阅读说明：本技术 一种高断裂伸长率二烯烃橡胶复合物及其制备方法 (High-elongation-at-break diene rubber compound and preparation method thereof ) 是由 杨小牛 王晓建 郇彦 郑书铁 于 2020-07-17 设计创作，主要内容包括：本发明涉及一种高断裂伸长率二烯烃橡胶复合物及其制备方法,属于橡胶技术领域。解决了现有技术中,添加补强剂后,二烯烃硫化橡胶的断裂伸长率降低至100-550％之间的技术问题。本发明的橡胶复合物,由100重量份二烯烃橡胶、10-40重量份炭黑、1-20重量份白炭黑、1-8重量份偶联剂、3-6重量份氧化锌、1-4重量份硬脂酸、2-8重量份防护剂、0.6-2.5重量份硫磺和0.6-2重量份促进剂组成。该橡胶复合物的断裂伸长率超过650％,硬度大于60A,并且具有可观的疲劳性能,可为高形变橡胶材料应用领域提供技术潜力。(The invention relates to a diene rubber compound with high elongation at break and a preparation method thereof, belonging to the technical field of rubber. Solves the technical problem that the elongation at break of the diene vulcanized rubber is reduced to between 100 and 550 percent after the reinforcing agent is added in the prior art. The rubber compound comprises 100 parts by weight of diene rubber, 10-40 parts by weight of carbon black, 1-20 parts by weight of white carbon black, 1-8 parts by weight of coupling agent, 3-6 parts by weight of zinc oxide, 1-4 parts by weight of stearic acid, 2-8 parts by weight of protective agent, 0.6-2.5 parts by weight of sulfur and 0.6-2 parts by weight of accelerator. The rubber compound has the elongation at break of more than 650 percent and the hardness of more than 60A, has considerable fatigue performance, and can provide technical potential for the application field of high-deformation rubber materials.)

1. The diene rubber compound with high elongation at break is characterized by comprising the following components:

the diene rubber is one or a mixture of more of natural rubber, polyisoprene rubber and butadiene rubber, and when the diene rubber contains the butadiene rubber, the mass fraction of the butadiene rubber in the diene rubber is within 70 wt%;

the carbon black has a nitrogen adsorption specific surface area of > 160m²(iv)/g, compressed DBP value less than 80cm³/100g；

The primary particle size of the white carbon black is less than 30nm, and the BET absorption value is more than 180m³/g；

The coupling agent is a mixture of SI75 and KH570 in a mass ratio of (1-3) to 1;

the protective agent is a mixture of at least two of 0-2 parts by weight of RD, 0-2 parts by weight of 4010NA, 0-2 parts by weight of 2-mercaptobenzimidazole, 0-1 part by weight of CTP and 0-2 parts by weight of N, N' -phenylene bismaleimide.

2. High elongation at break diene rubber compound according to claim 1, characterised in that the accelerator is a mixture of one or more of DM, NS, DZ, D, CZ, DPG in any proportion.

3. The process for preparing a diene rubber compound having a high elongation at break according to claim 1 or 2, characterized by the steps of:

step one, weighing raw materials according to composition and parts by weight;

step two, putting the diene rubber into an internal mixer for internal mixing;

and step three, firstly, putting the protective agent, the zinc oxide, the stearic acid, the carbon black, the white carbon black and the coupling agent into the internal mixer in the step two for internal mixing, then discharging rubber to an open mill for mixing, then adding the accelerator and the sulfur, thinly passing through, discharging the sheet, placing the sheet at room temperature for more than 12 hours to obtain rubber compound, and vulcanizing to obtain the diene rubber compound with high elongation at break.

4. The method for preparing the diene rubber compound with high elongation at break according to claim 3, wherein in the second step, the banburying temperature is 60-80 ℃, the time is 1-3min, and the banbury mixer rotation speed is 20-40 rpm.

5. The method for preparing the diene rubber compound with high elongation at break according to claim 3, wherein in the third step, the banburying temperature is 60-80 ℃, the banburying time is 4-8min, and the banbury mixer rotation speed is 20-40 rpm.

6. The process for preparing diene rubber compound with high elongation at break according to claim 3, wherein in the third step, the roll temperature of the open mill is 60-80 ℃.

7. The process for preparing diene rubber compound with high elongation at break according to claim 3, wherein in the third step, the thin pass is performed 3-4 times.

8. The method for preparing diene rubber compound with high elongation at break as claimed in claim 3, wherein in the third step, the vulcanization temperature is 134-150 ℃, the pressure is 0.2-20MPa, and the time is 0.4-1.2 h.

Technical Field

The invention belongs to the technical field of rubber, and particularly relates to a diene rubber compound with high elongation at break and a preparation method thereof.

Background

Rubber (Rubber) is a high-elasticity polymer material with reversible deformation, is rich in elasticity at room temperature, can generate large deformation under the action of small external force, and can recover the original shape after the external force is removed.

The rubber has high elongation at break, the elongation at break of diene vulcanized rubber without reinforcing agent can reach more than 700 percent, but the fatigue and modulus of rubber without reinforcing agent are low, and the rubber has no use. The elongation at break of the rubber is reduced by adding the reinforcing agent, for example, the elongation at break of the diene vulcanized rubber is between 100% and 550% by adding the reinforcing agent.

Disclosure of Invention

The invention aims to solve the technical problem that after a reinforcing agent is added, the elongation at break of diene vulcanized rubber is reduced to between 100 and 550 percent, and provides a diene rubber compound with high elongation at break and a preparation method thereof.

The technical scheme adopted by the invention for solving the technical problems is as follows.

The diene rubber compound with high elongation at break comprises the following components:

the diene rubber is one or a mixture of more of natural rubber (IR), polyisoprene rubber (IR) and Butadiene Rubber (BR), and when the diene rubber contains the butadiene rubber, the mass fraction of the butadiene rubber in the diene rubber is within 70 wt%;

the carbon black has a nitrogen adsorption specific surface area of > 160m²(iv)/g, compressed DBP value less than 80cm³/100g；

The primary particle size of the white carbon black is less than 30nm, and the BET absorption value is more than 180m³/g；

The coupling agent is a mixture of SI75 and KH570 in a mass ratio of (1-3) to 1;

the protective agent is a mixture of at least two of 0-2 parts by weight of RD, 0-2 parts by weight of 4010NA, 0-2 parts by weight of 2-mercaptobenzimidazole, 0-1 part by weight of CTP and 0-2 parts by weight of N, N' -phenylene bismaleimide.

Preferably, the accelerator is one or more of DM, NS, DZ, D, CZ and DPG mixed according to any proportion.

The invention also provides a preparation method of the diene rubber compound with high elongation at break, which comprises the following steps:

step one, weighing raw materials according to composition and parts by weight;

step two, putting the diene rubber into an internal mixer for internal mixing;

and step three, firstly, putting the protective agent, the zinc oxide, the stearic acid, the carbon black, the white carbon black and the coupling agent into the internal mixer in the step two for internal mixing, then discharging rubber to an open mill for mixing, then adding the accelerator and the sulfur, thinly passing through, discharging the sheet, placing the sheet at room temperature for more than 12 hours to obtain rubber compound, and vulcanizing to obtain the diene rubber compound with high elongation at break.

Preferably, in the second step, the banburying temperature is 60-80 ℃, the time is 1-3min, and the banburying speed is 20-40 rpm.

Preferably, in the third step, the banburying temperature is 60-80 ℃, the time is 4-8min, and the banbury mixer rotation speed is 20-40 rpm.

Preferably, in the third step, the roller temperature of the open mill is 60-80 ℃.

Preferably, in the third step, the thin passing is performed 3-4 times.

Preferably, in the third step, the vulcanization temperature is 134-150 ℃, the pressure is 0.2-20MPa, and the time is 0.4-1.2 h.

Compared with the prior art, the invention has the beneficial effects that:

the diene rubber compound with high elongation at break is based on three common diene rubbers, and the proper reinforcing material and a vulcanization system are selected, so that the reinforced rubber material has the elongation at break of more than 650 percent and the hardness of more than 60A, has considerable fatigue performance, and can provide technical potential for the application field of high-deformation rubber materials. Through test detection, the high elongation at break diene rubber compound has the advantages that the Mooney viscosity (ML1+4) of the rubber compound is 60-80, the elongation at break of the rubber compound vulcanized at the temperature of 134 ℃ and 150 ℃ for 0.4-1.2h is more than 650%, the tensile strength is more than 24MPa, and the number of 1-level cracking at room temperature is more than 5 ten thousand.

Detailed Description

For a further understanding of the invention, reference will now be made in detail to the embodiments of the invention, but it is to be understood that the description is intended to illustrate further features and advantages of the invention, and not to limit the scope of the claims.

The diene rubber compound with high elongation at break comprises 100 parts by weight of diene rubber, 10-40 parts by weight of carbon black, 1-20 parts by weight of white carbon black, 1-8 parts by weight of coupling agent, 3-6 parts by weight of zinc oxide, 1-4 parts by weight of stearic acid, 2-8 parts by weight of protective agent, 0.6-2.5 parts by weight of sulfur and 0.6-2 parts by weight of accelerator.

In the technical scheme, the diene rubber is one or a mixture of more of natural rubber, polyisoprene rubber and butadiene rubber, and when the diene rubber contains the butadiene rubber, the mass fraction of the butadiene rubber in the diene rubber is within 70 wt%;

the nitrogen adsorption specific surface area of the carbon black is more than 160m²(iv)/g, compressed DBP value less than 80cm³/100g；

The primary particle size of the white carbon black is less than 30nm, and the BET absorption value is more than 180m³/g；

The coupling agent is a mixture of SI75 and KH570 in a mass ratio of (1-3) to 1;

the protective agent is a mixture of at least two of 0-2 parts by weight of RD, 0-2 parts by weight of 4010NA, 0-2 parts by weight of 2-mercaptobenzimidazole, 0-1 part by weight of CTP and 0-2 parts by weight of N, N' -phenylene bismaleimide;

the accelerant is one or a mixture of DM, NS, DZ, D, CZ and DPG according to any proportion;

zinc oxide, stearic acid, sulphur may be obtained in a manner well known to those skilled in the art, e.g. commercially available.

The preparation method of the diene rubber compound with high elongation at break comprises the following steps:

step one, weighing raw materials according to composition and parts by weight;

step two, putting the diene rubber into an internal mixer for internal mixing;

and step three, firstly, putting the protective agent, the zinc oxide, the stearic acid, the carbon black, the white carbon black and the coupling agent into the internal mixer in the step two for internal mixing, then discharging rubber to an open mill for mixing, then adding the accelerator and the sulfur, thinly passing through, discharging the sheet, placing the sheet at room temperature for more than 12 hours to obtain rubber compound, and vulcanizing to obtain the diene rubber compound with high elongation at break.

In the technical scheme, in the second step, the banburying temperature is 60-80 ℃, the time is 1-3min, and the rotating speed of the banbury mixer is 20-40 rpm.

In the technical scheme, in the third step, the banburying temperature is 60-80 ℃, the time is 4-8min, and the rotating speed of the banbury mixer is 20-40 rpm.

In the third step, the roller temperature of the open mill is 60-80 ℃.

In the technical scheme, in the third step, the thin tube is passed for 3-4 times.

In the third step, the vulcanization temperature is 134-150 ℃, the pressure is 0.2-20MPa, and the time is 0.4-1.2 h.

The present invention is further illustrated by the following examples, but the scope of the present invention is not limited to the following examples.

High elongation at break diene rubber compounds were prepared according to the formulations of comparative examples 1 to 5 and examples 1 to 5 shown in Table 1. The preparation method comprises the following steps:

step one, weighing raw materials according to composition and parts by weight;

step two, putting the diene rubber into an internal mixer for internal mixing, wherein the internal mixing temperature is 60-80 ℃, the time is 1-3min, and the rotating speed of the internal mixer is 20-40 rpm;

and step three, firstly, putting the protective agent, the zinc oxide, the stearic acid, the carbon black, the white carbon black and the coupling agent into an internal mixer in the step two for internal mixing at the temperature of 60-80 ℃ for 4-8min at the rotating speed of 20-40rpm, then discharging rubber to an open mill for open mixing at the roller temperature of 60-80 ℃, adding the accelerator and the sulfur, thinly passing for 3-4 times, taking out the sheet, placing the sheet at room temperature for more than 12 hours to obtain mixed rubber, and vulcanizing at the temperature of 134-. The properties of the rubber compounds prepared are shown in Table 2.

TABLE 1 formulations for the preparation of vulcanizates (in parts by weight) for comparative examples 1 to 5 and examples 1 to 5

TABLE 2 Properties of comparative examples 1 to 5 and examples 1 to 5 for preparing vulcanizates

In the table, the hardness test standard is GB/T531.1-2008, the deflection test standard is GB/T13934-. As can be seen from Table 2, the diene rubber is reinforced properly, so that the stress at definite elongation, the hardness and the flexibility at break are greatly improved, and a high level of elongation at break is maintained, thereby providing technical potential for the application field of high-deformation rubber materials.

The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.