CN109929207B - Rubber composition for shoe sole, vulcanized rubber, and preparation method and application thereof - Google Patents
Rubber composition for shoe sole, vulcanized rubber, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the field of rubber, and discloses a rubber composition and vulcanized rubber for soles, and a preparation method and application thereof. When the vulcanized rubber prepared from the composition provided by the invention is used for preparing rubber of soles, the vulcanized rubber has excellent comprehensive properties such as improved strength, improved wear resistance and improved dynamic fatigue.
Description
Technical Field
The invention relates to the field of rubber, in particular to a rubber composition for soles, a method for preparing vulcanized rubber, the vulcanized rubber prepared by the method and application of the vulcanized rubber in preparing the soles.
Background
The beauty of the sole directly influences the beauty of the whole shoe, and a plurality of international large brands produce soles more, which brings a high-end and fashionable feeling to people.
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 a sole has good wear resistance, skid resistance and vamp adhesion, and a colored cowhells sole can be processed, and the white carbon black is widely applied to light-colored semi-soles (including undersoles, 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.
CN105440341A discloses an antiskid sole material, and the prior art discloses the application of white carbon black in sole materials, wherein the white carbon black is added with a silane coupling agent to improve the dispersibility, and the silane coupling agent is a sulfur-containing compound, and has a high requirement on process control during high-temperature mixing, and scorching may be caused by improper control, which may affect the overall performance of the composite material.
Since the above prior art cannot fully satisfy the requirements of high strength, good abrasion resistance and good dynamic flexibility of shoe soles containing white carbon black, there is a need for a rubber composition with improved properties.
Disclosure of Invention
The invention aims to overcome the defects of low rubber strength, poor wear resistance and poor dynamic flexibility when the rubber composition containing white carbon black provided by the prior art is used for preparing soles, and provides a novel rubber composition and a preparation method of vulcanized rubber.
In order to achieve the above object, a first aspect of the present invention provides a rubber composition for shoe soles, which contains a rubber matrix, an initiator, a rubber modifier, white carbon black, carbonate, an activator, an anti-aging agent, a softener, an accelerator and a vulcanizing agent, wherein the rubber modifier is an acrylic monomer, and the rubber matrix is butadiene rubber.
In a second aspect, the present invention provides a process for preparing a vulcanizate, the process comprising:
(1) carrying out first mixing on a component A containing a rubber matrix, an initiator and a rubber modifier to obtain a section of master batch;
(2) carrying out second mixing on the first-stage masterbatch and a component B containing white carbon black, an activating agent, carbonate, an anti-aging agent and a softening agent to obtain a second-stage masterbatch;
(3) performing third mixing on the second-stage masterbatch and a component C containing an accelerator and a vulcanizing agent to obtain a final rubber compound;
(4) vulcanizing the final rubber;
the rubber modifier is an acrylic monomer, and the rubber matrix is butadiene rubber.
In a third aspect, the present invention provides a vulcanizate prepared by the method of the second aspect described above.
In a fourth aspect, the present invention provides the use of a vulcanizate according to the third aspect as described above for the preparation of a shoe sole.
The vulcanized rubber is obtained by a novel mixing method, wherein a rubber matrix, an initiator and a matrix modifier are mixed to prepare a matrix master batch; then adding white carbon black, an activating agent, an anti-aging agent, a softening agent and the like into the matrix master batch, and mixing to prepare a second-stage master batch; and then adding a vulcanizing agent and an accelerator into the secondary masterbatch to prepare final rubber, and finally vulcanizing the final rubber to obtain the vulcanized rubber.
The processing technology of the invention has the advantages that: in the processing technology, the bridge function of the rubber modifier in the rubber matrix and the white carbon black can be better played, the white carbon black in the rubber matrix is favorably divided, the strength of vulcanized rubber prepared by further vulcanization can be better improved, the wear resistance of the vulcanized rubber is improved, and the bending resistance and flexibility of the vulcanized rubber material are improved.
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 for shoe soles, which contains a rubber matrix, an initiator, a rubber modifier, white carbon black, carbonate, an activator, an anti-aging agent, a softener, an accelerator and a vulcanizing agent, wherein the rubber modifier is an acrylic monomer, and the rubber matrix is butadiene rubber.
The acrylic monomer can modify a rubber matrix, thereby being beneficial to the interaction between the rubber matrix and the white carbon black, being beneficial to the dispersion of the white carbon black in the rubber matrix, better improving the strength of vulcanized rubber prepared by further vulcanization and improving the wear resistance of the vulcanized rubber.
Preferably, the acrylic monomer is selected from at least one of acrylic acid, methacrylic acid, alkyl methacrylate, and glycidyl methacrylate.
More preferably, the acrylic monomer is an alkyl methacrylate and/or a glycidyl methacrylate.
Preferably, in the present invention, the "alkyl group" of the alkyl methacrylate includes C1-6Linear or branched alkyl groups of (a).
More preferably, the alkyl methacrylate is at least one of methyl methacrylate, ethyl methacrylate and propyl methacrylate.
Preferably, the carbonate is at least one of magnesium carbonate, zinc carbonate and calcium carbonate. The inventors of the present invention have found that the rubber composition for shoe soles of the present invention formed therefrom has more excellent properties when zinc carbonate is used.
Preferably, the cis content in the butadiene rubber is 90 to 99 wt%.
Preferably, the content of the initiator is 0.2 to 1 part by weight, the content of the rubber modifier is 5 to 10 parts by weight, the content of the white carbon black is 40 to 70 parts by weight, the content of the carbonate is 2 to 8 parts by weight, the content of the activator is 1 to 5 parts by weight, the content of the anti-aging agent is 0.5 to 3 parts by weight, the content of the softener is 10 to 25 parts by weight, the content of the accelerator is 2 to 6 parts by weight, and the content of the vulcanizing agent is 1 to 4 parts by weight, relative to 100 parts by weight of the rubber matrix.
According to the present invention, it is preferable that the initiator is selected from at least one of dicumyl peroxide, dibenzoyl peroxide, bis (2, 4-dichlorobenzoyl) peroxide, diacetyl peroxide and dilauroyl peroxide.
According to the present invention, preferably, the white carbon black is silica; more preferably, the nitrogen adsorption specific surface area of the white carbon black is 10-200m2(ii) in terms of/g. For example, the white carbon black is 115GR (Rodiya, France) and/or 165GR (Rodiya, France).
Preferably, the activator is a fatty acid; the fatty acid is preferably stearic acid.
Preferably, the antioxidant is at least one of a phenol antioxidant, an amine antioxidant, a quinoline antioxidant and a benzimidazole antioxidant. For example, the antioxidant is antioxidant 264.
Preferably, the softening agent is at least one of aromatic oil, paraffin oil, naphthenic oil, petroleum resin, white mineral oil and polyethylene glycol. More preferably, the softener is white mineral oil, and can be, for example, 10# white mineral oil.
Preferably, the accelerator is at least one of a sulfenamide accelerator, a thiazole accelerator, a thiuram accelerator and a guanidine accelerator. Preferably, the accelerator is at least one of 2,2' -Dithiodibenzothiazole (DM), diphenylguanidine (accelerator D), and tetramethylthiuram disulfide (TMTD).
Preferably, the vulcanizing agent is a sulfur donor. The sulfur donor is a substance capable of providing sulfur. The sulfur comprises at least one of insoluble sulfur, soluble sulfur and oil-extended sulfur. For example, the vulcanizing agent IS ordinary sulfur S, oil-extended insoluble sulfur IS, or the like.
As previously mentioned, a second aspect of the present invention provides a process for preparing a vulcanized rubber, the process comprising:
(1) carrying out first mixing on a component A containing a rubber matrix, an initiator and a rubber modifier to obtain a section of master batch;
(2) carrying out second mixing on the first-stage masterbatch and a component B containing white carbon black, an activating agent, carbonate, an anti-aging agent and a softening agent to obtain a second-stage masterbatch;
(3) performing third mixing on the second-stage masterbatch and a component C containing an accelerator and a vulcanizing agent to obtain a final rubber compound;
(4) vulcanizing the final rubber;
the rubber modifier is an acrylic monomer, and the rubber matrix is butadiene rubber.
Component a, component B and component C referred to in the second aspect of the present invention together form the rubber composition for shoe soles described in the first aspect of the present invention, and therefore, each of the substances referred to in the second aspect of the present invention has the corresponding same properties as the same substances in the first aspect of the present invention, and in order to avoid repetition, the present invention will not be repeated in the second aspect with respect to certain features of the substances (e.g., optional kinds of substances, etc.), and those skilled in the art will not be construed as limiting the second aspect of the present invention.
The inventors of the present invention have found in their studies that the composition provided by the first aspect of the present invention can achieve more excellent properties, e.g., higher strength and better abrasion resistance, when a vulcanized rubber is produced by using the method described in the second aspect of the present invention, as compared to other methods of producing vulcanized rubbers in the prior art.
Preferably, in the second aspect, the acrylic monomer is at least one selected from the group consisting of acrylic acid, methacrylic acid, alkyl methacrylate, and glycidyl methacrylate. More preferably, in the second aspect, the acrylic monomer is an alkyl methacrylate and/or a glycidyl methacrylate.
Preferably, in the second aspect, the alkyl methacrylate is at least one of methyl methacrylate, ethyl methacrylate, and propyl methacrylate.
Preferably, in the second aspect, the carbonate is at least one of magnesium carbonate, zinc carbonate, and calcium carbonate; it is particularly preferred that the carbonate is zinc carbonate.
Preferably, in the second aspect, the cis content in the cis-butadiene rubber is 90 to 99% by weight.
Preferably, in the second aspect, the initiator is used in an amount of 0.2 to 1 part by weight, the rubber modifier is used in an amount of 5 to 10 parts by weight, the white carbon black is used in an amount of 40 to 70 parts by weight, the carbonate is used in an amount of 2 to 8 parts by weight, the activator is used in an amount of 1 to 5 parts by weight, the antioxidant is used in an amount of 0.5 to 3 parts by weight, the softener is used in an amount of 10 to 25 parts by weight, the accelerator is used in an amount of 2 to 6 parts by weight, and the vulcanizing agent is used in an amount of 1 to 4 parts by weight, based on 100 parts by weight of the rubber matrix.
Preferably, in the second aspect, the conditions for the first mixing include: the temperature is 130-; more preferably, the conditions of the first mixing include: the temperature is 150 ℃ and 170 ℃, and the time is 5-8 min.
Preferably, in the second aspect, the conditions for the second mixing include: the temperature is 100-150 ℃, and the time is 5-15 min; more preferably, the conditions of the second mixing include: the temperature is 110 ℃ and 130 ℃, and the time is 6-8 min.
Preferably, in the second aspect, the third mixing conditions include: the temperature is not more than 120 deg.C, and the time is 5-7 min.
Preferably, in the second aspect, the vulcanization conditions include: the temperature is 150 ℃ and 170 ℃, the pressure is 10-20MPa, and the time is 30-50 min.
In a second aspect of the present invention, according to a preferred embodiment, the conditions of the first mixing include: the temperature is 150-; the conditions of the second mixing include: the temperature is 110-; the conditions of the third mixing include: the temperature is not more than 120 ℃, and the time is 5-7 min; and the conditions of the vulcanization include: the temperature is 150 ℃ and 170 ℃, the pressure is 10-20MPa, and the time is 30-50 min. The vulcanized rubber prepared by the preferred embodiment has better mechanical properties (improved strength and better wear resistance) and better dynamic fatigue properties.
To specifically illustrate the process of the present invention for preparing a vulcanizate, a preferred embodiment is provided below for illustration:
(1) placing the rubber matrix in an internal mixer, plasticating at the rotation speed of 50-120 rpm, the initial mixing temperature of 70-90 ℃ and the raw rubber plasticating time of 0.1-1 min; then introducing the component A containing an initiator and a rubber modifier into the internal mixer for first mixing to obtain a section of master batch;
(2) adding the primary masterbatch and a component B containing white carbon black, an activating agent, an anti-aging agent, carbonate and a softening agent into an internal mixer for second mixing, discharging and standing for 3-5 hours to obtain secondary masterbatch;
(3) setting the rotation speed of an internal mixer to be 50-100 rpm, setting the initial mixing temperature to be 25-50 ℃, plasticating the two-stage masterbatch for 0.5-1.5 min, and adding a component C containing an accelerator and a vulcanizing agent to carry out third mixing to obtain final rubber;
(4) putting the final rubber compound into a vulcanizing press for vulcanization;
the rubber modifier is an acrylic monomer, and the rubber matrix is butadiene rubber.
The pressures used in the present invention are gage pressures.
As previously mentioned, a third aspect of the present invention provides a vulcanizate prepared by the method of the second aspect described above.
As previously mentioned, a fourth aspect of the invention provides the use of the vulcanizate of the third aspect described above for the preparation of a shoe sole.
The present invention will be described in detail below by way of examples.
Unless otherwise specified, various commercial products used below are commercially available.
The following examples and comparative examples the equipment for the preparation of vulcanizates are shown in Table 1.
The apparatus for testing the vulcanized rubbers obtained in the examples and comparative examples is shown in Table 2, and the test conditions are shown in Table 3.
The chemicals used in the examples and comparative examples are commercially available and are specified below:
butadiene rubber: BR9000, a yanshan petrochemical (wherein, the cis content is 97.8 wt%);
white carbon black: 165GR, Rodiya, France, nitrogen adsorption specific surface area 170m2/g；
Initiator: dicumyl peroxide (DCP), dibenzoyl peroxide (BPO) Haiyin chemical Co., Ltd, analytically pure;
carbonate salt: zinc carbonate, industrial grade, deep certified xin source chemostat limited; calcium carbonate, industrial grade, shanghai calcium carbonate plant; magnesium carbonate, technical grade, hebei magical technologies ltd;
rubber modifier: glycidyl methacrylate, Shanghai Michelin Biochemical technology, Inc.; methyl methacrylate, alatin reagent (shanghai) ltd; ethyl methacrylate, alatin reagent (shanghai) ltd; methacrylic acid, alatin reagent (shanghai) ltd; acrylic acid, alatin reagent (shanghai) ltd; bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide (Si69) (jerincha chemical ltd, hangzhou);
softening agent: white mineral oil No. 10 (10 # white oil for short), Shandong Taichang petrochemical science and technology Co., Ltd;
activating agent: stearic acid, Weifang Hengfeng chemical Limited;
an anti-aging agent: 4, 6-di-tert-butyl-p-cresol (anti-aging agent 264), Panhua chemistry (Shanghai) Co., Ltd;
vulcanizing agent: sulfur, Heicheng Hechenghuai chemical Limited;
accelerator (b): 2,2' -Dithiodibenzothiazyl (DM), diphenylguanidine (accelerator D), tetramethylthiuram disulfide (TMTD), Shanghai Yongzhen chemical technology Co., Ltd.
The components in the following examples and comparative examples were used in parts by weight, each representing 1 g.
The examples are intended to illustrate the rubber compositions, vulcanizates, and methods of making the same of the present invention.
TABLE 1
| Serial number | Device name | Model number | Manufacturer of the product |
| 1 | Internal mixer | BR1600 | Farrel America Ltd |
| 2 | Flat vulcanizing machine | XLB-D400*400*2 | Shanghai first rubber machinery plant |
TABLE 2
TABLE 3
Example 1
The rubber composition formula comprises: 100 parts of butadiene rubber, 40 parts of white carbon black, 0.2 part of DCP, 5 parts of glycidyl methacrylate, 8 parts of zinc carbonate, 10 parts of 10# white oil, 5 parts of stearic acid, 1 part of sulfur, 3 parts of accelerator DM, 1.5 parts of accelerator TMTD, 1.5 parts of accelerator D and 0.5 part of anti-aging agent 264.
The preparation process of the vulcanized rubber comprises the following steps:
(1) carrying out first mixing on a rubber matrix, an initiator and a rubber modifier to obtain a section of master batch; specifically, adding butadiene rubber into an internal mixer, setting the rotating speed to be 80rpm, setting the initial mixing temperature to be 80 ℃, and setting the raw rubber plastication time to be 0.5 min; adding an initiator and a rubber modifier into the internal mixer for mixing at the mixing temperature of 150 ℃ for 8min to obtain a section of master batch;
(2) performing second mixing on the first-stage master batch, white carbon black, carbonate, an activator, an anti-aging agent and a softener, specifically, adding the white carbon black, 10# white oil, zinc carbonate, stearic acid and the anti-aging agent 264 into an internal mixer, performing second mixing with the first-stage master batch, wherein the mixing time is 8min, the rubber discharge temperature is 110 ℃, discharging and standing for 4 hours to obtain a second-stage master batch;
(3) carrying out third mixing on the second-stage masterbatch, an accelerant and a vulcanizing agent to obtain final rubber; specifically, setting the rotation speed of an internal mixer to be 80rpm, setting the initial mixing temperature to be 40 ℃, plasticating the two-stage masterbatch for 1min, adding a vulcanizing agent and an accelerator to perform third mixing, setting the mixing temperature to be 105 ℃, mixing for 5min, and discharging to obtain final mixed rubber;
(4) 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 50min, so that a vulcanized rubber sample S1 is obtained.
The cured rubber sample S1 was subjected to the performance test, and the results are shown in Table 4.
Example 2
The rubber composition formula comprises: 100 parts of butadiene rubber, 50 parts of white carbon black, 0.6 part of BPO, 8 parts of methyl methacrylate, 5 parts of zinc carbonate, 18 parts of 10# white oil, 3 parts of stearic acid, 4 parts of sulfur, 4 parts of accelerator DM and 2 parts of anti-aging agent 264.
The preparation process of the vulcanized rubber comprises the following steps:
(1) carrying out first mixing on a rubber matrix, an initiator and a rubber modifier to obtain a section of master batch; specifically, adding butadiene rubber into an internal mixer, setting the rotating speed to be 80rpm, setting the initial mixing temperature to be 80 ℃, and setting the raw rubber plastication time to be 0.5 min; adding an initiator and a rubber modifier into the internal mixer for mixing at 160 ℃ for 6min to obtain a section of master batch;
(2) adding the primary masterbatch and white carbon black, carbonate, an activator, an anti-aging agent and a softener into an internal mixer for second mixing to obtain secondary masterbatch, specifically adding the white carbon black, 10# white oil, zinc carbonate, stearic acid and the anti-aging agent 264 into the internal mixer, and carrying out second mixing with the primary masterbatch, wherein the mixing time is 7min, the rubber discharge temperature is 120 ℃, discharging and standing for 4 hours to obtain secondary masterbatch;
(3) carrying out third mixing on the second-stage masterbatch, an accelerant and a vulcanizing agent to obtain final rubber; specifically, setting the rotation speed of an internal mixer to be 80rpm, setting the initial mixing temperature to be 40 ℃, plasticating the two-stage masterbatch for 1min, adding a vulcanizing agent and an accelerator to perform third mixing, setting the mixing temperature to be 110 ℃, mixing for 7min, and discharging to obtain final mixed rubber;
(4) and (3) putting the final rubber compound into a flat vulcanizing machine for vulcanization, wherein the vulcanization temperature is 170 ℃, the vulcanization pressure is 10MPa, and the vulcanization time is 30min, so that a vulcanized rubber sample S2 is obtained.
The cured rubber sample S2 was subjected to the performance test, and the results are shown in Table 4.
Example 3
The rubber composition formula comprises: 100 parts of butadiene rubber, 70 parts of white carbon black, 1 part of DCP, 10 parts of ethyl methacrylate, 2 parts of zinc carbonate, 25 parts of 10# white oil, 1 part of stearic acid, 2 parts of sulfur, 2 parts of accelerator D and 3 parts of anti-aging agent 264.
The preparation process of the vulcanized rubber comprises the following steps:
(1) carrying out first mixing on a rubber matrix, an initiator and a rubber modifier to obtain a section of master batch; specifically, adding solution polymerized styrene-butadiene rubber into an internal mixer, setting the rotating speed to be 80rpm, setting the initial mixing temperature to be 80 ℃, and setting the raw rubber plastication time to be 0.5 min; adding an initiator and a rubber modifier into the internal mixer for mixing at the mixing temperature of 170 ℃ for 5min to obtain a section of master batch;
(2) adding the primary masterbatch, white carbon black, carbonate, an activator, an anti-aging agent and a softener into an internal mixer for secondary mixing, specifically adding the white carbon black, 10# white oil, zinc carbonate, stearic acid and the anti-aging agent 264 into the internal mixer, and carrying out secondary mixing with the primary masterbatch, wherein the mixing time is 6min, the rubber discharge temperature is 130 ℃, discharging and standing for 4 hours to obtain secondary masterbatch;
(3) carrying out third mixing on the second-stage masterbatch, an accelerant and a vulcanizing agent to obtain final rubber; specifically, setting the rotation speed of an internal mixer to be 80rpm, setting the initial mixing temperature to be 40 ℃, plasticating the two-stage master batch for 1min, adding a vulcanizing agent and an accelerator to perform third mixing, setting the mixing temperature to be 120 ℃, mixing for 6min, and discharging to obtain final mixed rubber;
(4) and (3) putting the final rubber compound into a flat vulcanizing machine for vulcanization, wherein the vulcanization temperature is 160 ℃, the vulcanization pressure is 15MPa, and the vulcanization time is 40min, so that a vulcanized rubber sample S3 is prepared.
The cured rubber sample S3 was subjected to the performance test, and the results are shown in Table 4.
Example 4
This example uses a rubber composition formulation similar to that of example 3, except that the same weight of methacrylic acid was used in place of the ethyl methacrylate in example 3, specifically:
the rubber composition formula comprises: 100 parts of butadiene rubber, 70 parts of white carbon black, 1 part of DCP, 10 parts of methacrylic acid, 2 parts of zinc carbonate, 25 parts of No. 10 white oil, 1 part of stearic acid, 2 parts of sulfur, 2 parts of accelerator D and 3 parts of anti-aging agent 264.
The procedure for the preparation of the vulcanizates was the same as in example 3. A vulcanized rubber sample S4 was obtained.
The cured rubber sample S4 was subjected to the performance test, and the results are shown in Table 4.
Example 5
The rubber composition formulation of this example was the same as in example 3 and a vulcanized rubber was prepared in a similar manner to example 3, the vulcanized rubber being prepared in a similar manner to example 3 except that:
in the process of preparing the first-stage masterbatch, the temperature of first mixing is 130 ℃, and the time is 10 min;
in the process of preparing the second-stage masterbatch, the temperature of second mixing is 140 ℃ and the time is 5 min;
in the process of preparing the final rubber compound, the time of the third mixing is 6min, and the rubber discharging temperature is 120 ℃.
A vulcanized rubber sample S5 was obtained.
The cured rubber sample S5 was subjected to the performance test, and the results are shown in Table 4.
Example 6
This example uses a rubber composition formulation similar to that of example 2, except that the same weight of acrylic acid is used in place of the methyl methacrylate in example 2, specifically:
the rubber composition formula comprises: 100 parts of butadiene rubber, 50 parts of white carbon black, 0.6 part of BPO, 8 parts of acrylic acid, 5 parts of zinc carbonate, 18 parts of No. 10 white oil, 3 parts of stearic acid, 4 parts of sulfur, 4 parts of accelerator DM and 2 parts of anti-aging agent 264.
The procedure for the preparation of the vulcanizates was the same as in example 2. A vulcanized rubber sample S6 was obtained.
The cured rubber sample S6 was subjected to the performance test, and the results are shown in Table 4.
Example 7
The formulation of the rubber composition of this example was similar to that of example 1, and a vulcanized rubber was prepared in the same manner as in example 1, except that:
the carbonate used in this example was magnesium carbonate and was used in an amount of 8 parts by weight.
A vulcanized rubber sample S7 was obtained.
The cured rubber sample S7 was subjected to the performance test, and the results are shown in Table 4.
Example 8
The formulation of the rubber composition of this example was similar to that of example 2, and a vulcanized rubber was prepared in the same manner as in example 2, except that:
the carbonate used in this example was calcium carbonate and was used in an amount of 5 parts by weight.
A vulcanized rubber sample S8 was obtained.
The cured rubber sample S8 was subjected to the performance test, and the results are shown in Table 4.
Comparative example 1
The formulation of the rubber composition of this comparative example was similar to that of example 3, except that the rubber modifier of example 3 was replaced with the same weight of Si69 in this comparative example, specifically:
the rubber composition formula comprises: 100 parts of butadiene rubber, 70 parts of white carbon black, 1 part of DCP, 10 parts of Si69, 2 parts of zinc carbonate, 25 parts of No. 10 white oil, 1 part of stearic acid, 2 parts of sulfur, 2 parts of accelerator D and 3 parts of anti-aging agent 264.
The procedure for the preparation of the vulcanizates was the same as in example 3. A vulcanizate sample DS1 was prepared.
The cured rubber sample DS1 was subjected to performance testing and the results are shown in Table 4.
TABLE 4
| Sample numbering | S1 | S2 | S3 | S4 | S5 | S6 | S7 | S8 | DS1 |
| Tear Strength (MPa) | 11.0 | 10.2 | 10.5 | 9.6 | 9.0 | 9.7 | 10.2 | 9.8 | 7.3 |
| Akron abrasion (cm)3) | 0.28 | 0.32 | 0.30 | 0.38 | 0.48 | 0.42 | 0.45 | 0.39 | 0.68 |
| Fatigue life (thousands times) | 4.20 | 4.16 | 4.14 | 3.64 | 3.58 | 3.87 | 3.59 | 3.90 | 2.06 |
As can be seen from the results in Table 4, the rubber composition of the present invention can achieve better dispersibility of the components of the rubber composition in the rubber matrix, so that the further prepared vulcanized rubber can have excellent comprehensive properties such as improved strength, improved wear resistance, improved dynamic fatigue resistance, etc.
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 (16)
1. A method of preparing a vulcanized rubber for shoe soles, the method comprising:
(1) carrying out first mixing on a component A containing a rubber matrix, an initiator and a rubber modifier to obtain a section of master batch, wherein the first mixing conditions comprise that: the temperature is 150-;
(2) and carrying out second mixing on the first-stage masterbatch and a component B containing white carbon black, an activating agent, carbonate, an anti-aging agent and a softening agent to obtain a second-stage masterbatch, wherein the second mixing conditions comprise that: the temperature is 110-;
(3) and carrying out third mixing on the second-stage masterbatch and a component C containing an accelerator and a vulcanizing agent to obtain a final rubber compound, wherein the third mixing conditions comprise that: the temperature is not more than 120 ℃, and the time is 5-7 min;
(4) subjecting the final batch to vulcanization under conditions comprising: the temperature is 150-;
the rubber matrix comprises, by weight, 100 parts of a rubber matrix, 0.2-1 part of an initiator, 5-10 parts of a rubber modifier, 40-70 parts of white carbon black, 2-8 parts of carbonate, 1-5 parts of an activator, 0.5-3 parts of an anti-aging agent, 10-25 parts of a softener, 2-6 parts of an accelerator and 1-4 parts of a vulcanizing agent;
wherein the initiator is at least one selected from dicumyl peroxide, dibenzoyl peroxide, bis (2, 4-dichlorobenzoyl) peroxide, diacetyl peroxide and dilauryl peroxide.
2. The method according to claim 1, wherein the acrylic monomer is selected from at least one of acrylic acid, methacrylic acid, alkyl methacrylate, and glycidyl methacrylate.
3. The method of claim 1, wherein the acrylic monomer is an alkyl methacrylate and/or a glycidyl methacrylate.
4. The method of claim 2, wherein the "alkyl" of the alkyl methacrylate comprises C1-6Linear or branched alkyl groups of (a).
5. The method of claim 2, wherein the alkyl methacrylate is at least one of methyl methacrylate, ethyl methacrylate, and propyl methacrylate.
6. The method of claim 1, wherein the carbonate is at least one of magnesium carbonate, zinc carbonate, and calcium carbonate.
7. The method of claim 1, wherein the carbonate is zinc carbonate.
8. The process of claim 1, wherein the cis content in the butadiene rubber is 90-99 wt%.
9. The method according to any one of claims 1 to 8, wherein the silica has a nitrogen adsorption specific surface area of 10 to 200m2/g。
10. The method of any one of claims 1-8, wherein the activator is a fatty acid.
11. The method according to any one of claims 1 to 8, wherein the antioxidant is at least one of a phenolic antioxidant, an amine antioxidant, a quinoline antioxidant, and a benzimidazole antioxidant.
12. The method according to any one of claims 1 to 8, wherein the softening agent is at least one of aromatic oil, paraffin oil, naphthenic oil, petroleum resin, white mineral oil, and polyethylene glycol.
13. The process of any one of claims 1-8, wherein the accelerator is at least one of a sulfenamide accelerator, a thiazole accelerator, a thiuram accelerator, and a guanidine accelerator.
14. The method according to any one of claims 1-8, wherein the vulcanizing agent is a sulfur donor.
15. A vulcanized rubber produced by the process of any one of claims 1-14.
16. Use of the vulcanizate of claim 15 for the preparation of shoe soles.
Priority Applications (1)
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| CN106566022A (en) * | 2016-10-26 | 2017-04-19 | 罗娟如 | Sole rubber for industrial shoes |
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