CN112239572B

CN112239572B - Rubber composition for shoe sole, vulcanized rubber, and preparation method and application thereof

Info

Publication number: CN112239572B
Application number: CN201910657039.3A
Authority: CN
Inventors: 解希铭; 王丽丽
Original assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Current assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Priority date: 2019-07-19
Filing date: 2019-07-19
Publication date: 2022-08-19
Anticipated expiration: 2039-07-19
Also published as: CN112239572A

Abstract

The invention relates to the field of rubber, and discloses a rubber composition for soles, vulcanized rubber, a preparation method and application thereof, wherein the composition contains a rubber substrate, a rubber modifier, white carbon black, polyethylene glycol, a surface modifier, an activator, an anti-aging agent, a softener, a vulcanizing agent and an accelerator, wherein the rubber modifier is represented by the general formula (R) ₁ O) ₃ SiCH ₂ CH ₂ CH ₂ Organosilanes of formula X, R ₁ O is a hydrolyzable group; x is SH; the rubber matrix is solution polymerized styrene-butadiene rubber and optionally butadiene rubber. The vulcanized rubber prepared from the rubber composition has moderate hardness, and excellent strength, rebound resilience and wear resistance.

Description

Rubber composition for shoe sole, vulcanized rubber, and preparation method and application thereof

Technical Field

The invention relates to the field of rubber, in particular to a rubber composition for soles, a method for preparing vulcanized rubber, the vulcanized rubber prepared by the method and application of the vulcanized rubber in preparing soles.

Background

The comfort of the sole directly influences the quality of the whole shoe, and the soles produced by a plurality of international large brands provide a comfortable, high-end and fashionable feeling for people.

In the prior art, the sole is produced by using PVC, TPR, TPU and other materials, and the materials are inferior to the sole made of rubber in the aspects of comfort and skid resistance.

In the prior art, white carbon black is used as a main reinforcing filler and is widely applied to shoe products, so that soles have good wear resistance, skid resistance and vamp adhesion, colored cowhells soles can be processed, and the white carbon black is widely applied to light-colored and colored soles (including undersoles, midsoles and foxings). Therefore, the shoe industry is always a large user of white carbon black.

The dispersion of white carbon black in a rubber matrix becomes extremely difficult due to the strong surface polarity of the white carbon black, so that the application is limited to a certain extent.

CN105440341A discloses an antiskid sole material, and the invention discloses the application of white carbon black in a sole material, wherein the white carbon black is added with a silane coupling agent to improve the dispersibility, and the silane coupling agent is a sulfur-containing compound, so that the requirement on process control is high in the high-temperature mixing process, scorching is possibly caused by improper control, and the overall performance of the composite material is influenced.

Since the above prior art cannot fully satisfy the requirements of high strength, good wear resistance and good elasticity of shoe soles containing white carbon black, there is a need for a rubber composition with improved properties.

Disclosure of Invention

The invention aims to overcome the defects of low rubber strength, poor wear resistance and low elasticity when vulcanized rubber in the prior art is used for preparing soles.

In order to achieve the above object, a first aspect of the present invention provides a rubber composition for shoe soles, wherein the composition comprises a rubber matrix, a rubber modifier, white carbon black, polyethylene glycol, a surface modifier, an activator, an anti-aging agent, a softener, a vulcanizing agent and an accelerator, wherein the rubber modifier is represented by the general formula (R) ₁ O) ₃ SiCH ₂ CH ₂ CH ₂ Organosilanes of formula X, R ₁ O is a hydrolyzable group; x is SH; the rubber matrix is solution polymerized styrene butadiene rubber and optionally butadiene rubber.

In a second aspect, the present invention provides a process for preparing a vulcanized rubber comprising:

(1) performing first mixing on a rubber matrix and a rubber modifier to obtain a section of master batch;

(2) carrying out second mixing on the first-stage masterbatch, a surface modifier, polyethylene glycol and part of white carbon black to obtain a second-stage masterbatch;

(3) performing third mixing on the second-stage masterbatch, an activating agent, an anti-aging agent, a softening agent and the residual white carbon black to obtain a third-stage masterbatch;

(4) carrying out fourth mixing on the three sections of master batch, an accelerant and a vulcanizing agent to obtain final rubber;

(5) vulcanizing the final rubber;

the weight ratio of the part of white carbon black to the rest of white carbon black is (3.5-4.5): 1;

the rubber base, the rubber modifier, the polyethylene glycol, the surface modifier, the activator, the antioxidant, the softener, the vulcanizing agent, and the accelerator are the same as those of the rubber composition for a shoe sole, and the partial white carbon black in step (2) and the remaining white carbon black in step (3) together constitute white carbon black in the rubber composition for a shoe sole in the first aspect.

A third aspect of the invention provides a vulcanizate made by the foregoing method.

A fourth aspect of the invention provides the use of the aforementioned vulcanized rubber in the preparation of shoe soles.

The vulcanized rubber provided by the invention has excellent strength and wear resistance and good elasticity, and the high-wear-resistance and high-resilience soft sole can be obtained from the vulcanized rubber provided by the invention.

The process for preparing the vulcanized rubber provided by the invention can play a synergistic effect of all the components in the composition provided by the invention, so that the vulcanized rubber prepared from all the components in the composition provided by the invention by adopting the method provided by the invention has higher strength, better wear resistance and elasticity.

Detailed Description

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

As described above, the first aspect of the invention provides a rubber composition for soles, wherein the composition comprises a rubber matrix, a rubber modifier, white carbon black, polyethylene glycol, a surface modifier, an activator, an anti-aging agent, a softener, a vulcanizing agent and an accelerator, wherein the rubber modifier is represented by the general formula (R) ₁ O) ₃ SiCH ₂ CH ₂ CH ₂ Organosilanes of formula X, R ₁ O is a hydrolyzable group; x is SH; the rubber matrix is solution polymerized styrene-butadiene rubber and optionally butadiene rubber.

The inventor of the invention finds that the organosilane containing the mercapto group can modify the rubber matrix containing the solution-polymerized styrene-butadiene rubber, the interaction force between the modified rubber matrix and the white carbon black is enhanced, the dispersibility of the white carbon black in the rubber matrix is improved, and the prepared vulcanized rubber has the characteristic of excellent resilience.

Preferably, in said organosilane, R ₁ O is methoxy or ethoxy.

Preferably, the vinyl content of the solution-polymerized styrene-butadiene rubber is 50 to 70 mass%.

Preferably, the cis content in the butadiene rubber is 90 to 99 mass%.

According to a preferred embodiment, the rubber matrix is butadiene rubber and solution polymerized styrene butadiene rubber. More preferably, the rubber matrix contains 60 to 80 mass% of butadiene rubber and 20 to 40 mass% of solution-polymerized styrene-butadiene rubber.

It is particularly preferable that the rubber matrix of the present invention is 20 to 40 mass% solution-polymerized styrene-butadiene rubber and 60 to 80 mass% butadiene rubber. The inventors have found that a rubber matrix comprising a solution-polymerized styrene-butadiene rubber is capable of reacting with the mercapto groups of the rubber modifier and that this particularly preferred embodiment enables the rubber matrix and the rubber modifier in the composition of the invention to act synergistically, thereby giving better resilience to the vulcanizate thus obtained.

Preferably, relative to 100 parts by weight of the rubber matrix, the content of the rubber modifier is 5-10 parts by weight, the content of the white carbon black is 40-60 parts by weight, the content of the polyethylene glycol is 5-10 parts by weight, the content of the surface modifier is 4-6 parts by weight, the content of the activator is 4-6 parts by weight, the content of the anti-aging agent is 1-5 parts by weight, the content of the softener is 6-12 parts by weight, the content of the vulcanizing agent is 2-5 parts by weight, and the content of the accelerator is 3-6 parts by weight.

Preferably, the white carbon black is fumed silica, and more preferably, the nitrogen adsorption specific surface area of the white carbon black is 350-420m ² (ii) in terms of/g. For example, the white carbon black can be A380 of Degussa, and the nitrogen adsorption specific surface area of the white carbon black is 380m ² /g。

Preferably, the molecular weight of the polyethylene glycol is 2000-. For example, the polyethylene glycol may be PEG4000, PEG2000 or PEG 6000.

Preferably, the surface modifier is at least one of bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide (Si69) and bis- [3- (triethoxysilyl) propyl ] -disulfide.

Preferably, the antioxidant is a phenolic antioxidant. For example, the antioxidant is antioxidant 264.

Preferably, the softening agent is naphthenic oil. For example, the softener is naphthenic oil ASTM # 103 oil.

Preferably, the activator is a fatty acid and/or a fatty acid metal soap salt. For example, the fatty acid may be stearic acid; the fatty acid metal soap salt may be zinc stearate.

Preferably, the accelerator is at least one of a thiazole accelerator, a thiuram accelerator and a guanidine accelerator. For example, the accelerator is at least one of 2,2' -Dithiodibenzothiazole (DM), tetramethylthiuram disulfide (TMTD), and diphenylguanidine (D).

Preferably, the vulcanizing agent is sulfur and/or a sulfur donor. The sulfur donor is a substance capable of providing sulfur. The sulfur comprises at least one of insoluble sulfur, soluble sulfur and oil-extended sulfur. For example, the vulcanizing agent IS ordinary sulfur S, oil-extended insoluble sulfur IS, or the like.

The composition provided by the invention can be used for preparing vulcanized rubber by adopting various methods in the prior art, and the prepared vulcanized rubber has better properties, such as better wear resistance and elasticity, higher strength and the like, compared with the vulcanized rubber obtained by the composition provided by the prior art.

However, the inventor of the present invention found through a great deal of experimental studies that, by using the composition provided by the present invention, vulcanized rubber is prepared by adopting a staged mixing and stepwise feeding manner, in particular, the rubber matrix and the rubber modifier in the composition of the present invention are firstly mixed, then the masterbatch obtained by the mixing and the other components in the composition of the present invention are mixed (in particular, staged mixing), and the white carbon black in the composition is added in two parts, the white carbon black added for the first time is mixed with the primary masterbatch, the surface modifier and the polyethylene glycol, the white carbon black added for the second time is mixed with the secondary masterbatch, the activator, the anti-aging agent and the softening agent, and the ratio of the mass of the white carbon black added for the first time to the mass of the white carbon black added for the second time is controlled to be (3.5-4.5): 1, the vulcanizates thus obtained have a clear advantage in terms of resilience compared to the vulcanizates obtained by the processes of the prior art. Thus, the inventors of the present invention provide a preferred method for producing a vulcanized rubber as described in the second aspect below.

Specifically, as described above, the second aspect of the present invention provides a method for producing a vulcanized rubber, comprising:

(1) carrying out first mixing on a rubber matrix and a rubber modifier to obtain a section of master batch;

(3) carrying out third mixing on the second-section masterbatch, an activating agent, an anti-aging agent, a softening agent and the residual white carbon black to obtain third-section masterbatch;

(5) vulcanizing the final rubber;

the rubber base, the rubber modifier, the polyethylene glycol, the surface modifier, the activator, the antioxidant, the softener, the vulcanizing agent, and the accelerator are the same as those of the rubber composition for a sole in the first aspect, and the partial white carbon black in step (2) and the remaining white carbon black in step (3) together constitute white carbon black in the rubber composition for a sole in the first aspect.

The types and characteristics of the components and the relative amounts (or contents) of the components in the second aspect of the present invention are the same as those described in the first aspect of the present invention, and the present invention is not described in detail in the second aspect, and those skilled in the art should not be construed as limiting the present invention.

Preferably, the conditions of the first mixing include: the temperature is 90-130 deg.C, and the time is 3-7 min. More preferably, the conditions of the first mixing include: the temperature is 110-120 ℃, and the time is 4-6 min. Particularly, the control of the first mixing condition as described above enables the rubber matrix and the rubber modifier to exert better synergistic effect, so that the subsequently added white carbon black can have better dispersibility in the primary rubber obtained thereby, and the vulcanized rubber obtained by the method of the present invention has obviously better resilience performance.

Preferably, the conditions of the second mixing include: the temperature is 110-160 ℃, and the time is 2-6 min. More preferably, the conditions of the second mixing include: the temperature is 130-150 ℃, and the time is 3-5 min.

Preferably, the conditions of the third mixing include: the temperature is 120-160 ℃, and the time is 1-5 min. More preferably, the third mixing conditions include: the temperature is 140 ℃ and 150 ℃, and the time is 2-4 min.

Preferably, the fourth mixing conditions include: the temperature is not more than 120 deg.C, and the time is 3-5 min.

Preferably, the vulcanization conditions include: the temperature is 150 ℃ and 170 ℃, the pressure is 10-20MPa, and the time is 20-40 min.

As previously mentioned, a third aspect of the present invention provides a vulcanizate made by the method of the second aspect described above.

As previously mentioned, a fourth aspect of the invention provides the use of the aforementioned vulcanizates in the preparation of shoe soles.

In the present invention, the pressure used is a gauge pressure unless otherwise specified.

The present invention will be described in detail below by way of examples. In the following examples, various raw materials used below were commercially available unless otherwise specified.

The following examples and comparative examples the equipment for the preparation of vulcanizates are shown in Table 1.

The apparatus for testing the vulcanized rubbers obtained in the examples and comparative examples is shown in Table 2, and the test conditions are shown in Table 3.

The chemicals used in the examples and comparative examples are commercially available and are specified below:

butadiene rubber: BR9000, a yanshan petrochemical (wherein, the cis content is 97.8 mass%);

solution polymerized styrene-butadiene rubber: SSBR2506, a yanshan petrochemical (wherein the vinyl content is 60 mass%);

white carbon black: a380, Degussa, nitrogen adsorption specific surface area 380m ² /g；

PEG2000, PEG4000, PEG 6000: industrial grade, dow chemical company, usa;

rubber modifier: 3-mercaptopropyltriethoxysilane (X is SH, R) ₁ O is ethoxy), 3-mercaptopropyltrimethoxysilane (X is SH, R) ₁ O is methoxy), alatin chemical company;

softening agent: ASTM103# naphthenic oil, Shandong Taichang petrochemical Co., Ltd;

activating agent: stearic acid, Weifang Hengfeng chemical Limited;

an anti-aging agent: 4. 6-di-tert-butyl-p-cresol (anti-aging agent 264), Panhua chemistry (Shanghai) Co., Ltd.;

vulcanizing agent: sulfur, Heicheng Hechenghuai chemical Limited;

accelerator (b): 2. 2' -Dithiodibenzothiazole (DM), tetramethylthiuram disulfide (TMTD), Shanghai Yongji chemical technology, Inc.

The components in the following examples and comparative examples were used in parts by weight, each representing 1 g.

TABLE 1

Serial number	Device name	Model number	Manufacturer of the product
				1	Internal mixer	BR1600	Rall of American Farad
2	Flat vulcanizing machine	XLB-D4004002	Shanghai first rubber machinery plant

TABLE 2

Serial number	Test items	Model of the test apparatus	Manufacturer of the product
				1	Hardness of	TH210	Yingkou material testing machine factory
2	Mechanical properties	Universal tensile machine, SHIMADZU, AG-20KNG	Shimadzu Japan Ltd
				3	Rebound resilience	GT-7012-D	Taiwan high-speed railway, China
4	DIN abrasion	Zwick/Roell 5109	Zwick, Germany
				5	Rubber processing analyzer	RPA2000	Alpha company of USA

TABLE 3

Example 1

The rubber composition formula comprises: 60 parts of butadiene rubber, 40 parts of solution-polymerized styrene-butadiene rubber, 10 parts of 3-mercaptopropyltriethoxysilane, 694 parts of Si, 40 parts of white carbon black, 05 parts of PEG 40005, 12 parts of ASTM (American society for testing and materials) 103#, 4 parts of stearic acid, 5 parts of sulfur, 1.5 parts of DM, 1.5 parts of TMTD and 2641 parts of anti-aging agent.

The preparation process of the vulcanized rubber comprises the following steps:

(1) adding the rubber matrix into an internal mixer, setting the rotating speed to be 90rpm, setting the initial mixing temperature to be 110 ℃, and setting the raw rubber plastication time to be 0.5 min; adding a rubber modifier into the internal mixer for mixing at 110 ℃ for 6min to obtain a section of master batch;

(2) adding the surface modifier, polyethylene glycol and 4/5 white carbon black into an internal mixer, and carrying out second mixing with the first-stage masterbatch for 5min at the rubber discharge temperature of 130 ℃ to obtain a second-stage masterbatch;

(3) adding an activator, an anti-aging agent, a softener and the remaining white carbon black into an internal mixer, and carrying out third mixing with the second-stage masterbatch for 4min at the rubber discharge temperature of 140 ℃ to obtain third-stage masterbatch;

(4) setting the rotation speed of an internal mixer to be 60rpm, setting the initial mixing temperature to be 50 ℃, plasticating the three sections of master batch for 0.5min, adding a vulcanizing agent and an accelerant to carry out fourth mixing, setting the mixing temperature to be 100 ℃, mixing for 5min, and discharging to obtain final mixed rubber;

(5) and (3) putting the final rubber compound into a flat vulcanizing machine for vulcanization, wherein the vulcanization temperature is 150 ℃, the vulcanization pressure is 20MPa, and the vulcanization time is 40min, so that a vulcanized rubber sample S1 is obtained.

The cured rubber sample S1 was subjected to the performance test, and the results are shown in Table 4.

Example 2

The rubber composition formula comprises: 70 parts of butadiene rubber, 30 parts of solution-polymerized styrene-butadiene rubber, 8 parts of 3-mercaptopropyltrimethoxysilane, 695 parts of Si, 50 parts of white carbon black, 20008 parts of PEG, 9 parts of ASTM103#9, 5 parts of stearic acid, 3 parts of sulfur, 3 parts of DM, 1.5 parts of TMTD and 2643 parts of anti-aging agent.

The preparation process of the vulcanized rubber comprises the following steps:

(1) adding a rubber matrix into an internal mixer, setting the rotating speed to be 90rpm, the initial mixing temperature to be 115 ℃, and the raw rubber plasticating time to be 0.5 min; adding a rubber modifier into the internal mixer for mixing at 115 ℃ for 5min to obtain a section of master batch;

(2) adding the surface modifier, polyethylene glycol and 7/9 white carbon black into an internal mixer, and carrying out second mixing with the first-stage masterbatch for 4min at the rubber discharge temperature of 140 ℃ to obtain a second-stage masterbatch;

(3) adding an activating agent, an anti-aging agent, a softening agent and the rest white carbon black into an internal mixer, and carrying out third mixing with the second-section masterbatch for 3min at the rubber discharge temperature of 145 ℃ to obtain third-section masterbatch;

(4) setting the rotation speed of an internal mixer to be 60rpm, setting the initial mixing temperature to be 50 ℃, plasticating the three-section master batch for 0.5min, adding a vulcanizing agent and an accelerator to perform fourth mixing, wherein the mixing temperature is 110 ℃, the mixing time is 4min, and discharging to obtain final mixed rubber;

(5) and (3) putting the final rubber compound into a flat vulcanizing machine for vulcanization, wherein the vulcanization temperature is 170 ℃, the vulcanization pressure is 10MPa, and the vulcanization time is 20min, so that a vulcanized rubber sample S2 is obtained.

The cured rubber sample S2 was subjected to the performance test, and the results are shown in Table 4.

Example 3

The rubber composition formula comprises the following components: 80 parts of butadiene rubber, 20 parts of solution-polymerized styrene-butadiene rubber, 5 parts of 3-mercaptopropyltriethoxysilane, 696 parts of Si, 60 parts of white carbon black, 2 parts of PEG 400010, 6 parts of ASTM103#6, 6 parts of stearic acid, 2 parts of sulfur, 4 parts of DM, 2 parts of TMTD and 2645 parts of anti-aging agent.

The preparation process of the vulcanized rubber comprises the following steps:

(1) adding the rubber matrix into an internal mixer, setting the rotating speed to be 90rpm, the initial mixing temperature to be 120 ℃, and the raw rubber plasticating time to be 0.5 min; adding a rubber modifier into the internal mixer for mixing at 120 ℃ for 4min to obtain a section of master batch;

(2) adding a surface modifier, polyethylene glycol and 9/11 white carbon black into an internal mixer, and carrying out second mixing with the primary masterbatch for 3min at the rubber discharge temperature of 150 ℃ to obtain secondary masterbatch;

(3) adding an activating agent, an anti-aging agent, a softening agent and the remaining white carbon black into an internal mixer, and carrying out third mixing with the second-section masterbatch for 2min at a rubber discharge temperature of 150 ℃ to obtain third-section masterbatch;

(4) setting the rotation speed of an internal mixer to be 60rpm, setting the initial mixing temperature to be 50 ℃, plasticating the three-section master batch for 0.5min, adding a vulcanizing agent and an accelerator to perform fourth mixing, setting the mixing temperature to be 115 ℃, mixing the mixture for 3min, and discharging to obtain final mixed rubber;

(5) and (3) putting the final rubber compound into a flat vulcanizing machine for vulcanization, wherein the vulcanization temperature is 160 ℃, the vulcanization pressure is 15MPa, and the vulcanization time is 30min, so that a vulcanized rubber sample S3 is obtained.

The cured rubber sample S3 was subjected to the performance test, and the results are shown in Table 4.

Example 4

The formulation of the rubber composition of this example was similar to that of example 1, except that the solution-polymerized styrene-butadiene rubber was 10 parts by weight and the butadiene rubber was 90 parts by weight.

A vulcanized rubber sample S4 was obtained.

The cured rubber sample S4 was subjected to the performance test, and the results are shown in Table 4.

Example 5

The rubber composition formulation of this example was the same as that of example 1.

The preparation process of the vulcanized rubber comprises the following steps:

(1) adding the rubber matrix into an internal mixer, setting the rotating speed to be 90rpm, the initial mixing temperature to be 110 ℃, and the raw rubber plasticating time to be 0.5 min; adding a rubber modifier into the internal mixer for mixing at 110 ℃ for 6min to obtain a section of master batch;

(2) mixing the surface modifier, polyethylene glycol, white carbon black, an activator, an anti-aging agent and a softener with the primary masterbatch for the second time, wherein the mixing time is 5min, and the rubber discharge temperature is 130 ℃, so as to obtain secondary masterbatch;

(3) setting the rotation speed of an internal mixer to be 60rpm, setting the initial mixing temperature to be 50 ℃, plasticating the two-section master batch for 0.5min, adding a vulcanizing agent and an accelerant to mix, setting the mixing temperature to be 100 ℃, setting the mixing time to be 5min, and discharging to obtain final mixed rubber;

(4) and putting the final rubber compound into a flat vulcanizing machine for vulcanization, wherein the vulcanization temperature is 150 ℃, the vulcanization pressure is 20MPa, and the vulcanization time is 40 min.

A vulcanized rubber sample S5 was obtained.

The cured rubber sample S5 was subjected to the performance test, and the results are shown in Table 4.

Example 6

The process for preparing the vulcanized rubber was similar to that of example 1, except that all the white carbon black was added in step (2) and no white carbon black was added in step (3).

A vulcanized rubber sample S6 was obtained.

The vulcanized rubber sample S6 was subjected to the performance test, and the results are shown in Table 4.

Example 7

The process for producing vulcanized rubber was similar to that of example 1, except that the amount ratio of white carbon black in step (2) to that in step (3) was 1: 1.

a vulcanized rubber sample S7 was obtained.

The cured rubber sample S7 was subjected to the performance test, and the results are shown in Table 4.

Example 8

The procedure for producing a vulcanized rubber was similar to that of example 1, except that the temperature for kneading in step (1) was 135 ℃ and the kneading time was 2.5 min.

A vulcanized rubber sample S8 was obtained.

The vulcanized rubber sample S8 was subjected to the performance test, and the results are shown in Table 4.

Comparative example 1

The formulation of the rubber composition of this comparative example was similar to that of the rubber composition of example 1, except that the same parts by weight of natural rubber (No. 20 standard rubber available from shanghai duo kang, inc.) was used in place of the solution-polymerized styrene-butadiene rubber of example 1.

The procedure for the preparation of the vulcanizates was exactly the same as that in example 1.

A vulcanizate sample DS1 was prepared.

The cured rubber sample DS1 was subjected to performance testing and the results are shown in Table 4.

Comparative example 2

The formulation of the rubber composition of this comparative example was similar to that of the rubber composition of example 1, except that the same parts by weight of gamma- (2, 3-glycidoxy) propyltriethoxysilane (Toshiai chemical industry development Co., Ltd.) was used in place of 3-mercaptopropyltriethoxysilane in example 1.

A vulcanizate sample DS2 was prepared.

The cured rubber sample DS2 was subjected to performance testing and the results are shown in Table 4.

TABLE 4

From the above results, it can be seen that the vulcanized rubber prepared from the rubber composition of the present invention has excellent comprehensive properties of strength improvement, wear resistance improvement, rebound resilience improvement, etc., and the method of the present invention has the advantage of significantly improving the properties of the vulcanized rubber compared with the methods of the prior art.

The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims

1. The vulcanized rubber composition for the soles comprises a rubber matrix, a rubber modifier, white carbon black, polyethylene glycol, a surface modifier, an activator, an anti-aging agent, a softener, a vulcanizing agent and an accelerator, wherein the rubber modifier is represented by the general formula (R) ₁ O) ₃ SiCH ₂ CH ₂ CH ₂ Organosilanes of formula X, R ₁ O is a hydrolyzable group; x is SH; the rubber matrix is solution polymerized styrene-butadiene rubber and optional butadiene rubber;

the rubber matrix comprises a rubber matrix, a surface modifier, an activator, an antioxidant and a vulcanizing agent, wherein relative to 100 parts by weight of the rubber matrix, the content of the rubber modifier is 5-10 parts by weight, the content of white carbon black is 40-60 parts by weight, the content of polyethylene glycol is 5-10 parts by weight, the content of the surface modifier is 4-6 parts by weight, the content of the activator is 4-6 parts by weight, the content of the antioxidant is 1-5 parts by weight, the content of the softener is 6-12 parts by weight, the content of the vulcanizing agent is 2-5 parts by weight, and the content of the accelerator is 3-6 parts by weight;

the preparation method of the vulcanized rubber composition comprises the following steps:

(4) performing fourth mixing on the three-section master batch, an accelerator and a vulcanizing agent to obtain final rubber;

(5) vulcanizing the final rubber;

the part of white carbon black in the step (2) and the rest of white carbon black in the step (3) form white carbon black in the vulcanized rubber composition for the shoe sole;

wherein the first mixing conditions include: the temperature is 110-;

the conditions of the second mixing include: the temperature is 130-150 ℃, and the time is 3-5 min;

the conditions of the third mixing include: the temperature is 140 ℃ and 150 ℃, and the time is 2-4 min;

the fourth mixing conditions include: the temperature is not more than 120 deg.C, and the time is 3-5 min.

2. The rubber composition according to claim 1, wherein R in the organosilane is ₁ O is methoxy or ethoxy.

3. The rubber composition according to claim 1 or 2, wherein the vinyl content of the solution-polymerized styrene-butadiene rubber is 50 to 70 mass%.

4. The composition according to claim 1 or 2, wherein the cis content in the butadiene rubber is 90 to 99 mass%.

5. The rubber composition according to claim 1 or 2, wherein the rubber matrix is butadiene rubber and solution-polymerized styrene-butadiene rubber.

6. The composition according to claim 1 or 2, wherein the rubber matrix contains 60 to 80 mass% of butadiene rubber and 20 to 40 mass% of solution-polymerized styrene-butadiene rubber.

7. The composition according to claim 1 or 2, wherein the silica is fumed silica.

8. The composition as claimed in claim 7, wherein the silica white has a nitrogen adsorption specific surface area of 350-420m ² /g。

9. The composition as claimed in claim 1 or 2, wherein the molecular weight of the polyethylene glycol is 2000-6000.

10. The composition of claim 1 or 2, wherein the surface modifier is at least one of bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide, bis- [3- (triethoxysilyl) propyl ] -disulfide.

11. The composition according to claim 1 or 2, wherein the antioxidant is a phenolic antioxidant.

12. The composition of claim 1 or 2, wherein the softening agent is naphthenic oil.

13. A composition according to claim 1 or 2, wherein the activator is a fatty acid and/or a fatty acid metal soap salt.

14. A composition according to claim 1 or 2, wherein the accelerator is at least one of a thiazole accelerator, a thiuram accelerator and a guanidine accelerator.

15. The composition of claim 14, wherein the accelerator is selected from at least one of 2,2' -dithiodibenzothiazole, tetramethylthiuram disulfide, diphenylguanidine.

16. The composition according to claim 1 or 2, wherein the vulcanizing agent is sulfur and/or a sulfur donor.

17. The composition of claim 1 or 2, wherein the vulcanization conditions comprise: the temperature is 150 ℃ and 170 ℃, the pressure is 10-20MPa, and the time is 20-40 min.

18. Use of the vulcanized rubber composition for shoe soles according to any one of claims 1 to 17 for the preparation of shoe soles.