阅读说明：本技术 一种br/sbr复合橡胶、热塑性弹性体及abs增强塑料 (BR/SBR composite rubber, thermoplastic elastomer and ABS reinforced plastic ) 是由 彭旭锵 金辉乐 王宗垒 王舜 尹德武 于 2020-12-30 设计创作，主要内容包括：本发明属于高分子材料领域,具体涉及一种BR/SBR复合橡胶、热塑性弹性体及ABS增强塑料。本发明发现SBR与BR在适当配比下能够克服单一橡胶的缺点,BR的优良弹性和耐磨性能够在硫化剂的共同作用下弥补SBR弹性差、抗撕裂性能差的缺点。本发明通过ABS对TPE进行补强,使TPE的强度增强。(The invention belongs to the field of high polymer materials, and particularly relates to BR/SBR composite rubber, a thermoplastic elastomer and ABS reinforced plastic. The invention discovers that the SBR and the BR can overcome the defect of single rubber under the proper proportion, and the excellent elasticity and wear resistance of the BR can make up the defects of poor elasticity and poor tear resistance of the SBR under the combined action of a vulcanizing agent. The TPE is reinforced by the ABS, so that the strength of the TPE is enhanced.)

1. The BR/SBR composite rubber is characterized by comprising the following components in parts by mass: 20 parts of natural rubber, 320 parts of styrene-butadiene rubber SBR, 320 parts of butadiene rubber BR9000, 16 parts of sulfur, 24 parts of zinc oxide, 24 parts of stearic acid, 120 parts of white carbon black, 24 parts of a promoter, 240 parts of calcium carbonate and 200 parts of white oil.

2. The BR/SBR composite rubber according to claim 1, wherein said rubber is prepared by the following steps:

step 1: preparing raw materials;

step 2: the raw materials are put into an internal mixer for banburying, and the process setting is as follows: controlling the material temperature at 60 ℃, mixing for 12min, and rotating at 25 r/min to obtain dense rubber;

and step 3: the banburying rubber is put into an open mill for open milling, and the process is set as follows: the temperature of the front roller is 60 ℃, the temperature of the rear roller is 55 ℃, and the frequency conversion of the front roller is 50 Hz; carrying out frequency conversion on a rear roller at 50Hz to obtain rubber;

and 4, step 4: and (3) vulcanizing the rubber obtained in the step (3), wherein the process is as follows: the temperature of the upper template is 160 ℃; the temperature of the lower template is 160 ℃; the automatic cycle time is 10 min; automatic exhaust time 40 s; the pressure between the templates was 12t, and a vulcanized rubber was obtained.

3. A PP/BR/SBR composite rubber thermoplastic elastomer, which is obtained by blending the BR/SBR composite rubber as claimed in claim 1 or 2 with PP and dynamically vulcanizing.

4. An ABS-reinforced PP/BR/SBR composite rubber thermoplastic elastomer plastic characterized in that it is obtained by the blend injection molding of the PP/BR/SBR composite rubber thermoplastic elastomer as claimed in claim 3 and ABS.

Technical Field

The invention belongs to the field of high polymer materials, and particularly relates to BR/SBR composite rubber, a thermoplastic elastomer and ABS reinforced plastic.

Background

With the rapid development of modern industry, the problems of treatment and recycling of waste rubber become more and more severe, and the processing and vulcanizing technology of traditional rubber also becomes mature day by day along with the increasing pursuit of people for better high-quality life. Therefore, the rubber with high strength, high wear resistance and high oil resistance and excellent performance is developed and produced by technologies such as the joint growth of the bamboo shoots in spring after rain.

Thermoplastic elastomer composite rubber both possessed the high elastic energy of traditional vulcanize crosslinked rubber, possessed the processability of general plastics again, for traditional rubber, thermoplastic elastomer proportion is lighter, and the modulus scope is wideer, and the intermediate product is mostly the plastic granule, greatly reduced processing transportation and stored the degree of difficulty, available moulding plastics in addition, processing methods such as extrusion, leftover bits and parts are retrieved the rubber material and can be smashed the back and directly process and recycle. The existing thermoplastic elastomer is not enough in strength, and the application of the thermoplastic elastomer is limited.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provide BR/SBR composite rubber, thermoplastic elastomer and ABS reinforced plastic.

The technical scheme adopted by the invention is as follows: a BR/SBR composite rubber comprises the following components in parts by mass: 20 parts of natural rubber, 320 parts of styrene-butadiene rubber SBR, 320 parts of butadiene rubber BR9000, 16 parts of sulfur, 24 parts of zinc oxide, 24 parts of stearic acid, 120 parts of white carbon black, 24 parts of a promoter, 240 parts of calcium carbonate and 200 parts of white oil.

The preparation process comprises the following steps:

step 1: preparing raw materials;

step 2: the raw materials are put into an internal mixer for banburying, and the process setting is as follows: controlling the material temperature at 60 ℃, mixing for 12min, and rotating at 25 r/min to obtain dense rubber;

and step 3: the banburying rubber is put into an open mill for open milling, and the process is set as follows: the temperature of the front roller is 60 ℃, the temperature of the rear roller is 55 ℃, and the frequency conversion of the front roller is 50 Hz; carrying out frequency conversion on a rear roller at 50Hz to obtain rubber;

and 4, step 4: and (3) vulcanizing the rubber obtained in the step (3), wherein the process is as follows: the temperature of the upper template is 160 ℃; the temperature of the lower template is 160 ℃; the automatic cycle time is 10 min; automatic exhaust time 40 s; the pressure between the templates was 12t, and a vulcanized rubber was obtained.

The rubber is obtained by blending and dynamically vulcanizing the BR/SBR composite rubber and PP.

An ABS reinforced PP/BR/SBR composite rubber thermoplastic elastomer plastic is obtained by blending and injection molding the PP/BR/SBR composite rubber thermoplastic elastomer and ABS.

The invention has the following beneficial effects: the invention discovers that the SBR and the BR can overcome the defect of single rubber under the proper proportion, and the excellent elasticity and wear resistance of the BR can make up the defects of poor elasticity and poor tear resistance of the SBR under the combined action of a vulcanizing agent. The TPE is reinforced by the ABS, so that the strength of the TPE is enhanced.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is within the scope of the present invention for those skilled in the art to obtain other drawings based on the drawings without inventive exercise.

FIG. 1 is a graph showing the torque capacity of the vulcanizates obtained in examples 1-4, plotted on the abscissa for the examples;

FIG. 2 is a graph showing the minimum torque of the vulcanizates obtained in examples 1-4, plotted on the abscissa for the examples;

FIG. 3 shows the tensile strengths of the vulcanizates obtained in examples 1 to 4, on the abscissa of the examples;

FIG. 4 is a graph showing the tensile elongations of the vulcanizates obtained in examples 1-4, plotted on the abscissa for the examples;

FIG. 5 is a graph showing the tear strength of the vulcanizates of examples 1-4, plotted on the abscissa for the examples;

FIG. 6 is the tensile tear elongation of the vulcanizates from examples 1-4, plotted on the abscissa for the examples.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings.

Examples 1 to 4:

the samples of examples 1-4 were prepared according to the following preparation:

step 1: preparing raw materials of natural rubber NR1052R, styrene-butadiene rubber SBR, butadiene rubber BR9000, sulfur, zinc oxide, stearic acid, white carbon black, a catalyst, calcium carbonate and white oil according to a formula in a table 1;

step 2: the raw materials are put into an internal mixer for banburying, and the process setting is as follows: controlling the material temperature at 60 ℃, mixing for 12min, and rotating at 25 r/min to obtain dense rubber;

and step 3: the banburying rubber is put into an open mill for open milling, and the process is set as follows: the temperature of the front roller is 60 ℃, the temperature of the rear roller is 55 ℃, and the frequency conversion of the front roller is 50 Hz; carrying out frequency conversion on a rear roller at 50Hz to obtain rubber;

and 4, step 4: and (3) vulcanizing the rubber obtained in the step (3), wherein the process is as follows: the temperature of the upper template is 160 ℃; the temperature of the lower template is 160 ℃; the automatic cycle time is 10 min; automatic exhaust time 40 s; the pressure between the templates was 12t, and a vulcanized rubber was obtained.

As shown in FIG. 1, the maximum torque of the vulcanized rubber obtained in the four examples is 3/2.7/2.5/2.4 (N/m) in sequence, which means that the vulcanization shear modulus of the compounded rubber decreases in sequence with the increase of the SBR proportion content and the decrease of the BR proportion content, that is, the increase of the SBR rubber weakens the shear modulus of the compounded rubber, the increase of the BR rubber increases the shear modulus of the compounded rubber, and the shear modulus of the vulcanized rubber is related to the crosslinking density of the rubber and reflects the elasticity and hardness of the vulcanized rubber, so that the crosslinking performance of the SBR rubber is proved to be weaker, and the BR mainly contributes to the rubber vulcanization crosslinking and the mechanical properties of the vulcanized rubber.

As shown in FIG. 2, the minimum torque of the vulcanized rubbers obtained in the four examples is 1.38/1.35/1.28/1.22 (N/m) in the order, which means that the viscosity of the compounded rubber decreases with the increase of the compounding ratio of SBR and the decrease of the compounding ratio of BR, which means that the increase of SBR weakens the Mooney viscosity of the compounded rubber and the increase of BR increases the Mooney viscosity of the compounded rubber, and the compounding ratio of SBR and BR determines the difference of the processing techniques of the rubbers because the viscosity of the vulcanized rubber affects the processability of the rubber.

The difference value of the maximum torque and the minimum torque reflects the crosslinking degree of rubber vulcanization and directly influences the ultimate tensile strength, the elongation at break and the compression deformation degree of the rubber samples, the difference value of the maximum torque and the minimum torque of the four groups of samples is 1.62/1.35/1.22/1.18 (N/m) in sequence, and the torque difference of the four groups of samples proves that BR plays an important role in crosslinking in the compounded rubber again.

As shown in FIGS. 3-6, the ratios of tensile strengths of the vulcanizates obtained in the four examples were, in order: 5.5/5.6/6.3/6.4 (MPa), the ratio of the tensile elongation times being, in order: 7.2/7.5/7.7/8.1 (%), the ratio of the tear strength being in order: 14/16/18/13 (MPa), the ratio of the tensile tear elongation is: 2.2/2.4/3.0/2.5 (%).

Example 5:

the rubber prepared in step 3 of the third example and the polypropylene resin PP are subjected to dynamic vulcanization together by a double-screw extruder according to the process parameters shown in Table 2 according to the mass ratio of 2:3, and are extruded and granulated to obtain the thermoplastic elastomer (TPE).

The average tensile elastic modulus was found to be 310MPa, the average breaking stress was 17.2N, the average tensile yield stress was 15.6N, the average yield stress was 592N, and the average maximum force was 654N; the average flexural strain at break was 4.5MPa, the average flexural stress at break was 15.8N, and the average flexural modulus was 542 MPa.

Example 6:

the thermoplastic elastomer (TPE) prepared in example 5 and ABS were injection-molded in a mass ratio of 100:1, specifically using a vertical injection molding machine, with the process parameter settings shown in tables 3 and 4.

The average tensile elastic modulus of the ABS reinforced thermoplastic elastomer added with 1/100 proportion is 320MPa, the average breaking stress is 17.4N, the average tensile yield stress is 15.4N, the average yield stress is 582N, and the average maximum force is 663N; the average flexural strain at break was 4.5MPa, the average flexural stress at break was 16.7N, and the average flexural modulus was 590 MPa.

Example 7:

the thermoplastic elastomer (TPE) prepared in example 5 and ABS were injection-molded in a mass ratio of 100:2, specifically using a vertical injection molding machine, with the process parameter settings shown in tables 3 and 4.

The average tensile elastic modulus of the ABS reinforced thermoplastic elastomer added with 2/100 proportion is 326MPa, the average breaking stress is 18.8N, the average tensile yield stress is 15.7N, the average yield stress is 599N, and the average maximum force is 716N; the average flexural strain at break was 4.5MPa, the average flexural stress at break was 17.7N, and the average flexural modulus was 642 MPa.

Example 8:

the thermoplastic elastomer (TPE) prepared in example 5 and ABS were injection-molded in a mass ratio of 100:5, specifically using a vertical injection molding machine, with the process parameter settings shown in tables 3 and 4.

The average tensile elastic modulus of the ABS reinforced thermoplastic elastomer added with 5/100 proportion is 325MPa, the average breaking stress is 15.2N, the average tensile yield stress is 15.3N, the average yield stress is 580N, and the average maximum force is 607N; the average flexural strain at break was 4.5MPa, the average flexural stress at break was 18.1N, and the average flexural modulus was 640 MPa.

Example 9:

the thermoplastic elastomer (TPE) prepared in example 5 and ABS were injection-molded in a mass ratio of 100:8, specifically using a vertical injection molding machine, with the process parameter settings shown in tables 3 and 4.

The average tensile elastic modulus of the ABS reinforced thermoplastic elastomer added with 8/100 proportion is 295MPa, the average breaking stress is 13.8N, the average tensile yield stress is 14.9N, the average yield stress is 566N, and the average maximum force is 570N; the average flexural strain at break was 4.5MPa, the average flexural stress at break was 18.4N, and the average flexural modulus was 653 MPa; .

Example 10:

the thermoplastic elastomer (TPE) prepared in example 5 and ABS were injection-molded in a mass ratio of 100:10, specifically using a vertical injection-molding machine, with the process parameter settings shown in tables 3 and 4.

The average tensile elastic modulus of the ABS reinforced thermoplastic elastomer added with 10/100 proportion is 302MPa, the average breaking stress is 13.6N, the average tensile yield stress is 15N, the average yield stress is 571N, and the average maximum force is 571N; the average flexural strain at break was 4.5MPa, the average flexural stress at break was 19.8N, and the average flexural modulus was 692 MPa.

The elastic modulus of the ABS reinforced thermoplastic elastomer is increased along with the increase of the ABS proportion, the elastic modulus is sequentially reduced when the elastic modulus reaches the maximum value, the tensile elastic modulus is the maximum when the ABS/TPE is 2/100, namely the hardness of the TPE is also the maximum, and the tensile breaking stress and the yield stress of each group are also shown in the trend.

The maximum values of tensile strength and elongation at break at 2/100 for the ABS/TPE blend are shown by comparing the tensile strength and elongation at break of the thermoplastic elastomers in the sets 0/100, 1/100, 2/100, 5/100, 8/100 and 10/100. However, when the ABS proportion exceeds 2/100, the compatibility of the compounded rubber to ABS is exceeded, and the phenomenon of uneven distribution on the microstructure is caused, so that the optimal reinforcement effect cannot be achieved.

The above disclosure is only for the purpose of illustrating the preferred embodiments of the present invention, and it is therefore to be understood that the invention is not limited by the scope of the appended claims.