阅读说明：本技术 一种环保型轮胎用钢丝胶配方及其制备方法 (Environment-friendly steel wire adhesive formula for tire and preparation method thereof ) 是由 庄志宇 于 2020-07-03 设计创作，主要内容包括：本发明公开了一种环保型轮胎用钢丝胶配方及其制备方法,配方组成按重量计包含：100重量份天然橡胶,60-150重量份填充材,3-20重量份活性剂,0.1-5重量份芳烃油,0.1-5重量份防老剂,0.1-5重量份硫磺,0.1-5重量份促进剂,3-9重量份多巴胺及其衍生物。利用本发明配方做出的钢丝胶可替代间-甲-白-钴体系,借由多巴胺和少量的赖氨酸残基使之具备超强黏附力,通过DOPA中的邻苯二酚官能团之黏附和快速化学交联固化。多巴胺亦含有邻苯二酚和氨基官能团,也被证实具有优异黏附性能,且多巴胺亦有良好的生物相容性,可以大大降低对环境污染,故将多巴胺用于橡胶与轮胎胎唇钢丝中以期得到良好的粘合性能。(The invention discloses an environment-friendly steel wire adhesive formula for tires and a preparation method thereof, wherein the formula comprises the following components in parts by weight: 100 parts of natural rubber, 60-150 parts of filler, 3-20 parts of activator, 0.1-5 parts of aromatic oil, 0.1-5 parts of anti-aging agent, 0.1-5 parts of sulfur, 0.1-5 parts of accelerator and 3-9 parts of dopamine and derivatives thereof. The steel wire glue prepared by the formula can replace a meta-methyl-white-cobalt system, has super strong adhesion by dopamine and a small amount of lysine residues, and is cured by adhesion and rapid chemical crosslinking of catechol functional groups in DOPA. Dopamine also contains catechol and amino functional groups, and is proved to have excellent adhesion performance, and the dopamine also has good biocompatibility, so that the environmental pollution can be greatly reduced, and the dopamine is used for rubber and tire bead wires to obtain good adhesion performance.)

1. The environment-friendly steel wire adhesive formula for the tire is characterized by comprising the following components in parts by weight: 100 parts of natural rubber, 60-150 parts of filler, 3-20 parts of activator, 0.1-5 parts of aromatic oil, 0.1-5 parts of anti-aging agent, 0.1-5 parts of sulfur, 0.1-5 parts of accelerator and 3-9 parts of dopamine and derivatives thereof.

2. The formulation of claim 1, wherein the formulation comprises: the filler comprises carbon black, white carbon black and calcium carbonate.

3. The formulation of claim 1, wherein the formulation comprises: the active agent comprises 1-5 parts by weight of stearic acid and 2-15 parts by weight of zinc oxide.

4. The formulation of claim 1, wherein the formulation comprises: the dopamine and the derivatives thereof comprise dopamine hydrochloride and 3-hydroxytyrosine hydrobromide.

5. The method for preparing the steel wire rubber formulation for the environment-friendly tire as defined in any one of claims 1 to 5, comprising the steps of:

the method comprises the following steps: using an internal mixer, setting the initial temperature of the internal mixer to be 20-90 ℃, the rotating speed of the internal mixer to be 30-80 rpm, and the pressure of the internal mixer to be 0.2-0.8 MPa, firstly adding natural rubber into the internal mixer for mixing for 10-60 seconds, then adding 1/2 filler for mixing for 10-60 seconds, then adding 1/2 filler and aromatic oil for mixing for 10-60 seconds, then cleaning, and finally discharging;

step two: using an internal mixer, setting the initial temperature of the internal mixer to be 20-90 ℃, the rotating speed to be 30-80 rpm and the pressure to be 0.2-0.8 MPa, continuously mixing the rubber material obtained in the first step in the internal mixer for 10-60 seconds, then adding an anti-aging agent, stearic acid and zinc oxide for mixing for 10-60 seconds, cleaning, discharging, and standing the rubber material for one day after discharging;

step three: adjusting the temperature of a roller of the open mill to 40-60 ℃ by using an open mill, firstly, continuously mixing the rubber material obtained in the step two for 60-120 seconds in the open mill, and secondly, adding sulfur and an accelerator; then adding dopamine for mixing; and finally, discharging.

6. The method for preparing the environment-friendly steel wire rubber formula for the tire as claimed in claim 5, wherein the preparation method comprises the following steps: in the third step, the dopamine is put in last and the temperature of the rubber material is controlled below 45 ℃ in the mixing process.

Technical Field

The invention relates to the technical field of tire rubber preparation, in particular to an environment-friendly tire steel wire rubber and a preparation method thereof.

Background

The adhesion of rubber to the carcass material is critical to the safety of the tire, particularly the bead wire component in the tire, which needs to bear high load, has the functions of being tightly attached to the rim to avoid air leakage during vehicle running, overcoming the transverse force applied to the vehicle during turning running, avoiding the tire falling off the rim, and the like. At present, in order to provide good adhesion between rubber and steel wire, common adhesion systems include cobalt salt, m-methyl-white-cobalt, and the like. The meta-methyl-white system is a steel wire rubber formula system for improving the adhesive force between rubber and steel wires, and comprises resorcinol, methylene donor (formaldehyde donor) and silicon dioxide; the meta-methyl-white-cobalt system is a steel wire adhesive formula system for improving the adhesive force between rubber and steel wires, and comprises resorcinol, methylene donor (formaldehyde donor), silicon dioxide and cobalt salt. The m-methyl-white-cobalt system has the best effect, but the formula system needs to simultaneously have resorcinol, methylene donor (formaldehyde donor), white smoke and cobalt salt to highlight the effect, the price of the whole raw materials is high, and the formula system smells pungent after the tire is vulcanized and has great harm to human bodies and environment.

The best effect of the existing bonding system of rubber and framework material is a meta-methyl-white-cobalt system, but due to the factors of complex formula system, expensive raw materials, large influence on environment and the like, the invention develops a substitution method, can effectively increase the bonding property of the rubber and the framework material, and is environment-friendly.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provides the environment-friendly tire steel wire adhesive which is relatively simple in formula, relatively low in price and small in environmental hazard and the preparation method thereof.

In order to achieve the above purpose, the solution of the invention is:

the environment-friendly steel wire rubber formula for the tire comprises the following components in parts by weight: 100 parts of natural rubber, 60-150 parts of filler, 3-20 parts of activator, 0.1-5 parts of aromatic oil, 0.1-5 parts of anti-aging agent, 0.1-5 parts of sulfur, 0.1-5 parts of accelerator and 3-9 parts of dopamine and derivatives thereof.

Further, the filler comprises carbon black, white carbon black and calcium carbonate.

Further, the carbon black is any one or any combination of N110, N121, N134, N220, N231, N234, N242, N293, N299, N315, N326, N330, N332, N339, N343, N347, N351, N358, N375, N539, N550, N582, N630, N642, N650, N660, N683, N754, N762, N765, N770, N774, N787, N907, N908, N990 and N991.

Further, the specific surface area of the carbon black is 20-160 m²(g) the DBP absorption value is 20-140 cm³100g of; the white carbon black comprises gas phase white carbon black and precipitation white carbon black; the calcium carbonate includes light calcium carbonate, activated calcium carbonate and crystalline calcium carbonate.

Further, the active agent comprises 1-5 parts by weight of stearic acid and 2-15 parts by weight of zinc oxide.

Further, the dopamine and its derivatives comprise dopamine hydrochloride (also called 3-hydroxytyrosine hydrochloride) and 3-hydroxytyrosine hydrobromide.

A preparation method of an environment-friendly steel wire rubber formula for tires comprises the following steps:

the method comprises the following steps: using an internal mixer, setting the initial temperature of the internal mixer to be 20-90 ℃, the rotating speed of the internal mixer to be 30-80 rpm, and the pressure of the internal mixer to be 0.2-0.8 MPa, firstly adding natural rubber into the internal mixer for mixing for 10-60 seconds, then adding 1/2 filler for mixing for 10-60 seconds, then adding 1/2 filler and aromatic oil for mixing for 10-60 seconds, then cleaning, and finally discharging;

step two: using an internal mixer, setting the initial temperature of the internal mixer to be 20-90 ℃, the rotating speed to be 30-80 rpm and the pressure to be 0.2-0.8 MPa, continuously mixing the rubber material obtained in the first step in the internal mixer for 10-60 seconds, then adding an anti-aging agent, stearic acid and zinc oxide for mixing for 10-60 seconds, cleaning, discharging, and standing the rubber material for one day after discharging;

step three: adjusting the temperature of a roller of the open mill to 40-60 ℃ by using an open mill, firstly, continuously mixing the rubber material obtained in the step two for 60-120 seconds in the open mill, and secondly, adding sulfur and an accelerator; then adding dopamine for mixing; and finally, discharging.

Further, in the third step, the dopamine is put in last and the temperature of the rubber material is controlled below 45 ℃ in the mixing process.

By adopting the scheme, the environment-friendly steel wire adhesive for the tire can replace a meta-methyl-white-cobalt system, and compared with the meta-methyl-white-cobalt system, the steel wire adhesive disclosed by the invention is simpler in formula and relatively low in cost. The adhesive material can be adhered to the surfaces of various materials like byssus of marine mussels, has super-strong adhesion, and is cured by adhesion of catechol functional groups in DOPA and rapid chemical crosslinking through dopamine (L-3,4-dihydroxyphenyl alanine, DOPA) and a small amount of lysine residues. Dopamine also contains catechol and amino functional groups, and is proved to have excellent adhesion performance, and the dopamine also has good biocompatibility, so that the environmental pollution can be greatly reduced, and the dopamine is used for rubber and tire bead wires to obtain good adhesion performance.

Detailed Description

The invention discloses an environment-friendly steel wire adhesive formula for tires, which comprises the following components in parts by weight: 100 parts of natural rubber, 60-150 parts of filler, 3-20 parts of activator, 0.1-5 parts of aromatic oil, 0.1-5 parts of anti-aging agent, 0.1-5 parts of sulfur, 0.1-5 parts of accelerator and 3-9 parts of dopamine and derivatives thereof.

The filler comprises carbon black, white carbon black and calcium carbonate.

The carbon black is any one or any combination of N110, N121, N134, N220, N231, N234, N242, N293, N299, N315, N326, N330, N332, N339, N343, N347, N351, N358, N375, N539, N550, N582, N630, N642, N650, N660, N683, N754, N762, N765, N770, N774, N787, N907, N908, N990 and N991.

The specific surface area of the carbon black is 20-160 m²(g) the DBP absorption value is 20-140 cm³100g of; the white carbon black comprises gas phase white carbon black and precipitation white carbon black; the calcium carbonate includes light calcium carbonate, activated calcium carbonate and crystalline calcium carbonate.

The active agent comprises 1-5 parts by weight of stearic acid and 2-15 parts by weight of zinc oxide.

The dopamine and its derivatives comprise dopamine hydrochloride (also called 3-hydroxytyrosine hydrochloride) and 3-hydroxytyrosine hydrobromide.

The invention also discloses a method for preparing the environment-friendly tire steel wire adhesive formula, which comprises the following steps:

the method comprises the following steps: using an internal mixer, setting the initial temperature of the internal mixer to be 20-90 ℃, the rotating speed of the internal mixer to be 30-80 rpm, and the pressure of the internal mixer to be 0.2-0.8 MPa, firstly adding natural rubber into the internal mixer for mixing for 10-60 seconds, then adding 1/2 filler for mixing for 10-60 seconds, then adding 1/2 filler and aromatic oil for mixing for 10-60 seconds, then cleaning, and finally discharging;

step two: using an internal mixer, setting the initial temperature of the internal mixer to be 20-90 ℃, the rotating speed to be 30-80 rpm and the pressure to be 0.2-0.8 MPa, continuously mixing the rubber material obtained in the first step in the internal mixer for 10-60 seconds, then adding an anti-aging agent, stearic acid and zinc oxide for mixing for 10-60 seconds, cleaning, discharging, and standing the rubber material for one day after discharging;

step three: adjusting the temperature of a roller of the open mill to 40-60 ℃ by using an open mill, firstly, continuously mixing the rubber material obtained in the step two for 60-120 seconds in the open mill, and secondly, adding sulfur and an accelerator; then adding dopamine for mixing, wherein the dopamine is added at last, and the temperature of the rubber material is controlled below 45 ℃ in the mixing process; and finally, discharging.

The present invention will be further described with reference to the following examples, which describe formulation ratios and evaluation results for illustrating the present invention, and should not limit the formulation of the present invention.

Table 1 is a table of formulations for two comparative examples and four inventive examples, wherein comparative example 1 is the base formulation; comparative example 2 is a m-methyl-white-cobalt formulation; examples 1 to 4 are formulations of the environment-friendly steel wire rubber for tires according to the present invention.

Table one: prescription table

The second table is a table for evaluating physical properties and adhesion of comparative examples and examples, wherein the larger the value of each value is, the better the properties are, relative to the index of comparative example 1.

Wherein T-draw is a test to test the adhesion of the steel wire to the rubber. Preparing a T-shaped sample from the rubber and the steel wire to be tested, and drawing the steel wire out of the rubber on a tensile machine to obtain the drawing force (N) of the steel wire and the rubber.

The 100% stress at definite elongation is a stress value (MPa) corresponding to 100% strain when the rubber is physically stretched.

Table two: physical Property and adhesive force evaluation Table

The test results show that the hardness, 100% stress at definite elongation, strength at break, and elongation at break of examples 1 to 4 are less different from those of comparative examples 1 and 2.

The test results show that the steel wire T extraction of example 1 is improved by about 4% and that of examples 2-4 by about 10-20% compared to comparative example 1, with example 3 being the most effective and comparable to the T extraction of the m-methyl-white-cobalt formulation of comparative example 2. Therefore, when the addition amount of the dopamine is less than 3 parts by weight, the effect is not obvious; the addition amount is 3-9 parts by weight, so that the best effect of improving the steel wire adhesive force is achieved; when the addition amount is more than 6 parts by weight, the adhesive force promotion trend tends to be smooth, so that the addition amount of the dopamine is 3-6 parts by weight as the optimal formula parameter by considering the cost.

The above embodiments are not intended to limit the form and style of the present invention, and any suitable changes or modifications made by those skilled in the art should be considered as not departing from the scope of the present invention.