阅读说明：本技术 一种高粘接力天然胶配方 (Formula of high-adhesion natural rubber ) 是由 刘光超 周亮 刘春红 于 2020-06-30 设计创作，主要内容包括：本发明公开了一种高粘接力天然胶配方,涉及橡胶技术领域。本发明的一种高粘接力天然胶配方,所述天然胶配方包括以下重量份原料：天然胶40～50份、再生胶60～70份、炭黑5～8份、氧化锌0.8～0.9份、硬脂酸0.3～0.4份、防老剂2～3份、硫化促进剂1.5～2.0份、硫化剂1.2～1.8份、加工助剂0.6～1.0份,所述再生胶是以废旧钢丝载重外胎胎面为原料,经破碎、除杂后,加入活化剂、活化辅助颗粒,微波脱硫活化再生制成。本发明公开了一种高粘接力天然胶配方,以天然胶和再生胶作为主要原料,所使用的再生胶以废旧轮胎作为原料,经过破碎,脱硫活化后,与天然胶具有良好的相容性,且采用该配方制备得到的混炼胶具有较高的粘接力。(The invention discloses a formula of high-adhesion natural rubber, and relates to the technical field of rubber. The formula of the high-adhesion natural rubber comprises the following raw materials in parts by weight: 40-50 parts of natural rubber, 60-70 parts of reclaimed rubber, 5-8 parts of carbon black, 0.8-0.9 part of zinc oxide, 0.3-0.4 part of stearic acid, 2-3 parts of an anti-aging agent, 1.5-2.0 parts of a vulcanization accelerator, 1.2-1.8 parts of a vulcanizing agent and 0.6-1.0 part of a processing aid, wherein the reclaimed rubber is prepared by taking a waste steel wire load-bearing outer tire tread as a raw material, crushing, removing impurities, adding an activating agent and activating auxiliary particles, and performing microwave desulfurization, activation and regeneration. The invention discloses a formula of high-adhesion natural rubber, which takes natural rubber and reclaimed rubber as main raw materials, the used reclaimed rubber takes waste tires as raw materials, the natural rubber has good compatibility after crushing, desulfurization and activation, and the rubber compound prepared by the formula has higher adhesion.)

1. The formula of the natural glue with high adhesive force is characterized by comprising the following raw materials in parts by weight: 40-50 parts of natural rubber, 60-70 parts of reclaimed rubber, 5-8 parts of carbon black, 0.8-0.9 part of zinc oxide, 0.3-0.4 part of stearic acid, 2-3 parts of an anti-aging agent, 1.5-2.0 parts of a vulcanization accelerator, 1.2-1.8 parts of a vulcanizing agent and 0.6-1.0 part of a processing aid, wherein the reclaimed rubber is prepared by taking a waste steel wire load-bearing outer tire tread as a raw material, crushing, removing impurities, adding an activating agent and activating auxiliary particles, and performing microwave desulfurization, activation and regeneration.

2. The formula of the high-adhesion natural rubber as claimed in claim 1, wherein the formula of the natural rubber comprises the following raw materials in parts by weight: 45 parts of natural rubber, 65 parts of reclaimed rubber, 6 parts of carbon black, 0.8 part of zinc oxide, 0.4 part of stearic acid, 2 parts of anti-aging agent, 1.8 parts of vulcanization accelerator, 1.5 parts of vulcanizing agent and 0.9 part of processing aid.

3. The formula of the natural rubber with high adhesion force as claimed in any one of claims 1 or 2, wherein the activated auxiliary particles are prepared by taking modified carbon nanotubes as a carrier, adsorbing and loading ferric chloride, and then grafting isophorone diisocyanate.

4. The formula of the high-adhesion natural rubber as claimed in claim 3, wherein the modified carbon nanotubes are carbon nanotubes modified by titanium nitride quantum dots.

5. The formula of natural rubber with high adhesive force as claimed in claim 4, wherein the activating agent is a compound of hydroxyl-terminated liquid nitrile rubber and vegetable oil.

6. The formula of the high-adhesion natural rubber as claimed in claim 5, wherein the mass ratio of the hydroxyl-terminated liquid nitrile rubber, the vegetable oil and the activation auxiliary particles is 5:1: 1.

7. The formula of the natural gum with high adhesive force as claimed in claim 6, wherein the preparation method of the activation assisting particles comprises the following steps: weighing ferric chloride, stirring and dissolving the ferric chloride in deionized water to obtain a ferric chloride solution, soaking the pretreated modified carbon nano tube in the ferric chloride solution, performing ultrasonic dispersion, continuously stirring and adsorbing for 12-24h, taking out, stirring and dispersing in N, N-dimethylacetamide according to a solid-to-liquid ratio of 1:10, adding isophorone diisocyanate, heating to 80-85 ℃, continuously stirring and reacting for 6h at a speed of 2000-2500r/min, filtering while hot after the reaction is finished, washing, drying and grinding to obtain activated auxiliary particles.

8. The high-adhesion natural gum formulation as claimed in claim 7, wherein the pretreatment is: uniformly stirring and mixing 25 wt% of nitric acid and 30 wt% of sulfuric acid according to the volume ratio of 3:1 to obtain a mixed acid solution, stirring and dispersing the modified carbon nano tube into the mixed acid solution according to the solid-to-liquid ratio of 1:100g/ml, placing the mixed acid solution into an ultrasonic oscillator, heating to 70 ℃, keeping the temperature and continuously vibrating for 10 hours, filtering, washing with deionized water until the pH value is 6-7, and drying.

9. The formula of the high-adhesion natural adhesive according to claim 7, wherein the preparation method of the modified carbon nanotube comprises the following steps: weighing melamine, adding the melamine into methanol, magnetically stirring for 12 hours at room temperature, adding the carbon nano tube, continuously magnetically stirring for 6 hours, keeping the temperature at 70 ℃ until the methanol is completely volatilized, placing the remaining solid in a muffle furnace, and roasting for 4 hours at 550 ℃ to obtain the modified carbon nano tube.

Technical Field

The invention relates to the technical field of rubber, in particular to a formula of high-adhesion natural rubber.

Background

China is a large rubber application country, and the annual consumption of rubber is the first world; meanwhile, China is a country with serious shortage of rubber resources, 60% of annual consumption needs to be imported, and a fundamental solution is difficult to achieve in a short time. On the other hand, with the development of society, automobiles are increasingly popularized, and waste tires are produced in large quantities. The gold ore is a renewable resource, is a treasure in the field of new materials, and even can be said to be an inexhaustible gold ore. Particularly, under the condition of the current shortage of Chinese rubber resources, the recycling of waste rubber products has more positive significance.

The reclaimed rubber can replace part of raw rubber to be used for producing various rubber products, or 100 percent of reclaimed rubber is used for producing low-grade rubber products, which has been in the history of decades in China. The reclaimed rubber has excellent processing performance and low price, and the price of the reclaimed rubber is only about one third of that of the raw rubber, so the reclaimed rubber is widely applied. However, as the industry in which the amount of rubber used is the largest, the tire industry has been keenly interested in the application of reclaimed rubber, and there are few well-known tire manufacturers that issue articles on the application of reclaimed rubber to tires.

The quality problem after the conventional reclaimed rubber is applied to each part of the tire mainly shows that: the compatibility of the reclaimed rubber and the natural rubber is too poor, so that the strength is greatly reduced; the self-viscosity of the rubber compound is greatly reduced, and the self-viscosity of the semi-finished product is too poor, so that the delamination and air bubbles between components are easily caused, therefore, a tire formulation engineer has to consider the quality risk when designing the formulation of the tire component, and abandon the use of the reclaimed rubber in the tire components with high safety performance requirements such as a tire body, a base part, cushion rubber, a tire side wall and the like. Therefore, it is of far-reaching significance to develop a rubber compound formula with good self-adhesion and high adhesive force.

Disclosure of Invention

In order to solve the problems, the invention aims to disclose a high-adhesion natural rubber formula, which takes natural rubber and reclaimed rubber as main raw materials, the used reclaimed rubber takes waste tires as raw materials, the waste tires are crushed, desulfurized and activated, the reclaimed rubber has good compatibility with the natural rubber, and the rubber compound prepared by the formula has high adhesion.

Specifically, the formula of the high-adhesion natural rubber comprises the following raw materials in parts by weight: 40-50 parts of natural rubber, 60-70 parts of reclaimed rubber, 5-8 parts of carbon black, 0.8-0.9 part of zinc oxide, 0.3-0.4 part of stearic acid, 2-3 parts of an anti-aging agent, 1.5-2.0 parts of a vulcanization accelerator, 1.2-1.8 parts of a vulcanizing agent and 0.6-1.0 part of a processing aid, wherein the reclaimed rubber is prepared by taking a waste steel wire load-bearing outer tire tread as a raw material, crushing, removing impurities, adding an activating agent and activating auxiliary particles, and performing microwave desulfurization, activation and regeneration.

Further, the formula of the natural rubber comprises the following raw materials in parts by weight: 45 parts of natural rubber, 65 parts of reclaimed rubber, 6 parts of carbon black, 0.8 part of zinc oxide, 0.4 part of stearic acid, 2 parts of anti-aging agent, 1.8 parts of vulcanization accelerator, 1.5 parts of vulcanizing agent and 0.9 part of processing aid.

Further, the activated auxiliary particles are prepared by taking modified carbon nanotubes as carriers, adsorbing and loading ferric chloride, and then grafting isophorone diisocyanate.

The activated auxiliary particle of the invention has good absorption capacity of modified carbon nano-tube to electromagnetic wave, can better utilize microwave energy to promote the fracture of carbon-sulfur bond and disulfide bond in the microwave desulfurization activation process by adding the activated auxiliary particle, then through the reaction of isophorone diisocyanate grafted on the surface and the sulfydryl on the surface of colloidal particles, on one hand, eliminates the sulfydryl on the surface of the colloidal particles, prevents the fractured disulfide bond and polysulfide bond on the surface of the colloidal particles from being reconnected, and further achieves the aim of stabilizing Mooney viscosity, on the other hand, introduces isocyanate group on the reclaimed rubber, further introduces isocyanate group on the kneaded rubber, can form ureide-metal oxide complex by hydrogen bond chelation with metal compound, thereby increasing the adhesive property between the kneaded rubber and metal interface, and through loading ferric chloride on the surface of the modified carbon nano-tube, the grafting of isophorone diisocyanate on the modified carbon nano tube can be promoted through the coordination effect of ferric chloride, so that the introduction amount of isocyanate groups is increased, and the modified carbon nano tube can replace partial carbon black to serve as a reinforcing agent, so that the strength of the rubber compound is improved, and the addition amount of the carbon black is reduced to a certain extent.

Further, the modified carbon nanotube is a carbon nanotube modified by titanium nitride quantum dots.

Further, the activating agent is a compound of hydroxyl-terminated liquid nitrile rubber and vegetable oil.

By adding the hydroxyl-terminated liquid nitrile rubber, the addition of exogenous oil is reduced in the preparation process of the reclaimed rubber, so that the wrapping of the exogenous oil on rubber particles can be reduced, the generation of odor substances due to the decomposition of the exogenous oil in the preparation process can be reduced to a certain extent, and the vegetable oil used in the invention is more environment-friendly; meanwhile, the hydroxyl-terminated liquid nitrile rubber can react with the surface of the colloidal particle to prevent the surface of the colloidal particle from being reconnected with a broken disulfide bond and a broken polysulfide bond, so that the aim of stabilizing the Mooney viscosity is achieved, and meanwhile, in the preparation process, the added hydroxyl-terminated liquid nitrile rubber can also undergo self-crosslinking to form a rubber-like substance, so that the compatibility between the reclaimed rubber and the natural rubber can be increased.

Further, the mass ratio of the hydroxyl-terminated liquid nitrile rubber to the vegetable oil to the activation assisting particles is 5:1: 1.

Further, the preparation method of the activation assisting particle comprises the following steps: weighing ferric chloride, stirring and dissolving the ferric chloride in deionized water to obtain a ferric chloride solution, soaking the pretreated modified carbon nano tube in the ferric chloride solution, performing ultrasonic dispersion, continuously stirring and adsorbing for 12-24h, taking out, stirring and dispersing in N, N-dimethylacetamide according to a solid-to-liquid ratio of 1:10, adding isophorone diisocyanate, heating to 80-85 ℃, continuously stirring and reacting for 6h at a speed of 2000-2500r/min, filtering while hot after the reaction is finished, washing, drying and grinding to obtain activated auxiliary particles.

Further, the pretreatment is as follows: uniformly stirring and mixing 25 wt% of nitric acid and 30 wt% of sulfuric acid according to the volume ratio of 3:1 to obtain a mixed acid solution, stirring and dispersing the modified carbon nano tube into the mixed acid solution according to the solid-to-liquid ratio of 1:100g/ml, placing the mixed acid solution into an ultrasonic oscillator, heating to 70 ℃, keeping the temperature and continuously vibrating for 10 hours, filtering, washing with deionized water until the pH value is 6-7, and drying.

Further, the preparation method of the modified carbon nanotube comprises the following steps: weighing melamine, adding the melamine into methanol, magnetically stirring for 12 hours at room temperature, adding the carbon nano tube, continuously magnetically stirring for 6 hours, keeping the temperature at 70 ℃ until the methanol is completely volatilized, placing the remaining solid in a muffle furnace, and roasting for 4 hours at 550 ℃ to obtain the modified carbon nano tube.

The invention has the beneficial effects that:

the invention discloses a formula of high-adhesion natural rubber, which takes natural rubber and reclaimed rubber as main raw materials, improves the compatibility of the reclaimed rubber and the natural rubber by introducing an activating agent and activating auxiliary particles in the preparation process of the reclaimed rubber, avoids the strength reduction of rubber compound, introduces isocyanate groups on the reclaimed rubber, and further introduces the isocyanate groups on the rubber compound, thereby increasing the adhesive property of the rubber compound.

Detailed Description

The present invention will be described in detail with reference to specific examples below:

the invention relates to a formula of high-adhesion natural rubber, which takes natural rubber and reclaimed rubber as main raw materials, wherein the reclaimed rubber is prepared by taking a waste steel wire load-bearing outer tire tread as a raw material, crushing, removing impurities, adding an activating agent and activating auxiliary particles for desulfurization, activation and regeneration, the activating agent is a compound of hydroxyl-terminated liquid nitrile rubber and vegetable oil, the activating auxiliary particles are prepared by taking modified carbon nanotubes as a carrier, adsorbing and loading ferric chloride, and then grafting isophorone diisocyanate, and the modified carbon nanotubes are carbon nanotubes modified by titanium nitride quantum dots, and the formula specifically comprises the following steps: