CN113462043A

CN113462043A - Rubber composition containing matrix modifier, vulcanized rubber, and preparation method and application thereof

Info

Publication number: CN113462043A
Application number: CN202010239306.8A
Authority: CN
Inventors: 王丽丽; 解希铭
Original assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Current assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Priority date: 2020-03-30
Filing date: 2020-03-30
Publication date: 2021-10-01
Anticipated expiration: 2040-03-30
Also published as: CN113462043B

Abstract

The invention relates to the field of vulcanized rubber, and discloses a rubber composition containing a matrix modifier, vulcanized rubber, a preparation method and application thereof, wherein the composition contains: the rubber comprises a rubber matrix, a matrix modifier, white carbon black, carbonate, triethanolamine, polyethylene glycol, an organosilane coupling agent, an anti-aging agent and a vulcanizing agent, wherein the rubber matrix is butadiene rubber; the matrix modifier is L-cysteine, and the organosilane coupling agent is at least one selected from Si69 and Si 75. The vulcanized rubber prepared from the rubber composition has the advantages of good transparency, high strength, good wear resistance, excellent rebound resilience and the like.

Description

Rubber composition containing matrix modifier, vulcanized rubber, and preparation method and application thereof

Technical Field

The invention relates to the field of vulcanized rubber, in particular to a rubber composition containing a matrix modifier, a method for preparing vulcanized rubber, the vulcanized rubber prepared by the method and application of the vulcanized rubber in sole materials.

Background

The comfort of the sole directly affects the quality of the entire shoe. In the prior art, the sole is produced by using PVC, TPR, TPU and other materials, and the materials are inferior to the sole made of rubber in the aspects of comfort and skid resistance.

In the prior art, white carbon black is used as a main reinforcing filler and is widely applied to shoe products, so that soles have good wear resistance, skid resistance and vamp adhesion, colored cowhells soles can be processed, and the white carbon black is widely applied to transparent, light-colored and colored soles (including outsoles, midsoles and foxings). Therefore, the shoe industry is always a large user of white carbon black.

The dispersion of white carbon black in a rubber matrix becomes extremely difficult due to the strong surface polarity of the white carbon black, so that the application is limited to a certain extent.

That is, the prior art can not completely satisfy the characteristics of high transparency, abrasion resistance and strength required for transparent soles containing white carbon black, and there is a need to provide a rubber composition with improved properties.

Disclosure of Invention

The invention aims to solve the problems of improving the transmittance, strength and wear resistance of vulcanized rubber formed by a formula of a sole material containing white carbon black.

In order to achieve the above object, a first aspect of the present invention provides a matrix modifier-containing rubber composition comprising the following components stored in admixture or separately:

the rubber composition comprises a rubber matrix, a matrix modifier, white carbon black, carbonate, triethanolamine, polyethylene glycol, an organosilane coupling agent, an anti-aging agent and a vulcanizing agent;

wherein the rubber matrix is butadiene rubber; the matrix modifier is L-cysteine; the organosilane coupling agent is selected from at least one of Si69 and Si 75;

relative to 100 parts by weight of the rubber matrix, the content of the matrix modifier is 5-10 parts by weight, the content of the white carbon black is 10-30 parts by weight, the content of the carbonate is 2-6 parts by weight, the content of the triethanolamine is 1-4 parts by weight, the content of the polyethylene glycol is 3-6 parts by weight, the content of the organosilane coupling agent is 1-3 parts by weight, the content of the anti-aging agent is 1-5 parts by weight, and the content of the vulcanizing agent is 5-10 parts by weight.

A second aspect of the present invention provides a process for preparing a vulcanizate, prepared using the components of the composition described in the first aspect of the present invention, the process comprising:

(1) carrying out first mixing on a component A containing a rubber matrix and a matrix modifier to obtain a section of master batch, wherein the first mixing conditions comprise: the temperature is 80-120 deg.C, and the time is 1-5 min;

(2) and carrying out second mixing on the first-section masterbatch and a component B containing white carbon black, an organosilane coupling agent and polyethylene glycol to obtain a second-section masterbatch, wherein the second mixing conditions comprise that: the temperature is 100-;

(3) and (3) carrying out third mixing on the second-stage masterbatch and a component C containing carbonate, triethanolamine and an anti-aging agent to obtain the third-stage masterbatch, wherein the third mixing conditions comprise that: the temperature is 110-;

(4) and carrying out fourth mixing on the three sections of master batch and a component D containing a vulcanizing agent to obtain a final rubber compound, wherein the fourth mixing conditions comprise that: the temperature is not more than 120 ℃, and the time is 3-6 min;

(5) vulcanizing the final rubber.

A third aspect of the present invention provides a vulcanizate prepared by the foregoing method.

A fourth aspect of the invention provides the use of the aforementioned vulcanized rubber in a sole material.

According to the invention, through the mutual matching of the components in the composition, the prepared vulcanized rubber has good light transmittance, high strength, good wear resistance and excellent rebound resilience.

In addition, the specific method for preparing the vulcanized rubber provided by the invention can exert the synergistic effect of each component in the composition provided by the invention, so that the prepared vulcanized rubber has better performance.

Detailed Description

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

As described above, the first aspect of the present invention provides a rubber composition containing a matrix modifier, which contains the following components stored in admixture or separately:

a rubber matrix, a matrix modifier, white carbon black, carbonate, triethanolamine, polyethylene glycol, an organosilane coupling agent, an anti-aging agent and a vulcanizing agent;

Preferably, the cis content in the butadiene rubber is 95 to 99 wt%.

Preferably, the matrix modifier is L-cysteine represented by formula (1),

preferably, the white carbon black is produced by a gas phase method, and the nitrogen adsorption specific surface area is 350-420m²(iv) a white carbon black in an amount of, for example, A380. The inventor finds that the nitrogen produced by the gas phase method has the adsorption specific surface area of 350-420m²The white carbon black/g is used for preparing the vulcanized rubber of the composition of the invention, and the vulcanized rubber has better transparency, higher strength, wear resistance and rebound resilience.

Preferably, the number average molecular weight of the polyethylene glycol is 2000-6000, such as PEG4000 and the like.

Preferably, the carbonate is selected from at least one of zinc carbonate and calcium carbonate; preferably, the carbonate is zinc carbonate.

Preferably, the antioxidant is at least one of phenolic antioxidants; preferably, the antioxidant is at least one selected from the group consisting of antioxidant 2, 6-di-tert-butyl-4-methylphenol (antioxidant 264), 2, 2-methylenebis- (4-methyl-6-tert-butylphenol) (antioxidant 2246).

Preferably, the vulcanizing agent is selected from at least one of organic peroxide vulcanizing agents; preferably, the vulcanizing agent is at least one selected from dicumyl peroxide (DCP) and di-tert-butyl peroxide (DTBP).

As previously mentioned, a second aspect of the present invention provides a process for preparing a vulcanizate, using the components of the composition described in the first aspect of the present invention, which process comprises:

(5) vulcanizing the final rubber.

The raw materials for preparing the vulcanized rubber in the second aspect of the present invention constitute the composition described in the aforementioned first aspect of the present invention, therefore, the raw materials in the second aspect of the present invention are all the same in kind as those described in the first aspect of the present invention, and in order to avoid repetition, the present invention is not described in detail in the second aspect, and those skilled in the art should not be construed as limiting the present invention.

Preferably, the conditions of the first mixing include: the temperature is 90-100 deg.C, and the time is 2-4 min.

Preferably, the conditions of the second mixing include: the temperature is 110-120 ℃, and the time is 3-5 min.

Preferably, the conditions of the third mixing include: the temperature is 115 ℃ and 125 ℃, and the time is 3-4 min.

Preferably, the conditions of the vulcanization include: the temperature is 150 ℃ and 170 ℃, the pressure is 10-20MPa, and the time is 20-40 min.

Preferably, the matrix modifier is used in an amount of 5-10 parts by weight, the white carbon black is used in an amount of 10-30 parts by weight, the carbonate is used in an amount of 2-6 parts by weight, the triethanolamine is used in an amount of 1-4 parts by weight, the polyethylene glycol is used in an amount of 3-6 parts by weight, the organosilane coupling agent is used in an amount of 1-3 parts by weight, the anti-aging agent is used in an amount of 1-5 parts by weight, and the vulcanizing agent is used in an amount of 5-10 parts by weight, based on 100 parts by weight of the rubber matrix.

In order to clearly describe the process for preparing a vulcanized rubber of the present invention, a preferred embodiment is provided below for illustration:

(1) preheating an internal mixer to 80-120 ℃, adding a rubber matrix, plasticating for 0.1-3min at the rotating speed of 50-200rpm, adding a matrix modifier into the internal mixer, and carrying out first mixing, wherein the first mixing conditions comprise: the temperature is 80-120 deg.C, and the time is 1-5 min;

(2) adding white carbon black, an organic silane coupling agent and polyethylene glycol into an internal mixer, and carrying out second mixing at the temperature of 100-130 ℃, wherein the conditions of the second mixing comprise: the temperature is 100-;

(3) adding carbonate, triethanolamine and an anti-aging agent into an internal mixer, and carrying out third mixing at the temperature of 110-: the temperature is 110-;

(4) plasticating the mixed rubber for 0.1-3min at 20-80 ℃ and 20-150rpm, adding a vulcanizing agent into an internal mixer for fourth mixing, and discharging to obtain final rubber, wherein the fourth mixing conditions comprise: the temperature is not more than 120 ℃, and the time is 3-6 min;

(5) and putting the final rubber compound into a vulcanizing press for vulcanization.

It should be noted that the plastication process in step (1) and step (4) of the present invention is not essential, but is merely a preferred embodiment provided for better processability.

As previously mentioned, a third aspect of the present invention provides a vulcanizate prepared by the foregoing method.

As previously mentioned, a fourth aspect of the invention provides the use of the aforementioned vulcanized rubber in a sole material.

The pressures described herein are all expressed as gauge pressures unless otherwise specified.

The present invention will be described in detail below by way of examples. In the following examples, various raw materials used are commercially available without specific description.

Butadiene rubber: BR9000, a Yanshan petrochemical, having a cis content of 97.8 wt.%;

white carbon black: a380, Degussa, nitrogen adsorption specific surface area 380m²(ii)/g; AEROSIL R974, Degussa, nitrogen adsorption specific surface area 180m 2/g;

polyethylene glycol: PEG2000, PEG4000, PEG6000, technical grade, dow chemical company, usa;

matrix modifier: l-cysteine (. beta. -mercaptopropionic acid), analytically pure, Allantin reagent Inc.;

organosilane coupling agent: si69, Si75, technical grade, Pining coupling agent Co., Ltd;

zinc carbonate: the analysis is pure, and the product can be obtained by Hongda zinc industry company;

calcium carbonate: analytically pure, Hongxin mining, Inc.;

triethanolamine: analytical purification, purge chemical Co., Ltd;

an anti-aging agent: antioxidant 264, antioxidant 2246, Panhua chemical (Shanghai) Co., Ltd;

vulcanizing agent: DCP, DTBP, Aladdin reagent.

The rubber processing conditions in the following examples are shown in Table 1, the rubber test equipment conditions are shown in Table 2, and the test conditions are shown in Table 3:

TABLE 1

Serial number	Device name	Model number	Manufacturer of the product	Use of
					1	Internal mixer	BR1600	Farrel America Ltd	Mixing the raw materials
2	Flat vulcanizing machine	XLB-D4004002	Shanghai first rubber machinery plant	Vulcanization

TABLE 2

TABLE 3

The amounts of the components in the following examples are all parts by weight (or parts), each part by weight representing 1 g.

Example 1

The composition formulations are listed in table 4.

The internal mixer was preheated to 90 ℃, the rubber matrix was added, mastication was carried out at a rotational speed of 70rpm for 0.5min (in the case where nothing is specifically mentioned, the same conditions were also employed in the other examples for mastication, and then the first mixing was carried out), the matrix modifier was added to the internal mixer, and the first mixing was carried out for 4 min. Then adding white carbon black, an organic silane coupling agent and polyethylene glycol into the internal mixer, and carrying out second mixing for 5min at 110 ℃. Then, carbonate, triethanolamine and an anti-aging agent were added to the internal mixer, and the mixture was subjected to third mixing at 115 ℃ for 4 min. Subsequently, the above-mentioned rubber composition was masticated at 60 ℃ and 60rpm for 0.5min (in the case where no specific description is given, the same conditions were employed in the other examples for mastication, and then the fourth mixing was performed), and then, a vulcanizing agent was continuously added to the internal mixer to perform the fourth mixing at 100 ℃ for 5min, and the mixture was discharged to obtain a final rubber composition. And (3) putting the final rubber compound into a flat vulcanizing machine for vulcanization, wherein the vulcanization temperature is 150 ℃, the vulcanization pressure is 20MPa, and the vulcanization time is 40min, so that a vulcanized rubber sample S1 is obtained.

The remaining examples were carried out using the same procedure as in example 1, except for example 6, and the specific process conditions are shown in Table 4.

Example 6

The composition formulation was the same as in example 1.

The preparation method of the vulcanized rubber comprises the following steps: a process similar to example 1 was carried out, except that the first mixing was not carried out. Specifically, the method comprises the following steps:

preheating an internal mixer to 90 ℃, adding the rubber matrix and the matrix modifier, and plasticating for 0.5min at the rotating speed of 70 rpm. Then adding white carbon black, an organic silane coupling agent and polyethylene glycol into the internal mixer, and carrying out second mixing for 5min at 110 ℃. Then, carbonate, triethanolamine and an anti-aging agent were added to the internal mixer, and the mixture was subjected to third mixing at 115 ℃ for 4 min. And plasticating the mixed rubber at 60 ℃ and 60rpm for 0.5min, continuously adding a vulcanizing agent into an internal mixer for fourth mixing, wherein the mixing temperature is 100 ℃, the mixing time is 5min, and discharging to obtain the final rubber. And (3) putting the final rubber compound into a flat vulcanizing machine for vulcanization, wherein the vulcanization temperature is 150 ℃, the vulcanization pressure is 20MPa, and the vulcanization time is 40min, so that a vulcanized rubber sample S6 is obtained.

The composition formulations of comparative example 1, comparative example 2, comparative example 3 and comparative example 4 are listed in table 4. The preparation process was the same as in example 1, and the specific parameters are listed in Table 4.

TABLE 4

Table 4 (continuation watch)

Test example

The examples and comparative products were subjected to the relevant performance tests, and the results are shown in Table 5.

TABLE 5

Test items	Example 1	Example 2	Example 3	Example 4	Example 5
						Light transmittance (%)	75.3	72.2	74.1	62.0	60.6
Hardness (°)	58	57	56	64	63
						Tear Strength (MPa)	9.2	9.6	9.9	8.3	8.5
Tear Strength (kN/m)	30	32	29	25	26
						DIN abrasion (mm)³)	54	56	50	69	65
Rebound value (%)	50.3	51.4	52.7	48.2	49.7

Table 5 (continuation watch)

Test items	Example 6	Comparative example 1	Comparative example 2	Comparative example 3	Comparative example 4
						Light transmittance (%)	56.3	45.3	28.7	26.4	25.9
Hardness (°)	67	69	76	75	78
						Tear Strength (MPa)	8.0	7.2	5.0	5.7	6.0
Tear Strength (kN/m)	23	20	17	16	19
						DIN abrasion (mm)³)	72	89	135	142	138
Rebound value (%)	45.2	39.4	24.2	25.6	22.7

From the results in Table 5, it can be seen that the formulations of the present invention provide significant improvements in light transmittance, strength, abrasion resistance and rebound resilience of the vulcanizates as compared to the prior art.

The rubber composition disclosed by the invention can better disperse white carbon black in a rubber matrix, and further exerts the characteristics and advantages of a matrix modifier; therefore, the further prepared vulcanized rubber has the properties of good transparency, high strength, good wear resistance, excellent rebound resilience and the like.

The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims

1. A rubber composition containing a matrix modifier, characterized by comprising the following components stored in admixture or independently:

2. The composition of claim 1, wherein the cis content in the butadiene rubber is 95-99 wt%.

3. The composition as claimed in claim 1 or 2, wherein the silica white is produced by a gas phase method and has a nitrogen adsorption specific surface area of 350-420m²White carbon black per gram;

preferably, the number average molecular weight of the polyethylene glycol is 2000-.

4. The composition of any one of claims 1-3, wherein the carbonate is selected from at least one of zinc carbonate and calcium carbonate; preferably, the carbonate is zinc carbonate.

5. The composition of any one of claims 1-3, wherein the antioxidant is at least one of a phenolic antioxidant; preferably, the anti-aging agent is at least one selected from 2, 6-di-tert-butyl-4-methylphenol and 2, 2-methylenebis- (4-methyl-6-tert-butylphenol);

preferably, the vulcanizing agent is selected from at least one of organic peroxide vulcanizing agents; preferably, the vulcanizing agent is selected from at least one of dicumyl peroxide and di-tert-butyl peroxide.

6. A process for preparing a vulcanized rubber, characterized by using the components of the composition of any one of claims 1 to 5, which comprises:

(5) vulcanizing the final rubber.

7. The method of claim 6, wherein the conditions of the first mixing comprise: the temperature is 90-100 deg.C, and the time is 2-4 min.

8. The method of claim 6 or 7, wherein the conditions of the second mixing comprise: the temperature is 110-120 ℃, and the time is 3-5 min.

9. The method of any of claims 6-8, wherein the conditions of the third mixing comprise: the temperature is 115 ℃ and 125 ℃, and the time is 3-4 min.

10. The method of any of claims 6-9, wherein the vulcanization conditions include: the temperature is 150 ℃ and 170 ℃, the pressure is 10-20MPa, and the time is 20-40 min.

11. The method according to any one of claims 6 to 10, wherein the matrix modifier is used in an amount of 5 to 10 parts by weight, the white carbon black is used in an amount of 10 to 30 parts by weight, the carbonate is used in an amount of 2 to 6 parts by weight, the triethanolamine is used in an amount of 1 to 4 parts by weight, the polyethylene glycol is used in an amount of 3 to 6 parts by weight, the organosilane coupling agent is used in an amount of 1 to 3 parts by weight, the anti-aging agent is used in an amount of 1 to 5 parts by weight, and the vulcanizing agent is used in an amount of 5 to 10 parts by weight, relative to 100 parts by weight of the rubber matrix.

12. A vulcanized rubber produced by the method of any one of claims 6 to 11.

13. Use of the vulcanizate of claim 12 in shoe sole materials.