阅读说明：本技术 一种具有自修复功能的丁苯橡胶及制备方法 (Styrene butadiene rubber with self-repairing function and preparation method thereof ) 是由 李志喜 杨琨 王宝亮 于 2018-08-28 设计创作，主要内容包括：本发明属于高分子材料技术领域,公开了一种具有自修复功能的丁苯橡胶及制备方法。所述硫化橡胶由以下按重量份数计的组分组成：丁苯橡胶100份,氧化锌3份,硬脂酸1份,促进剂1-2份,硫磺1.5-2.5份,石蜡油0-10份,二硫键交换反应催化剂0-0.5份。投放到混炼设备中混炼,在硫化温度160℃,压力10MPa,根据硫化仪测得的硫化时间硫化,得到具有自修复功能的丁苯橡胶。本发明所述的硫化橡胶不仅原料易得、制备方法简单,还能实现多次的自修复,有利于延长橡胶制品的使用寿命、减轻环境污、节约石油资源。(The invention belongs to the technical field of high polymer materials, and discloses styrene butadiene rubber with a self-repairing function and a preparation method thereof. The vulcanized rubber comprises the following components in parts by weight: 100 parts of styrene butadiene rubber, 3 parts of zinc oxide, 1 part of stearic acid, 1-2 parts of an accelerant, 1.5-2.5 parts of sulfur, 0-10 parts of paraffin oil and 0-0.5 part of a disulfide bond exchange reaction catalyst. And putting the mixture into mixing equipment for mixing, and vulcanizing at the vulcanization temperature of 160 ℃ and the pressure of 10MPa according to the vulcanization time measured by a vulcanizer to obtain the styrene-butadiene rubber with the self-repairing function. The vulcanized rubber provided by the invention has the advantages of easily available raw materials and simple preparation method, can realize repeated self-repair, and is beneficial to prolonging the service life of rubber products, reducing environmental pollution and saving petroleum resources.)

1. A preparation method of styrene butadiene rubber with a self-repairing function comprises the following specific steps:

2. the self-repairing styrene-butadiene rubber of claim 1, wherein: the accelerator is N-cyclohexyl-2-benzothiazole sulfonamide and tetramethyl thiuram disulfide.

3. The self-repairing styrene-butadiene rubber of claim 1, wherein: the disulfide bond exchange reaction catalyst is one or a mixture of more of cuprous chloride, cupric chloride, smelly copper, copper sulfate, ferric chloride, ferric sulfate and germanium chloride.

4. The self-repairing styrene-butadiene rubber of claim 1, wherein: the paraffin oil is used as a dispersant, and the small materials are dispersed more uniformly.

5. The preparation method of the self-repairing styrene-butadiene rubber is characterized by comprising the following steps of: 100 parts of styrene butadiene rubber, 3 parts of zinc oxide, 1 part of stearic acid, 1-2 parts of accelerator, 1.5-2.5 parts of sulfur, 0-10 parts of paraffin oil and 0-0.5 part of catalyst are mixed in an open mill, the temperature of a mixing roller is controlled to be 50-60 ℃, and the temperature of a front roller is 5-10 ℃ lower than that of a rear roller so as to be wrapped in the front roller. And vulcanizing the rubber compound on a flat vulcanizing machine, wherein the pressure during vulcanization is 10MPa, the vulcanization temperature is 160 ℃, the vulcanization time is t90+1min, and after vulcanization is finished, the vulcanized rubber is placed according to the specification (more than 16 h) to obtain the self-repairing styrene-butadiene rubber.

6. Use of the vulcanizate prepared according to claim 5 in self-healing.

7. The application of the self-repairing rubber as claimed in claim 6, wherein the self-repairing method comprises the step of enabling the cross sections of the vulcanized rubber to be in contact with each other at 100-120 ℃ in an air atmosphere for 6-12 hours.

Technical Field

The invention belongs to the field of self-repair of rubber products, and particularly relates to self-repair styrene-butadiene rubber and a preparation method thereof

Background

In the manufacturing, transporting and using processes of the polymer material, the polymer material is easily damaged due to the influence of environmental factors such as heat, force, chemistry and the like, so that the performance of the polymer material is reduced, and the service life of the polymer material is shortened. By simulating the self-repairing mechanism of organisms on damage, self-repairing materials are produced at the same time and are widely concerned. Self-repairing materials can be divided into two main categories, namely, exopathic type and intrinsic type. At present, the technology about self-repairing of rubber mainly depends on the addition of microcapsules containing repairing agents and ionic polymers. Because rubber needs to be subjected to procedures of banburying, roll milling and the like, the microcapsules containing the repairing agent are required to be stably and losslessly present, and meanwhile, the microcapsules have good compatibility with a rubber substrate, otherwise, the rubber strength is affected. The ionic polymer is composed of ionic bonds, and has low strength and poor creep resistance compared with covalent bonds.

In the manufacturing, transporting and using processes of the polymer material, the polymer material is easily damaged due to the influence of environmental factors such as heat, force, chemistry and the like, so that the performance of the polymer material is reduced, and the service life of the polymer material is shortened. By simulating the self-repairing mechanism of organisms on damage, self-repairing materials are produced at the same time and are widely concerned. Self-repairing materials can be divided into two main categories, namely, exopathic type and intrinsic type. At present, the technology about self-repairing of rubber mainly depends on the addition of microcapsules containing repairing agents and ionic polymers. Because rubber needs to be subjected to procedures of banburying, roll milling and the like, the microcapsules containing the repairing agent are required to be stably and losslessly present, and meanwhile, the microcapsules have good compatibility with a rubber substrate, otherwise, the rubber strength is affected. The ionic polymer is composed of ionic bonds, and has low strength and poor creep resistance compared with covalent bonds.

The styrene butadiene rubber has the advantages of wear resistance, cold resistance, low heat generation, good rebound resilience and the like, has the comprehensive properties of excellent wet skid resistance and general rolling resistance, and can be used in tread rubber of tires, shoe industry and other rubber industrial products in batches. The styrene butadiene rubber is easy to be damaged, cracks are easy to generate in the material and on the surface of the material, and the damage is discovered in time, so that the mechanical property of the material is seriously reduced, the use performance is influenced, the safety performance is reduced, the use period of the material is shortened, and the waste of material resources is caused.

The molecular structure of vulcanized rubber is a three-dimensional network structure formed by the cross-linking reaction of linear rubber macromolecular chains, sulfur, an accelerator and the like, wherein the cross-linking bond of the vulcanized rubber is composed of a monothio bond, a disulfide bond, a polysulfide bond and the like, and the disulfide bond has the characteristic of dynamic reversible exchange. The vulcanized rubber with self-repairing and recoverable properties is prepared by utilizing the dynamic reversible disulfide bonds of the vulcanized rubber system towel, the method is simple and convenient, the service life of the material can be prolonged, the environmental pollution can be reduced, and the rubber resources are saved.

Disclosure of Invention

The invention aims to provide styrene butadiene rubber with a self-repairing function and a preparation method thereof, and the styrene butadiene rubber is endowed with the self-repairing performance by adding a catalyst to catalyze a disulfide bond exchange reaction. In order to achieve the purpose, the invention adopts the following technical scheme:

the purpose of the invention can be realized by the following scheme:

the self-repairing styrene-butadiene rubber comprises the following components in parts by weight:

preferably, the accelerator is N-cyclohexyl-2-benzothiazole sulfonamide and tetramethylthiuram disulfide combined use

Preferably, the disulfide bond exchange reaction catalyst is one or a mixture of more of cuprous chloride, copper chloride, smelly copper, copper sulfate, ferric chloride, ferric sulfate and germanium chloride.

Preferably, the self-repairing styrene-butadiene rubber is characterized in that: the paraffin oil is used as a dispersant, and the small materials are dispersed more uniformly.

The invention discloses a preparation method of self-repairing styrene-butadiene rubber, which comprises the following steps: 100 parts of styrene butadiene rubber, 3 parts of zinc oxide, 1 part of stearic acid, 1-2 parts of accelerator, 1.5-2.5 parts of sulfur, 0-10 parts of paraffin oil and 0-0.5 part of catalyst are mixed in an open mill, the temperature of a mixing roller is controlled to be 50-60 ℃, and the temperature of a front roller is 5-10 ℃ lower than that of a rear roller so as to be wrapped in the front roller. The rubber compound is vulcanized and prepared on a plate vulcanizing machine, the pressure during vulcanization is 10MPa, the vulcanization temperature is 160 ℃, and the vulcanization time is t₉₀+1min, after vulcanization, the vulcanizate is as specifiedAfter standing for more than 16h, the self-repairing styrene-butadiene rubber is obtained.

Meanwhile, the inventor discovers through research that the increase of the sulfur consumption is beneficial to the increase of the content of disulfide bonds in vulcanized rubber and the improvement of the recovery performance of the vulcanized rubber.

In the preparation method of the vulcanized rubber, the paraffin oil is used as a dispersing agent, so that small materials and a catalyst are dispersed more uniformly, and the self-repairing performance of the vulcanized rubber is further enhanced.

The working principle of the self-repairing and recyclable vulcanized rubber is as follows: after sulfur vulcanization, the rubber can form a three-dimensional network structure with a single sulfur bond, a double sulfur bond and a polysulfide bond as cross-linking bonds. In order to endow the rubber with self-repairing performance, a metal salt catalyst capable of promoting disulfide bond dynamic reversible exchange reaction is added, the using amount of sulfur is changed to increase the content of disulfide bonds, and simultaneously paraffin oil and the using amount of an accelerant are added, so that the metal salt catalyst is easier to diffuse, and is more uniformly distributed in a rubber system. When the cross sections of the rubber materials are contacted with each other, the disulfide cross-linking bonds can perform exchange reaction under the action of a catalyst and at a certain temperature, so that the network structure at the cross sections is untied, the molecules are diffused, re-entangled and cross-linked, and new rubber materials are formed

The dynamic network structure rejoins the sections together to realize the repair of the cracks.

The vulcanized rubber self-repairing method provided by the invention comprises the steps of enabling the sections of the vulcanized rubber to be in contact at 100-120 ℃ in an air atmosphere, and repairing for 6-2 hours;

the invention has the following advantages and beneficial effects:

the vulcanized rubber is commonly used in industry, the preparation process is simple, the repairing agent and the regenerating agent are not needed during repairing and recovering, the good self-repairing and recovering effects can be achieved, the energy consumption in the self-repairing and recovering process is low, the inert gas protection is not needed, and the method can be carried out in the atmosphere. Because the disulfide bond exchange reaction in the vulcanized rubber has dynamic reversibility, the prepared vulcanized rubber has multiple repairing and recycling performances, thereby effectively prolonging the service life of the industrial vulcanized rubber and relieving the black pollution problem.

Detailed Description

The invention is further described with reference to the following examples:

in the performance test, the mechanical property, namely the self-repairing property measured by a common tensile machine after tabletting is that a sample is cut by a blade, then a certain pressure is applied to cling to the tangent plane of the tangent plane, and after heat treatment is carried out for 12 hours at 120 ℃, the ratio of the front tensile strength and the rear tensile strength of the sample can obtain the self-repairing rate, so that the self-repairing property is reflected.

Example 1

The preparation method of the self-repairing styrene-butadiene rubber comprises the following steps: (1) 100phr of SBR, 3phr of zinc oxide, 1phr of stearic acid, 1phr of accelerator CZ, 0.1phr of accelerator TMTD, 1.5phr of S and 0.125phr of copper chloride are added in sequence by using an open mill, the materials are uniformly mixed by using an inclined knife method, triangular packaging is carried out for 7 times, and sheets are taken out after six passes. The vulcanization characteristic of the rubber compound is measured according to the GB/T16584-₉₀. The vulcanized strong sheet is vulcanized and prepared on a flat vulcanizing machine, the pressure during vulcanization is 10MPa, the vulcanization temperature is 160 ℃, and the vulcanization time is t₉₀+1min, after vulcanization, standing the vulcanized rubber according to the specification (more than 16 h), and measuring the mechanical property by a tensile test

After the tensile sample strip is broken and damaged, the two sections are fully contacted, the material is repaired for 12 hours in the air at 120 ℃, and the tensile property of the material is tested again; the properties thereof were measured and shown in Table 1.

Example 2

The preparation method of the self-repairing styrene-butadiene rubber comprises the following steps: (1) 100phr of SBR, 3phr of zinc oxide, 1phr of stearic acid, 1.25phr of accelerator CZ, 0.25phr of accelerator TMTD, 0.125phr of copper chloride and 2phr of sulfur are added in sequence by using an open mill, the materials are uniformly mixed by using an inclined knife method, triangular packaging is carried out for 7 times, and sheets are taken out after six passes. The vulcanization characteristics of the rubber compound are determined according to the GB/T16584-1996 standard, and the process positive vulcanization time T90 is obtained. The vulcanized strong sheet is vulcanized and prepared on a flat vulcanizing machine, the pressure during vulcanization is 10MPa, the vulcanization temperature is 160 ℃, and the vulcanization time is t₉₀+1min, after vulcanizationAfter the formation, the vulcanized rubber is placed according to the specification (more than 16 h), and then the mechanical property is measured by a tensile test.

After the tensile sample strip is broken and damaged, the two sections are fully contacted, the material is repaired for 12 hours in the air at 120 ℃, and the tensile property of the material is tested again; the properties thereof were measured and shown in Table 1.

Example 3

The preparation method of the self-repairing styrene-butadiene rubber comprises the following steps: (1) 100phr of SBR, 3phr of zinc oxide, 1phr of stearic acid, 1phr of accelerator CZ, 0.1phr of TMTD, 0.25phr of copper chloride and 2phr of S are added in sequence by using an open mill, the materials are uniformly mixed by using a slant knife method, triangular bags are formed for 7 times, and sheets are taken out after six passes. The vulcanization characteristic of the rubber compound is measured according to the GB/T16584-₉₀. The vulcanized strong sheet is vulcanized and prepared on a flat vulcanizing machine, the pressure during vulcanization is 10MPa, the vulcanization temperature is 160 ℃, and the vulcanization time is t₉₀And+ 1min, after vulcanization, standing the vulcanized rubber according to the specification (more than 16 h), and measuring the mechanical property by a tensile test.

After the tensile sample strip is broken and damaged, the two sections are fully contacted, the material is repaired for 12 hours in the air at 120 ℃, and the tensile property of the material is tested again; the properties thereof were measured and shown in Table 1.

Example 4

The preparation method of the self-repairing styrene-butadiene rubber comprises the following steps: (1) 100phr of SBR, 3phr of zinc oxide, 1phr of stearic acid, 1phr of accelerator CZ, 0.1phr of TMTD, 0.25phr of copper chloride, 10phr of paraffin oil and 2phr of S are added in sequence by using an open mill, the materials are uniformly mixed by using a slant knife method, triangular packaging is carried out for 7 times, and sheets are taken out after six times of thin passing. The vulcanization characteristic of the rubber compound is measured according to the GB/T16584-₉₀. The vulcanized strong sheet is vulcanized and prepared on a flat vulcanizing machine, the pressure during vulcanization is 10MPa, the vulcanization temperature is 160 ℃, and the vulcanization time is t₉₀And+ 1min, after vulcanization, standing the vulcanized rubber according to the specification (more than 16 h), and measuring the mechanical property by a tensile test.

After the tensile sample strip is broken and damaged, the two sections are fully contacted, the material is repaired for 12 hours in the air at 120 ℃, and the tensile property of the material is tested again; the properties thereof were measured and shown in Table 1.

Comparative example 1

The preparation method of the self-repairing styrene-butadiene rubber comprises the following steps: (1) 100phr of SBR, 3phr of zinc oxide, 1phr of stearic acid, 1phr of accelerator CZ, 0.1phr of TMTD and 2phr of S are added in sequence by using an open mill, the materials are uniformly mixed by using a slant knife method, triangular wrapping is carried out for 7 times, and sheets are taken out after six passes. The vulcanization characteristic of the rubber compound is measured according to the GB/T16584-₉₀. The vulcanized strong sheet is vulcanized and prepared on a flat vulcanizing machine, the pressure during vulcanization is 10MPa, the vulcanization temperature is 160 ℃, and the vulcanization time is t₉₀And+ 1min, after vulcanization, standing the vulcanized rubber according to the specification (more than 16 h), and measuring the mechanical property by a tensile test.

After the tensile sample strip is broken and damaged, the two sections are fully contacted, the material is repaired for 12 hours in the air at 120 ℃, and the tensile property of the material is tested again; the properties thereof were measured and shown in Table 1.

Table 1 shows the results of the self-repairing styrene-butadiene rubber performance test