阅读说明：本技术 一种具有阻燃功能的新型高性能橡胶鞋底及其制备方法 (Novel high-performance rubber sole with flame-retardant function and preparation method thereof ) 是由 刘晓清 张秀龙 黄忠达 黄庆宝 于 2020-12-18 设计创作，主要内容包括：本发明公开了一种具有阻燃功能的新型高性能橡胶鞋底及其制备方法,原料包括以下组分：天然橡胶、顺丁橡胶、改性芳纶纤维、隔离剂、润滑剂、白炭黑；其中,改性芳纶纤维的制备方法,包括：对位芳纶纤维浸入含碳纳米管的硅烷偶联剂稀溶液中,形成碳硅改性的对位芳纶纤维；将碳硅改性的芳纶纤维与三聚氰胺焦磷酸盐混合,共同加入至乙醇溶剂中,所得产物经干燥处理后得到所述改性芳纶纤维。本发明提供了一种兼具提升阻燃性能和耐磨性能的鞋底材料及其制备方法,扩展了鞋底材料的类型和应用领域,提升了阻燃型鞋底材料的研发能力,增强了阻燃性鞋底材料的应用前景,满足了鞋底材料市场的多样需求。(The invention discloses a novel high-performance rubber sole with a flame-retardant function and a preparation method thereof, wherein the novel high-performance rubber sole comprises the following raw materials: natural rubber, butadiene rubber, modified aramid fiber, a separant, a lubricant and white carbon black; the preparation method of the modified aramid fiber comprises the following steps: soaking the para-aramid fiber into a silane coupling agent dilute solution containing carbon nano tubes to form carbon-silicon modified para-aramid fiber; mixing carbon-silicon modified aramid fiber and melamine pyrophosphate, adding the mixture into an ethanol solvent together, and drying the obtained product to obtain the modified aramid fiber. The invention provides the sole material with the improved flame retardant property and the improved wear resistance and the preparation method thereof, the type and the application field of the sole material are expanded, the research and development capability of the flame-retardant sole material is improved, the application prospect of the flame-retardant sole material is enhanced, and various requirements of the sole material market are met.)

1. The novel high-performance rubber sole with the flame retardant function is characterized by comprising the following raw materials in parts by weight: 70-80 parts of natural rubber, 20-30 parts of butadiene rubber, 0.5-5 parts of modified aramid fiber, 1-3 parts of separant, 2-6 parts of lubricant and 2-5 parts of white carbon black;

the preparation method of the modified aramid fiber comprises the following steps:

step 1, adding a solvent into a silane coupling agent to prepare a silane coupling agent dilute solution with the mass fraction of 0.5-1%, then immersing the carbon nano tube into the prepared silane coupling agent dilute solution, and uniformly mixing to form the silane coupling agent dilute solution containing the carbon nano tube;

step 2, soaking the para-aramid fiber into a silane coupling agent dilute solution containing the carbon nano tube, stirring for 1-6 h at the temperature of 25-40 ℃, and carrying out vacuum drying on the obtained product at the temperature of 70-90 ℃ to form carbon-silicon modified para-aramid fiber;

step 3, mixing the carbon-silicon modified aramid fiber and melamine pyrophosphate according to a mass ratio of 0.2-0.4: 1, mixing, adding into an ethanol solvent together, uniformly mixing, and drying the obtained product to obtain the modified aramid fiber.

2. The novel high-performance rubber shoe sole with flame retardant function as claimed in claim 1, wherein said release agent comprises: polyisobutylene.

3. The novel high-performance rubber shoe sole with flame retardant function as claimed in claim 2, wherein said polyisobutylene has a molecular weight of 1000.

4. The novel high-performance rubber shoe sole with flame retardant function according to claim 1, wherein said lubricant comprises: a paraffinic oil.

5. The novel high-performance rubber shoe sole with flame retardant function according to claim 1, wherein in step 1, the solvent comprises: any one or more of methanol, ethanol, propanol, and isopropanol.

6. The novel high-performance rubber sole with the flame retardant function according to claim 1, wherein in step 1, the addition amount of the carbon nanotubes is as follows: 30-50% of the mass of the silane coupling agent.

7. The preparation method of the novel high-performance rubber sole with the flame retardant function according to any one of claims 1 to 6, characterized by comprising the following steps:

s1, putting the modified aramid fiber, the release agent and the lubricant in parts by weight into a high-speed stirrer, and stirring and blending for 0.5-2 h at the rotating speed of 6000-10000 rpm to obtain a fiber pretreatment substance;

s2, mixing the fiber pretreatment substance with the natural rubber and the butadiene rubber in parts by weight, then placing the mixture into an internal mixer for internal mixing, heating to 95-100 ℃, and carrying out internal mixing for 5-10 min, then adding the white carbon black in parts by weight, heating to 110-115 ℃, and continuing internal mixing for 3-5 min, and guiding out an internal mixing mixture;

s3, feeding the banburying mixture into an open mill, and thinning for 2-3 times to obtain a rubber sheet;

and S4, standing the rubber sheet, stamping to obtain a sole model, and vulcanizing to obtain the novel high-performance rubber sole with the flame retardant function.

8. The method according to claim 7, wherein the temperature at the time of the thinning is controlled to 75 to 80 ℃ in S3.

9. The method according to claim 7, wherein the standing time in S4 is 36 to 48 hours.

Technical Field

The invention belongs to the technical field of rubber soles, and relates to a novel high-performance rubber sole with a flame-retardant function and a preparation method thereof.

Background

With the rapid development of the shoe material industry, the requirements on shoe materials, particularly sole materials, are also continuously improved, and on the basis of the traditional performance indexes such as wear resistance, skid resistance and comfort, the sole materials are required to have the performances such as high temperature resistance, corrosion resistance, puncture resistance and static electricity resistance according to the difference of shoe types. In recent years, the technology for improving the flame retardant property of the sole material becomes an important direction for shoe material enterprises to improve the performance of the shoe material.

At present, the flame retardant substance is usually added into shoe material raw materials in the manufacturing process of the sole material to improve the flame retardant property, but because the flame retardant substance is generally poor in compatibility with the shoe material raw materials and poor in dispersion uniformity in the shoe material raw materials, when a certain amount of flame retardant substance is added for the purpose of improving the flame retardant property, the wear resistance and other mechanical properties of the sole material are reduced, and the product quality of the sole material is seriously affected.

Therefore, in view of the above technical problems, it is desirable to provide a sole material with improved flame retardant property and wear resistance and a preparation method thereof, so as to expand the type and application field of the sole material, improve the research and development capability of the flame retardant sole material, enhance the application prospect of the flame retardant sole material, and meet various demands of the sole material market.

Disclosure of Invention

In order to achieve the purpose, the invention provides a novel high-performance rubber sole with a flame-retardant function and a preparation method thereof, and solves the problems that in the prior art, a flame-retardant material is single, the flame-retardant performance is poor, and the performance of the sole material is reduced due to the addition of the flame-retardant material.

The invention adopts the technical scheme that a novel high-performance rubber sole with a flame-retardant function comprises the following raw materials in parts by weight: 70-80 parts of natural rubber, 20-30 parts of butadiene rubber, 0.5-5 parts of modified aramid fiber, 1-3 parts of separant, 2-6 parts of lubricant and 2-5 parts of white carbon black;

the preparation method of the modified aramid fiber comprises the following steps:

step 1, adding a solvent into a silane coupling agent to prepare a silane coupling agent dilute solution with the mass fraction of 0.5-1%, then immersing the carbon nano tube into the prepared silane coupling agent dilute solution, and uniformly mixing to form the silane coupling agent dilute solution containing the carbon nano tube;

step 2, soaking the para-aramid fiber into a silane coupling agent dilute solution containing the carbon nano tube, stirring for 1-6 h at the temperature of 25-40 ℃, and carrying out vacuum drying on the obtained product at the temperature of 70-90 ℃ to form carbon-silicon modified para-aramid fiber;

step 3, mixing the carbon-silicon modified aramid fiber and melamine pyrophosphate according to a mass ratio of 0.2-0.4: 1, mixing, adding into an ethanol solvent together, uniformly mixing, and drying the obtained product to obtain the modified aramid fiber.

The para-aramid fiber adopted by the invention has excellent properties of high strength, high modulus, high temperature resistance, acid and alkali resistance, corrosion resistance and the like, and is used as a modified reinforcing material, so that the mechanical property of the prepared sole material is effectively improved.

Further, the release agent comprises: polyisobutylene.

Further, the molecular weight of the polyisobutylene is 1000.

Further, the lubricant comprises: a paraffinic oil.

Further, in step 1, the solvent comprises: any one or more of methanol, ethanol, propanol, and isopropanol.

Further, in step 1, the addition amount of the carbon nanotubes is: 30-50% of the mass of the silane coupling agent.

The invention also aims to provide a preparation method of the novel high-performance rubber sole with the flame retardant function, which comprises the following steps:

s1, putting the modified aramid fiber, the release agent and the lubricant in parts by weight into a high-speed stirrer, and stirring and blending for 0.5-2 h at the rotating speed of 6000-10000 rpm to obtain a fiber pretreatment substance;

s2, mixing the fiber pretreatment substance with the natural rubber and the butadiene rubber in parts by weight, then placing the mixture into an internal mixer for internal mixing, heating to 95-100 ℃, and carrying out internal mixing for 5-10 min, then adding the white carbon black in parts by weight, heating to 110-115 ℃, and continuing internal mixing for 3-5 min, and guiding out an internal mixing mixture;

s3, feeding the banburying mixture into an open mill, and thinning for 2-3 times to obtain a rubber sheet;

and S4, standing the rubber sheet, stamping to obtain a sole model, and vulcanizing to obtain the novel high-performance rubber sole with the flame retardant function.

Further, in S3, the temperature during thinning was controlled to 75 to 80 ℃.

Further, in S4, the standing time is 36 to 48 hours.

The invention has the beneficial effects that:

1. the modified aramid fiber is adopted to toughen and modify the sole material, so that the mechanical property and the flame retardance of the sole material can be effectively improved, and the wear resistance and the flame retardance of the sole material are improved.

2. The method adopts the steps that the para-aramid fiber is modified by a silane coupling agent dilute solution containing carbon nano tubes to form the carbon-silicon modified para-aramid fiber, on one hand, the surface of the para-aramid fiber is subjected to multifunctional modification to construct a multifunctional fiber reinforced rubber material, the problem of surface inertia of the aramid fiber is solved on the premise of not sacrificing the fiber strength, the effect of having both a chemical bond effect and a physical connection point effect between the fiber and a rubber matrix is realized, the physical-chemical double-reinforcement effect is realized, and the mechanical property of the rubber material is improved to the maximum extent; on the other hand, the surface activity of the constructed carbon-silicon modified para-aramid fiber is enhanced, the carbon-silicon modified para-aramid fiber is convenient to synthesize and modify with melamine pyrophosphate, a modified flame-retardant fiber containing phosphorus, carbon and silicon elements is formed, the mechanical property of a base material is greatly improved, the flame-retardant function is realized, and the use safety of the material is effectively improved.

3. On the basis of the previous research, the invention adopts a high-speed stirrer to pretreat the fibers, so that auxiliaries such as a separant (high-activity polyisobutylene with the molecular weight of 1000), a lubricant (paraffin oil) and the like are fully permeated among the fibers, a fiber dispersion structure is kept, then, a premix, carrier rubber and a supplementary separant (white carbon black) are subjected to high-shear banburying and blending in an internal mixer, and then, the high-activity and easily-dispersible sole material is prepared through open mixing treatment, the dispersibility and uniformity of the modified aramid fibers in the carrier rubber are further improved, and the performance index of the finished sole material is further improved.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

A preparation method of modified aramid fiber comprises the following steps:

(1) adding a methanol solvent into a silane coupling agent to prepare a silane coupling agent dilute solution with the mass fraction of 0.5%, then immersing carbon nano tubes with the mass fraction of 30% of the silane coupling agent into the prepared silane coupling agent dilute solution, and uniformly mixing to form the silane coupling agent dilute solution containing the carbon nano tubes;

(2) soaking the para-aramid fiber into a silane coupling agent dilute solution containing the carbon nano tube, stirring for 6 hours at the temperature of 25 ℃, and carrying out vacuum drying on the obtained product at the temperature of 70 ℃ to form carbon-silicon modified para-aramid fiber;

(3) mixing carbon-silicon modified aramid fiber and melamine pyrophosphate according to a mass ratio of 0.2: 1, mixing, adding into an ethanol solvent together, uniformly mixing, and drying the obtained product to obtain the modified aramid fiber.

Example 2

A preparation method of modified aramid fiber comprises the following steps:

(1) adding a propanol solvent into a silane coupling agent to prepare a silane coupling agent dilute solution with the mass fraction of 1%, then soaking carbon nano tubes with the mass fraction of 50% of the silane coupling agent into the prepared silane coupling agent dilute solution, and uniformly mixing to form the silane coupling agent dilute solution containing the carbon nano tubes;

(2) soaking the para-aramid fiber into a silane coupling agent dilute solution containing the carbon nano tube, stirring for 1h at the temperature of 40 ℃, and carrying out vacuum drying on the obtained product at the temperature of 90 ℃ to form carbon-silicon modified para-aramid fiber;

(3) mixing carbon-silicon modified aramid fiber and melamine pyrophosphate according to a mass ratio of 0.4: 1, mixing, adding into an ethanol solvent together, uniformly mixing, and drying the obtained product to obtain the modified aramid fiber.

Example 3

A preparation method of modified aramid fiber comprises the following steps:

(1) adding a mixed solvent of ethanol and isopropanol into a silane coupling agent to prepare a silane coupling agent dilute solution with the mass fraction of 0.75%, then soaking carbon nano tubes with the mass fraction of 40% of the silane coupling agent into the prepared silane coupling agent dilute solution, and uniformly mixing to form a silane coupling agent dilute solution containing carbon nano tubes; the volume ratio of ethanol to isopropanol in the mixed solvent is 3: 1;

(2) soaking the para-aramid fiber into a silane coupling agent dilute solution containing the carbon nano tube, stirring for 4 hours at the temperature of 35 ℃, and carrying out vacuum drying on the obtained product at the temperature of 80 ℃ to form carbon-silicon modified para-aramid fiber;

(3) mixing carbon-silicon modified aramid fiber and melamine pyrophosphate according to a mass ratio of 0.3: 1, mixing, adding into an ethanol solvent together, uniformly mixing, and drying the obtained product to obtain the modified aramid fiber.

Example 4

A novel high-performance rubber sole with a flame-retardant function comprises the following raw materials in parts by weight: 70 parts of natural rubber, 20 parts of butadiene rubber, 0.5 part of modified aramid fiber, 1 part of polyisobutylene with the molecular weight of 1000, 2 parts of paraffin oil and 2 parts of white carbon black; the modified aramid fiber prepared in example 3 was used;

the preparation method of the novel high-performance rubber sole with the flame retardant function comprises the following steps:

(1) putting the modified aramid fiber, the release agent and the lubricant in parts by weight into a high-speed stirrer, and stirring and blending for 0.5h at the rotating speed of 6000rpm to obtain a fiber pretreatment substance;

(2) mixing the fiber pretreatment substance with the natural rubber and the butadiene rubber in parts by weight, then placing the mixture into an internal mixer for internal mixing, heating to 95 ℃, and carrying out internal mixing for 5min, then adding the white carbon black in parts by weight, heating to 110 ℃, and continuing internal mixing for 3min, and exporting an internal mixing mixture;

(3) feeding the banburying mixture into an open mill, and thinning for 2 times at 75 ℃ to obtain a rubber sheet;

(4) and standing the rubber sheet for 36h, stamping to obtain a sole model, and vulcanizing to obtain the novel high-performance rubber sole with the flame retardant function.

Example 5

A novel high-performance rubber sole with a flame-retardant function comprises the following raw materials in parts by weight: 80 parts of natural rubber, 30 parts of butadiene rubber, 5 parts of modified aramid fiber, 3 parts of polyisobutylene with the molecular weight of 1000, 6 parts of paraffin oil and 5 parts of white carbon black; the modified aramid fiber prepared in example 3 was used;

the preparation method of the novel high-performance rubber sole with the flame retardant function comprises the following steps:

(1) putting the modified aramid fiber, the release agent and the lubricant in parts by weight into a high-speed stirrer, and stirring and blending for 2 hours at the rotating speed of 10000rpm to obtain a fiber pretreatment substance;

(2) mixing the fiber pretreatment substance with the natural rubber and the butadiene rubber in parts by weight, then placing the mixture into an internal mixer for internal mixing, heating to 100 ℃, carrying out internal mixing for 10min, then adding the white carbon black in parts by weight, heating to 115 ℃, continuing internal mixing for 5min, and guiding out to obtain an internal mixing mixture;

(3) feeding the banburying mixture into an open mill, and thinning for 3 times at 80 ℃ to obtain a rubber sheet;

(4) and standing the rubber sheet for 48h, stamping to obtain a sole model, and vulcanizing to obtain the novel high-performance rubber sole with the flame retardant function.

Example 6

A novel high-performance rubber sole with a flame-retardant function comprises the following raw materials in parts by weight: 75 parts of natural rubber, 25 parts of butadiene rubber, 3 parts of modified aramid fiber, 2 parts of polyisobutylene with the molecular weight of 1000, 4 parts of paraffin oil and 3.5 parts of white carbon black; the modified aramid fiber prepared in example 3 was used;

the preparation method of the novel high-performance rubber sole with the flame retardant function comprises the following steps:

(1) putting the modified aramid fiber, the release agent and the lubricant in parts by weight into a high-speed stirrer, and stirring and blending for 1.5h at the rotating speed of 8000rpm to obtain a fiber pretreatment substance;

(2) mixing the fiber pretreatment substance with the natural rubber and the butadiene rubber in parts by weight, then placing the mixture into an internal mixer for internal mixing, heating to 98 ℃, and carrying out internal mixing for 7.5min, then adding the white carbon black in parts by weight, heating to 112 ℃, and continuing internal mixing for 4min to obtain an internal mixing mixture;

(3) feeding the banburying mixture into an open mill, and thinning for 3 times at 78 ℃ to obtain a rubber sheet;

(4) and standing the rubber sheet for 40h, stamping to obtain a sole model, and vulcanizing to obtain the novel high-performance rubber sole with the flame retardant function.

Comparative example 1

The rubber sole comprises the following raw materials in parts by weight: 75 parts of natural rubber, 25 parts of butadiene rubber, 2 parts of polyisobutylene with the molecular weight of 1000, 4 parts of paraffin oil and 3.5 parts of white carbon black;

the preparation method of the rubber sole comprises the following steps:

(1) mixing the natural rubber and the butadiene rubber in parts by weight, then placing the mixture into an internal mixer for internal mixing, heating to 98 ℃, carrying out internal mixing for 7.5min, then adding the white carbon black in parts by weight, heating to 113 ℃, continuing internal mixing for 4min, and guiding out an internal mixing mixture;

(2) feeding the banburying mixture into an open mill, and thinning for 3 times at 78 ℃ to obtain a rubber sheet;

(3) and standing the rubber sheet for 40h, stamping to obtain a sole model, and vulcanizing to obtain the rubber sole.

Comparative example 2

The rubber sole comprises the following raw materials in parts by weight: 75 parts of natural rubber, 25 parts of butadiene rubber, 3 parts of commercially available aramid fiber, 2 parts of polyisobutylene with the molecular weight of 1000, 4 parts of paraffin oil and 3.5 parts of white carbon black;

the preparation method of the rubber sole comprises the following steps:

(1) putting the commercially available aramid fiber, the release agent and the lubricant in parts by weight into a high-speed stirrer, and stirring and blending for 1.5h at the rotating speed of 8000rpm to obtain a fiber pretreatment substance;

(2) mixing the fiber pretreatment substance with the natural rubber and the butadiene rubber in parts by weight, then placing the mixture into an internal mixer for internal mixing, heating to 98 ℃, and carrying out internal mixing for 7.5min, then adding the white carbon black in parts by weight, heating to 112 ℃, and continuing internal mixing for 4min to obtain an internal mixing mixture;

(3) feeding the banburying mixture into an open mill, and thinning for 3 times at 78 ℃ to obtain a rubber sheet;

(4) and standing the rubber sheet for 40h, stamping to obtain a sole model, and vulcanizing to obtain the novel high-performance rubber sole with the flame retardant function.

Examples of the experiments

The novel high-performance rubber soles with flame retardant function prepared in examples 4 to 6 and the rubber soles prepared in comparative examples 1 to 2 were subjected to performance tests, and the test results are shown in table 1.

TABLE 1 sole Performance test results of the novel high-performance rubber sole with flame retardant function prepared according to the present invention

It is noted that, in the present application, relational terms such as first, second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.

All the embodiments in the present specification are described in a related manner, and the same and similar parts among the embodiments may be referred to each other, and each embodiment focuses on the differences from the other embodiments.

The above description is only for the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.