.8 part, 1.0 part of N-phenyl-2-naphthylamine, 24 parts of carbon black and the rubberized carbon fiber of step (1), banburying for 4.0 minutes, put the good rubber material of banburying on the open mixer, add disulfide 1.2 parts of tetramethylthiuram, 1.3 parts of dibenzothiazole disulfide, 1.0 parts of sulfur, thin pass 10 times and then filmed; put the mixed rubber film obtained after filming into a flat vulcanizing machine and vulcanize at 160 °C 15 minutes to get the final product.

Embodiment 4～8

The raw materials were prepared according to the components and proportions in Table 1 (wherein the number average molecular weight of the liquid nitrile rubber was 3000-3500; the length of the chopped carbon fibers was 2-10 mm), and the preparation method was the same as in Example 2.

Components and parts by weight proportioning in the embodiment 1-embodiment 8 of table 1

The performance test result of table 2 embodiment 1-embodiment 8

Claims (8)

1. A carbon fiber-based puncture-resistant rubber composite material, characterized in that: it comprises the following raw materials in parts by weight: 100 parts of rubber, 5 to 10 parts of 2,2'-diallyl bisphenol A, 8 parts of liquid nitrile rubber ～15 parts, chopped carbon fiber 0.5～2.0 parts, vulcanization activator 3～5 parts, surfactant 0.5～2.0 parts, crosslinking agent 0.5～2.5 parts, vulcanization accelerator 0.5～3.5 parts, antioxidant 0.5～3.0 parts , 15 to 30 parts of reinforcing agent; the rubber is composed of natural rubber and synthetic rubber, wherein the synthetic rubber is a mixture of nitrile rubber and styrene-butadiene rubber, or the synthetic rubber is a mixture of nitrile rubber and butadiene rubber, or , the synthetic rubber is a mixture of nitrile rubber, styrene-butadiene rubber and butadiene rubber; A method for preparing a carbon fiber-based puncture-resistant rubber composite material, comprising the steps of: (1) Chopped carbon fibers are dispersed in a mixture of 2,2'-diallyl bisphenol A and liquid nitrile rubber at 110-140°C to form rubberized carbon fibers; (2) Rubberized carbon fiber and rubber are mixed, vulcanized and cross-linked under the action of vulcanization active agent, surfactant, crosslinking agent, vulcanization accelerator, anti-aging agent and reinforcing agent to obtain carbon fiber-based puncture-resistant rubber composite material. 2. A carbon fiber-based puncture-resistant rubber composite material according to claim 1, characterized in that the number average molecular weight of the liquid nitrile rubber is 3000-3500. 3. A carbon fiber-based puncture-resistant rubber composite material according to claim 1, characterized in that the length of the chopped carbon fibers is 2-10 mm. 4. A carbon fiber-based puncture-resistant rubber composite material according to claim 1, wherein the vulcanization active agent is zinc oxide, the surfactant is stearic acid, the crosslinking agent is sulfur, and the reinforcing agent is carbon black. 5. A kind of carbon fiber-based puncture-resistant rubber composite material according to claim 1, characterized in that said vulcanization accelerator is zinc dimethyl dithiocarbamate, N-cyclohexyl-2-benzothiazole sulfenyl Amide, tetramethylthiuram disulfide, zinc diethyldithiocarbamate, 4,4'-dithiodimorpholine, dibenzothiazole disulfide, bispentamethylenethiuram hexasulfide, Any one or more of dipentamethylenethiuram tetrasulfide. 6. A kind of carbon fiber-based puncture-resistant rubber composite material according to claim 1, characterized in that said antioxidant is N-isopropyl-N'-phenyl-p-phenylenediamine, N,N'-bis( 2-naphthyl)-p-phenylenediamine, nickel dibutyldithiocarbamate, 2,2,4-trimethyl-1,2-dihydroquinoline polymer, N-phenyl-2-naphthylamine any one or more of them. 7. The preparation method of a kind of carbon fiber-based puncture-resistant rubber composite material according to any one of claims 1-6, characterized in that, comprising the steps of: (1) Chopped carbon fibers are dispersed in a mixture of 2,2'-diallyl bisphenol A and liquid nitrile rubber at 110-140°C to form rubberized carbon fibers; (2) Rubberized carbon fiber and rubber are mixed, vulcanized and cross-linked under the action of vulcanization active agent, surfactant, crosslinking agent, vulcanization accelerator, anti-aging agent and reinforcing agent to obtain carbon fiber-based puncture-resistant rubber composite material. 8. The preparation method of a kind of carbon fiber-based puncture-resistant rubber composite material according to claim 7, is characterized in that, comprises the steps: (1) Rubberized carbon fiber: first heat the mixture of 2,2'-diallyl bisphenol A and liquid nitrile rubber to 110-140°C, stir for 10-30 minutes, gradually add chopped carbon fiber, and stir for 2 ~6 hours to obtain rubberized carbon fiber; (2) Compounding of rubberized carbon fiber and rubber: firstly, the natural rubber is masticated on the open mixer, and the masticated natural rubber and synthetic rubber are put into the internal mixer together, and mixed for 0.5 to 2 minutes, and then mixed to the internal mixer. Add surfactant, vulcanization active agent, anti-aging agent, reinforcing agent and rubberized carbon fiber into the machine and banbury for 2 to 5 minutes, put the banburyed rubber into the open mixer, add vulcanization accelerator and crosslinking agent, After 6 to 10 times of thinning, the film is removed; the mixed rubber film obtained after the film is placed in a flat vulcanizer and vulcanized at 140 to 160°C for 10 to 20 minutes to obtain a carbon fiber-based puncture-resistant rubber composite material.