阅读说明：本技术 防静电一硫海绵胶料及其制备方法及应用 (Anti-static sulfur sponge rubber material and preparation method and application thereof ) 是由 毛昌虎 陈松雄 晋齐怀 周川泉 田吉 王春桥 于 2019-09-27 设计创作，主要内容包括：本发明公开了一种防静电一硫海绵胶料及其制备方法及应用,按重量份数计算,包括标准胶,绉片胶,原生胶,丁苯型CR橡胶,份再生胶(油法),精细再生胶,高强力再生胶,黑油膏,水口胶粉,改性石油树脂,塑解剂DS-T-1,硫磺,硫化促进剂,活性氧化锌,硬脂酸,陶土,发孔剂H,水杨酸,导电炭黑,防老剂及橡胶软化油。本发明对一硫海绵的胶料配方制备方法进行调整,使一硫海绵在满足其基本的性能要求的前提下,还具有防静电的作用,提高了其适用范围及应用前景,本发明材料来源广泛,制备方法简单,而且还提供了相应的应用方法。(The invention discloses an antistatic sulfur sponge rubber material and a preparation method and application thereof, and the antistatic sulfur sponge rubber material comprises, by weight, standard rubber, crepe rubber, virgin rubber, butylbenzene CR rubber, reclaimed rubber (oil process), fine reclaimed rubber, high-strength reclaimed rubber, black factice, nozzle rubber powder, modified petroleum resin, peptizer DS-T-1, sulfur, vulcanization accelerator, active zinc oxide, stearic acid, pottery clay, pore former H, salicylic acid, conductive carbon black, anti-aging agent and rubber softening oil. The invention adjusts the preparation method of the sizing material formula of the sulfur sponge, so that the sulfur sponge has the function of static prevention on the premise of meeting the basic performance requirements of the sulfur sponge, and the application range and the application prospect of the sulfur sponge are improved.)

1. An anti-static sulfur sponge sizing material is characterized in that: the rubber composition comprises, by weight, 60-72 parts of standard rubber, 15.5-17.5 parts of crepe rubber, 7.3-9.3 parts of virgin rubber, 7-11 parts of styrene-butadiene CR rubber, 193.4-203.4 parts of reclaimed rubber by oil process, 11.5-21.5 parts of fine reclaimed rubber, 6.3-10.3 parts of high-strength reclaimed rubber, 22.8-26.8 parts of black factice, 30-36 parts of nozzle rubber powder, 7-13 parts of modified petroleum resin, 1.3-3.3 parts of peptizer DS-T-1, 6.2-8.2 parts of sulfur, 11.6-17.6 parts of vulcanization accelerator, 6.6-8.6 parts of active zinc oxide, 30-40.5 parts of stearic acid, 18.7-24.7 parts of pottery clay, 14.3-18.3 parts of pore former H, 0.4-1 part of salicylic acid, 18.7.24.7 parts of conductive carbon black, 0.1-0.3 part of antioxidant and 4-17 parts of softening rubber.

2. An antistatic sulfur sponge compound according to claim 1, characterized in that: the rubber comprises, by weight, 66 parts of standard rubber, 16.5 parts of crepe rubber, 8.3 parts of virgin rubber, 9.2 parts of butylbenzene CR rubber, 198.4 parts of oil-process reclaimed rubber, 16.5 parts of fine reclaimed rubber, 8.3 parts of high-strength reclaimed rubber, 24.8 parts of black factice, 33 parts of nozzle rubber powder, 9.9 parts of modified petroleum resin, 16.3 parts of peptizer DS-T-1,7.2 parts of sulfur, 14.6 parts of vulcanization accelerator, 7.6 parts of active zinc oxide, 35.5 parts of stearic acid, 21.7 parts of pottery clay, 16.3 parts of pore former H, 0.7 part of salicylic acid, 21.7 parts of conductive carbon black, 0.2 part of anti-aging agent and 10.9 parts of rubber softening oil.

3. An antistatic sulfur sponge compound according to claim 1 or 2, characterized in that: the standard glue is 2# standard glue.

4. An antistatic sulfur sponge compound according to claim 1 or 2, characterized in that: the vulcanization accelerator is composed of 3.2 parts of accelerator B, 0.2 part of accelerator DS,4.3 parts of accelerator BM,6.5 parts of comprehensive accelerator and 0.4 part of accelerator TMTD per 14.6 parts of vulcanization accelerator.

5. An antistatic sulfur sponge compound according to claim 1 or 2, characterized in that: the anti-aging agent is anti-aging agent CD.

6. A process for the preparation of an antistatic sulfur sponge compound as claimed in claim 1, characterized in that: taking the components according to the weight fraction, comprising the following steps:

1) preparing a master batch: sequentially adding standard rubber, crepe rubber, virgin rubber, styrene-butadiene CR rubber, oil-process reclaimed rubber, fine reclaimed rubber, high-strength reclaimed rubber, black factice, nozzle rubber powder, modified petroleum resin, a peptizer DS-T-1 and 0.8-1 part of stearic acid into internal mixing, pressing for 7-9 minutes after a load pointer of an operating ammeter of the internal mixing machine rises to above 100A, discharging to an open type rubber mixing machine for mixing for 5-6 minutes, discharging, naturally cooling to room temperature, wherein the plasticity is 0.33-0.43, and standing for 24 hours for later use;

2) preparing a rubber compound: putting the prepared master batch, a vulcanization accelerator, active zinc oxide, residual stearic acid, a pore-forming agent H, an anti-aging agent, salicylic acid and sulfur into an internal mixer, refining for 1 minute, adding conductive carbon black, pottery clay and rubber softening oil, refining for 6-7 minutes, discharging to an open rubber refining machine, pulling through for 4-5 minutes under the condition that the roller spacing of the open rubber refining machine is 4-5 mm to uniformly refine the rubber compound, discharging, cooling with water, detecting and correcting to enable the vulcanization starting point of the rubber compound to be 2-2 minutes and 30 seconds and the plasticity to be 0.45-0.58, and thus obtaining the finished product of the anti-static sulfur sponge rubber material.

7. Use of an antistatic sulfur sponge compound according to claim 1, characterized in that: the method comprises the following steps of carrying out hot refining on the anti-static sulfur sponge sizing material on an open mill to obtain a piece with a corresponding thickness, putting the piece into an extruder, then laminating and calendering the piece through a calender and the sponge to obtain a piece with the thickness of 3.0-3.3 mm, punching and cutting the piece into a required film model according to a corresponding punching knife to obtain a semi-finished product of the anti-static sulfur sponge sizing material, pasting the semi-finished product of the sponge on a base fabric in an upper, vulcanizing and foaming the upper outsole and the lower outsole together to obtain a finished product of the anti-static sulfur sponge sizing material.

Technical Field

The invention relates to the field of rubber processing, in particular to an anti-static sulfur sponge rubber material and a preparation method and application thereof.

Background

Antistatic rubber shoes appear on the market due to the requirements of part of markets; generally, in the manufacturing process of rubber shoes, rubber sponge used as a key component of rubber shoe damping is usually manufactured by one-time vulcanization molding or mold vulcanization (disulfide for short), but the sponge used for the anti-static rubber shoes is the one-time vulcanization sponge. In order to better realize the anti-static effect and meet the requirements of people, the anti-static one-sulfur gelatin is the best to change the once-vulcanized sponge rubber. No one-time vulcanization antistatic sponge exists in the prior art. People can be better served in order to better meet the market demand; the anti-static sulfur sponge rubber material meets the market demand and has simple process and low cost.

Disclosure of Invention

The technical problem to be solved by the invention is as follows: the anti-static sulfur sponge sizing material and the preparation method and application thereof solve the technical problem that the sulfur sponge is not anti-static so as to overcome the defects of the prior art.

The invention is realized by the following steps: the antistatic sulfur-free sponge rubber material comprises, by weight, 60-72 parts of standard rubber, 15.5-17.5 parts of crepe rubber, 7.3-9.3 parts of virgin rubber, 7-11 parts of butadiene-styrene type CR rubber, 193.4-203.4 parts of reclaimed rubber by an oil process, 11.5-21.5 parts of fine reclaimed rubber, 6.3-10.3 parts of high-strength reclaimed rubber, 22.8-26.8 parts of black factice, 30-36 parts of nozzle rubber powder, 7-13 parts of modified petroleum resin, 1.3-3.3 parts of peptizer DS-T-1, 6.2-8.2 parts of sulfur, 11.6-17.6 parts of vulcanization accelerator, 6.6-8.6 parts of active zinc oxide, 30-40.5 parts of stearic acid, 18.7-24.7 parts of pottery clay, 14.3-18.3 parts of pore former H, 0.4-1 part of salicylic acid, 18.7-24.7 parts of conductive carbon black, 0.3-1.7 parts of softening oil and 4-17 parts of anti-aging agent.

More preferably, the rubber softening agent comprises, by weight, 66 parts of standard rubber, 16.5 parts of crepe rubber, 8.3 parts of virgin rubber, 9.2 parts of butylbenzene CR rubber, 198.4 parts of reclaimed rubber (oil process), 16.5 parts of fine reclaimed rubber, 8.3 parts of high-strength reclaimed rubber, 24.8 parts of black ointment, 33 parts of nozzle rubber powder, 9.9 parts of modified petroleum resin, 16.3 parts of peptizer DS-T-1,7.2 parts of sulfur, 14.6 parts of vulcanization accelerator, 7.6 parts of active zinc oxide, 35.5 parts of stearic acid, 21.7 parts of pottery clay, 16.3 parts of pore former H, 0.7 part of salicylic acid, 21.7 parts of conductive carbon black, 0.2 part of anti-aging agent and 10.9 parts of rubber softening oil.

The standard glue is 2# standard glue.

The vulcanization accelerator is composed of 3.2 parts of accelerator B, 0.2 part of accelerator DS,4.3 parts of accelerator BM,6.5 parts of comprehensive accelerator and 0.4 part of accelerator TMTD per 14.6 parts of vulcanization accelerator.

The anti-aging agent is anti-aging agent CD

The preparation method of the antistatic sulfur sponge sizing material comprises the following steps of:

1) preparing a master batch: the method comprises the steps of sequentially adding standard rubber, crepe rubber, virgin rubber, styrene-butadiene CR rubber, a reclaimed rubber oil method, fine reclaimed rubber, high-strength reclaimed rubber, black factice, nozzle rubber powder, modified petroleum resin, a peptizer DS-T-1 and 0.8-1 part of stearic acid into internal mixing, pressing for 7-9 minutes after a load pointer of an operating ammeter of the internal mixing machine rises to above 100A, discharging to an open type rubber mixing machine for rubber mixing for 5-6 minutes, discharging, naturally cooling to room temperature, setting the plasticity of 0.33-0.43, and standing for 24 hours for later use;

2) preparing a rubber compound: putting the prepared master batch, a vulcanization accelerator, active zinc oxide, residual stearic acid, a pore-forming agent H, an anti-aging agent, salicylic acid and sulfur into an internal mixer, refining for 1 minute, adding conductive carbon black, pottery clay and rubber softening oil, refining for 6-7 minutes, discharging to an open rubber refining machine, pulling through for 4-5 minutes under the condition that the roller spacing of the open rubber refining machine is 4-5 mm to uniformly refine the rubber compound, discharging, cooling with water, detecting and correcting to enable the vulcanization starting point of the rubber compound to be 2-2 minutes and 30 seconds and the plasticity to be 0.45-0.58, and thus obtaining the finished product of the anti-static sulfur sponge rubber material.

The application of the anti-static sulfur sponge sizing material comprises the steps of carrying out hot refining on the anti-static sulfur sponge sizing material on an open mill to obtain pieces with corresponding thickness, putting the pieces into an extruder, then laminating and calendering the pieces through a calender and a sponge to obtain pieces with the thickness of 3.0-3.3 mm, punching and cutting the pieces into required film models according to corresponding punching knives to obtain semi-finished products of the anti-static sulfur sponge sizing material, pasting the semi-finished products of the sponge on a bottom cloth in an upper, and vulcanizing and foaming the upper bottom and the lower bottom together to obtain the finished products of the anti-static sulfur sponge sizing material.

To further verify the effect of the present invention, the following experiment was performed:

first, the influence of Wei's plasticity of standard rubber and plastic compound on the foaming effect of sponge

TABLE 1

As can be seen from Table 1, the Weibull plasticity of the standard gum for sulfur-extended sponges is 0.63-0.68.

Secondly, the influence of the vulcanization matching system on the foaming effect and the resistance value

1. Influence of vulcanization system and pore generation system on quality of sulfur sponge

TABLE 2 test of the coordination system

Table 2 (continuation)

2. Influence of rubber softening system and reinforcing filling system on quality of sponge

TABLE 3 test of reinforcing filler system

Table 3 (continuation)

The optimal formula dosage is obtained through the following table 2 and table 3: 66 parts of standard rubber, 16.5 parts of crepe rubber, 8.3 parts of virgin rubber, 9.2 parts of butylbenzene CR rubber, 198.4 parts of reclaimed rubber (oil method), 16.5 parts of fine reclaimed rubber, 8.3 parts of high-tenacity reclaimed rubber, 24.8 parts of black factice, 33 parts of nozzle rubber powder, 9.9 parts of modified petroleum resin, 16.3 parts of peptizer DS-T-1,7.2 parts of sulfur, 14.6 parts of vulcanization accelerator, 7.6 parts of active zinc oxide, 35.5 parts of stearic acid, 21.7 parts of pottery clay, 16.3 parts of pore-forming agent H, 0.7 part of salicylic acid, 21.7 parts of conductive carbon black, 0.2 part of anti-aging agent and 10.9 parts of rubber softening oil.

Thirdly, researching vulcanization conditions:

TABLE 4 influence of vulcanization conditions on the quality of anti-static monosulfur sponges

TABLE 4 continuation

The test data in table 4 show that the optimal vulcanization conditions of the antistatic sulfur sponge are as follows: the working pressure of the vulcanizing machine is 20MPa, the vulcanizing temperature is 145 ℃, and the vulcanizing time is 2.1 min.

Fifthly, the quality influence of the accelerator combined system on the anti-static sulfur sponge

TABLE 5 Effect of accelerator combination system on the quality of anti-static monosulfur sponges

As can be seen from table 5, the optimum ratio of the accelerator is: every 14.6 parts of vulcanization accelerator consists of 3.2 parts of accelerator B, 0.2 part of accelerator DS,4.3 parts of accelerator BM,6.5 parts of comprehensive accelerator and 0.4 part of accelerator TMTD.

Due to the adoption of the technical scheme, compared with the prior art, the preparation method of the sizing material formula of the sulfur sponge is adjusted, so that the sulfur sponge has an antistatic effect on the premise of meeting the basic performance requirements of the sulfur sponge, the application range and the application prospect are improved, the material source is wide, the preparation method is simple, and the corresponding application method is provided. The invention is simple and easy to implement, low in cost and good in using effect of the product.

Detailed Description

3. The embodiment of the invention comprises the following steps: an antistatic sulfur sponge rubber material comprises, by weight, 66 parts of standard rubber, 16.5 parts of crepe rubber, 8.3 parts of virgin rubber, 9.2 parts of butylbenzene CR rubber, 198.4 parts of reclaimed rubber (oil method), 16.5 parts of fine reclaimed rubber, 8.3 parts of high-strength reclaimed rubber, 24.8 parts of black factice, 33 parts of nozzle rubber powder, 9.9 parts of modified petroleum resin, 16.3 parts of peptizer DS-T-1,7.2 parts of sulfur, 14.6 parts of vulcanization accelerator, 7.6 parts of active zinc oxide, 35.5 parts of stearic acid, 21.7 parts of pottery clay, 16.3 parts of pore former H, 0.7 part of salicylic acid, 21.7 parts of conductive carbon black, 0.2 part of anti-aging agent and 10.9 parts of rubber softening oil.

The preparation method of the antistatic sulfur sponge rubber material comprises the following steps of 1) preparing a master batch by taking the following components in parts by weight: the rubber is prepared by sequentially adding 66 parts of standard rubber, 16.5 parts of crepe rubber, 8.3 parts of virgin rubber, 9.2 parts of butylbenzene CR rubber, 198.4 parts of reclaimed rubber (oil method), 16.5 parts of fine reclaimed rubber, 8.3 parts of high-strength reclaimed rubber, 24.8 parts of black factice, 33 parts of glue powder at water gap, 9.9 parts of modified petroleum resin, 16.3 parts of peptizer DS-T-1 and 0.8 part of stearic acid into internal mixing, pressing for 7-9 minutes after a load pointer of a work ammeter of an internal mixer rises to be above 100A, discharging to an open type rubber mixing mill, smashing the rubber for 5-6 minutes, discharging, naturally cooling to room temperature, and keeping for 24 hours for later use, wherein the rubber has plasticity (0.33-0.43); 2) preparing a rubber compound: putting the prepared master batch, a vulcanization accelerator, active zinc oxide, residual stearic acid, a pore-forming agent H, an anti-aging agent, salicylic acid and sulfur into an internal mixer, refining for 1 minute, adding conductive carbon black, pottery clay and rubber softening oil, refining for 6-7 minutes, discharging to an open rubber refining machine, pulling through for 4-5 minutes under the condition that the roller spacing of the open rubber refining machine is 4-5 mm to uniformly refine the rubber compound, discharging, cooling with water, detecting and correcting to enable the vulcanization starting point of the rubber compound to be 2-2 minutes and 30 seconds and the plasticity to be 0.45-0.58, and thus obtaining the finished product of the anti-static sulfur sponge rubber material.

The application of the anti-static sulfur sponge sizing material comprises the steps of carrying out hot refining on the anti-static sulfur sponge sizing material on an open mill to obtain pieces with corresponding thickness, putting the pieces into an extruder, then laminating and calendering the pieces through a calender and a sponge to obtain pieces with the thickness of 3.0-3.3 mm, punching and cutting the pieces into required film models according to corresponding punching knives to obtain semi-finished products of the anti-static sulfur sponge sizing material, pasting the semi-finished products of the sponge on a bottom cloth in an upper, and vulcanizing and foaming the upper bottom and the lower bottom together to obtain the finished products of the anti-static sulfur sponge sizing material.