CN107955232B - Application of maleic acid monomer, rubber composition, vulcanized rubber and preparation method thereof - Google Patents
Application of maleic acid monomer, rubber composition, vulcanized rubber and preparation method thereof Download PDFInfo
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- CN107955232B CN107955232B CN201610908140.8A CN201610908140A CN107955232B CN 107955232 B CN107955232 B CN 107955232B CN 201610908140 A CN201610908140 A CN 201610908140A CN 107955232 B CN107955232 B CN 107955232B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention relates to the field of rubber, and discloses an application of a maleic acid monomer, a rubber composition, vulcanized rubber and a preparation method of the vulcanized rubber, wherein the rubber composition contains a component A, a component B, a component C and a component D which are independently stored, the component A contains a rubber matrix and a matrix modifier, the component B contains white carbon black, the component C contains an activator, an anti-aging agent, a softener and optionally carbon black, and the component D contains an accelerator and a vulcanizing agent; the matrix modifier is maleic acid monomer. In the processing technology, the bridge function of the matrix modifier in the matrix rubber and the white carbon black can be better exerted, the interaction of the white carbon black and the rubber matrix is facilitated, the strength of vulcanized rubber prepared by further vulcanization can be better improved, the heat generation of the vulcanized rubber is reduced, and the wet skid resistance of the vulcanized rubber material is improved.
Description
Technical Field
The invention relates to the field of rubber, in particular to application of a maleic acid monomer as a rubber matrix modifier, a rubber composition, a method for preparing vulcanized rubber and the vulcanized rubber prepared by the method.
Background
The dynamic hysteresis loss performance of the rubber formula is particularly important to influence the tire performance, and the hysteresis loss causes the energy consumption of the rubber material to be increased, the heat generation to be increased, the elasticity to be reduced and the rolling resistance to be increased in the dynamic deformation process. Heat generation also causes a decrease in the strength and wear resistance of the rubber, causing early damage to the tire, and also increases the rolling resistance of the tire, increasing fuel consumption and carbon dioxide emissions.
CN102382338A discloses an isoprene rubber blend, which comprises isoprene rubber, trans-1, 4-polyisoprene, a reinforcing filler, an in-situ grafting modification auxiliary agent, a compound rubber and a first additive. The in-situ grafting modification auxiliary agent adopted by the prior art performs a chemical reaction with the reinforcing filler and simultaneously performs a grafting reaction with functional groups such as double bonds on a rubber molecular chain, so that the interface bonding force between an organic polymer and the reinforcing filler and the dispersion level of the reinforcing filler in rubber are greatly improved, and the fatigue resistance of the isoprene rubber blend is improved.
CN103881161A discloses a trans-polyisoprene rubber and cis-polyisoprene rubber composition and a processing technology thereof, and specifically discloses a rubber total amount of 100 parts by mass, wherein the total amount of synthetic trans-polyisoprene and synthetic cis-polyisoprene is 5-60 parts by mass, 40-95 parts by mass of natural rubber, 5-90 parts by mass of white carbon black and 5-990 parts by mass of carbon black; the master batch process comprises the following steps: mixing the synthesized trans-polyisoprene or the composition of the synthesized trans-polyisoprene and the synthesized cis-polyisoprene rubber with white carbon black and a coupling agent to obtain white carbon black wood glue; mixing natural rubber and carbon black to obtain carbon black master batch; and (3) final rubber mixing process: and mixing the carbon black master batch, the white carbon black wood glue, the anti-aging agent, the activator, the accelerator and the vulcanizing agent to prepare the rubber composition. The rubber composition and the rubber material prepared by the process in the prior art have the characteristics of improving wear resistance and reducing heat generation, and can be applied to rubber products, particularly automobile tires, to reduce rolling resistance and reduce heat generation.
CN103703072A discloses a rubber composition for a tread, which contains solution-polymerized styrene-butadiene rubber, carbon black, silica and polyethylene glycol, wherein the content of the solution-polymerized styrene-butadiene rubber in 100 mass% of the rubber component is 60 mass% or more, the content of the carbon black is 10 parts by mass or less, the content of the silica is 50 parts by mass or more, and the content of the polyethylene glycol is 0.1 to 3.5 parts by mass, relative to 100 parts by mass of the rubber component. According to this prior art, rubber compositions containing solution-polymerized styrene-butadiene rubber, carbon black, silica and polyethylene glycol in respective prescribed amounts, which are applied to the tread of a tire, can provide a pneumatic tire improved in fuel economy and abrasion resistance in a well-balanced manner. Further, the vulcanization speed is good when the tire is manufactured, and the appearance of the manufactured tire is good.
CN103087365A discloses a rubber composition for anti-wet abrasion balancing tire tread, which comprises diene elastomer, inorganic reinforcing filler, coupling agent and plasticizer. In this prior art, when a tire comprising a rubber composition is used, the tread of the tire, which is used for manufacturing a semi-steel radial passenger tire, has excellent wet skid resistance, giving the tire a balance of properties of wet grip and abrasion resistance.
However, the above prior art provides rubbers which still do not satisfy the strength, heat generation reduction, and wet skid performance improvement required for tire tread rubbers, and there is a need for a rubber having improved properties.
Disclosure of Invention
The invention aims to solve the problems of improving the strength, reducing heat generation and improving wet skid resistance of rubber used for tire treads, and provides a matrix modifier, a rubber composition containing the matrix modifier, a vulcanized rubber prepared from the rubber composition and a preparation method of the vulcanized rubber.
In order to achieve the above object, the present invention provides, in a first aspect, use of a maleic acid-based monomer selected from the group consisting of maleic acid, maleic anhydride and dialkyl maleate as a modifier for a rubber matrix.
In a second aspect, the invention provides a rubber composition, which comprises a component A, a component B, a component C and a component D, wherein the component A, the component B, the component C and the component D are independently stored, the component A comprises a rubber matrix and a matrix modifier, the component B comprises white carbon black, the component C comprises an activator, an anti-aging agent, a softener and optionally carbon black, and the component D comprises an accelerator and a vulcanizing agent; the matrix modifier is a maleic acid monomer selected from the group consisting of maleic acid, maleic anhydride and dialkyl maleates.
In a third aspect, the present invention provides a process for preparing a vulcanizate, the process comprising:
(1) carrying out first mixing on a rubber matrix and a matrix modifier to obtain a section of master batch;
(2) carrying out second mixing on the first-stage masterbatch and white carbon black to obtain second-stage masterbatch;
(3) carrying out third mixing on the second-stage masterbatch, an activating agent, an anti-aging agent, a softening agent and optional carbon black to obtain third-stage masterbatch;
(4) carrying out fourth mixing on the three sections of master batch, an accelerant and a vulcanizing agent to obtain final rubber;
(5) vulcanizing the final rubber;
wherein the matrix modifier is a maleic acid monomer selected from the group consisting of maleic acid, maleic anhydride and dialkyl maleates.
In a fourth aspect, the present invention provides a vulcanizate prepared by the foregoing method.
The vulcanized rubber is obtained by a novel mixing method, wherein a rubber matrix and a matrix modifier are mixed to prepare a matrix master batch; then preparing a second-stage white carbon black master batch by adopting the matrix master batch; then adding an activating agent, an anti-aging agent, a softening agent and the like into the white carbon black master batch, mixing to prepare a three-section master batch, adding a vulcanizing agent and an accelerator into the three-section master batch to prepare a final rubber batch, and finally vulcanizing the final rubber batch to prepare the vulcanized rubber.
In the processing technology, the bridge function of the matrix modifier in the matrix rubber and the white carbon black can be better exerted, the interaction of the white carbon black and the rubber matrix is facilitated, the strength of vulcanized rubber prepared by further vulcanization can be better improved, the heat generation of the vulcanized rubber is reduced, and the wet skid resistance of the vulcanized rubber material is improved.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
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.
In a first aspect, the present invention provides the use of a maleic acid-based monomer selected from the group consisting of maleic acid, maleic anhydride and dialkyl maleates as a modifier for a rubber matrix.
The maleic acid monomer can modify a rubber matrix in the application of being used as a rubber matrix modifier, thereby being beneficial to the interaction between matrix rubber and white carbon black, being beneficial to improving the strength of vulcanized rubber prepared by subsequent vulcanization, reducing the heat generation of the vulcanized rubber and improving the wet skid resistance of a vulcanized rubber material.
In the application, the maleic acid-based monomer can be one or more of maleic acid, maleic anhydride and dialkyl maleate, that is, in the application of the present invention, the maleic acid-based monomer as the rubber matrix modifier can be in the form of a composition.
The carbon number of the alkyl group in the dialkyl maleate may be 1 to 12.
Preferably, in said application, the carbon number of the alkyl group in the dialkyl maleate is 1 to 6.
Preferably, the maleic acid-based monomer is at least one selected from the group consisting of maleic acid, maleic anhydride, dimethyl maleate, diethyl maleate, dibutyl maleate, dipropyl maleate and diisopropyl maleate; more preferably, the maleic acid-based monomer is maleic anhydride and/or diethyl maleate.
Preferably, the maleic acid-based monomer is used for the first mixing together with the rubber matrix in preparing the rubber composition.
Preferably, the rubber matrix is selected from at least one of solution-polymerized styrene-butadiene rubber, butadiene rubber and natural rubber.
Preferably, the solution-polymerized styrene-butadiene rubber contains 15 to 30 mass% of styrene structural units, 35 to 70 mass% of vinyl groups, 0 to 30 mass% of oil-containing components, and 45 to 70 Mooney viscosity.
In the present invention, the oil-containing component is 0 to 30% by mass, and the solution-polymerized styrene-butadiene rubber may or may not contain the oil-containing component.
Preferably, the cis content in the butadiene rubber is 90 to 99 mass%.
In the present invention, the natural rubber may be, for example, a standard rubber.
Preferably, the conditions of the first mixing include: the temperature is 130-; more preferably, the conditions of the first mixing include: the temperature is 140 ℃ and 150 ℃, and the time is 5-8 min.
In a second aspect, the invention provides a rubber composition, which comprises a component A, a component B, a component C and a component D, wherein the component A, the component B, the component C and the component D are independently stored, the component A comprises a rubber matrix and a matrix modifier, the component B comprises white carbon black, the component C comprises an activator, an anti-aging agent, a softener and optionally carbon black, and the component D comprises an accelerator and a vulcanizing agent; the matrix modifier is maleic acid monomer, and the maleic acid monomer is at least one selected from maleic acid, maleic anhydride and maleic acid dialkyl ester.
Preferably, in the rubber composition, the number of carbons of the alkyl group in the dialkyl maleate is 1 to 6.
Preferably, the maleic acid-based monomer is at least one selected from the group consisting of maleic acid, maleic anhydride, dimethyl maleate, diethyl maleate, dibutyl maleate, dipropyl maleate and diisopropyl maleate. More preferably, the maleic acid-based monomer is at least one selected from the group consisting of maleic acid, maleic anhydride, diethyl maleate and diisopropyl maleate; particularly preferably, the maleic acid-based monomer is maleic anhydride and/or diethyl maleate. When the maleic acid-based monomer is a mixture of maleic anhydride and diethyl maleate, the weight ratio of the two is particularly preferably 1: 1.5-3.
The kind of the matrix modifier in the second aspect of the present invention is identical to that described in the first aspect of the present invention, and the present invention will not be described herein again in order to avoid redundancy.
Preferably, in the rubber composition, the matrix modifier is contained in an amount of 2 to 20 parts by weight relative to 100 parts by weight of the rubber matrix; more preferably 5 to 10 parts by weight.
Preferably, in the rubber composition, the white carbon is contained in an amount of 20 to 120 parts by weight, more preferably 50 to 100 parts by weight, relative to 100 parts by weight of the rubber base.
The optional carbon black is that the rubber composition of the present invention may or may not contain carbon black, and preferably, the rubber composition contains carbon black.
Preferably, the activating agent is contained in the rubber composition in an amount of 1 to 15 parts by weight, more preferably 3 to 8 parts by weight, relative to 100 parts by weight of the rubber matrix.
Preferably, the antioxidant is contained in the rubber composition in an amount of 0.5 to 10 parts by weight, more preferably 1 to 6 parts by weight, based on 100 parts by weight of the rubber base.
Preferably, the softener is contained in the rubber composition in an amount of 5 to 30 parts by weight, more preferably 10 to 20 parts by weight, relative to 100 parts by weight of the rubber base.
Preferably, the carbon black is contained in the rubber composition in an amount of 0 to 30 parts by weight, more preferably 0 to 20 parts by weight, relative to 100 parts by weight of the rubber matrix. The content of the carbon black is 0 to 20 parts by weight, and represents that: when no carbon black is contained, the content of the carbon black is 0 part by weight; when carbon black is contained, the content of the carbon black is more than 0 and 20 parts by weight or less.
Preferably, the accelerator is contained in the rubber composition in an amount of 0.5 to 10 parts by weight, more preferably 1 to 6 parts by weight, relative to 100 parts by weight of the rubber base.
Preferably, the vulcanizing agent is contained in the rubber composition in an amount of 0.1 to 5 parts by weight, more preferably 0.5 to 3 parts by weight, relative to 100 parts by weight of the rubber matrix.
According to a preferred embodiment, in the rubber composition, the white carbon is contained in an amount of 20 to 120 parts by weight, the activator is contained in an amount of 1 to 15 parts by weight, the antioxidant is contained in an amount of 0.5 to 10 parts by weight, the softener is contained in an amount of 5 to 30 parts by weight, the carbon black is contained in an amount of 0 to 30 parts by weight, the accelerator is contained in an amount of 0.5 to 10 parts by weight, and the vulcanizing agent is contained in an amount of 0.1 to 5 parts by weight, based on 100 parts by weight of the rubber base.
According to another more preferred embodiment, the white carbon black is contained in an amount of 50 to 100 parts by weight, the activator is contained in an amount of 3 to 8 parts by weight, the antioxidant is contained in an amount of 1 to 6 parts by weight, the softener is contained in an amount of 10 to 20 parts by weight, the carbon black is contained in an amount of 0 to 20 parts by weight, the accelerator is contained in an amount of 1 to 6 parts by weight, and the vulcanizing agent is contained in an amount of 0.5 to 3 parts by weight, based on 100 parts by weight of the rubber base.
Preferably, in the rubber composition, the rubber matrix is selected from at least one of solution-polymerized styrene-butadiene rubber, and natural rubber.
Preferably, the rubber matrix is solution polymerized styrene-butadiene rubber or a mixture of solution polymerized styrene-butadiene rubber and butadiene rubber; relative to 100 parts by weight of the rubber matrix, the amount of the solution polymerized styrene-butadiene rubber in the rubber matrix is 60-100 parts by weight, and the amount of the butadiene rubber is 0-40 parts by weight.
Preferably, in the rubber composition, the solution-polymerized styrene-butadiene rubber has a styrene structural unit content of 15 to 30% by mass, a vinyl group content of 35 to 70% by mass, an oil-containing component of 0 to 30% by mass, and a Mooney viscosity of 45 to 70.
Preferably, in the rubber composition, the cis content in the cis-butadiene rubber is 90 to 99 mass%.
In a third aspect, the present invention provides a process for preparing a vulcanizate, the process comprising:
(1) carrying out first mixing on a rubber matrix and a matrix modifier to obtain a section of master batch;
(2) carrying out second mixing on the first-stage masterbatch and white carbon black to obtain second-stage masterbatch;
(3) carrying out third mixing on the second-stage masterbatch, an activating agent, an anti-aging agent, a softening agent and optional carbon black to obtain third-stage masterbatch;
(4) carrying out fourth mixing on the three sections of master batch, an accelerant and a vulcanizing agent to obtain final rubber;
(5) vulcanizing the final rubber;
wherein the matrix modifier is a maleic acid monomer, and the maleic acid monomer is at least one selected from maleic acid, maleic anhydride and dialkyl maleate.
Preferably, in the method, the number of carbons of the alkyl group in the dialkyl maleate is 1 to 6.
Preferably, the maleic acid-based monomer is at least one selected from the group consisting of maleic acid, maleic anhydride, dimethyl maleate, diethyl maleate, dibutyl maleate, dipropyl maleate and diisopropyl maleate; more preferably, the maleic acid-based monomer is at least one selected from the group consisting of maleic acid, maleic anhydride, diethyl maleate and diisopropyl maleate. Particularly preferably, the maleic acid-based monomer is maleic anhydride and/or diethyl maleate.
The kind of the matrix modifier in the third aspect of the present invention (i.e., in the process for producing a vulcanized rubber) is completely the same as that of the matrix modifier described in the first aspect of the present invention, and the description of the present invention is omitted herein for the sake of avoiding repetition.
Preferably, in the method for producing a vulcanized rubber, the matrix modifier is used in an amount of 2 to 20 parts by weight relative to 100 parts by weight of the rubber matrix; preferably 5 to 10 parts by weight.
Preferably, in the preparation method of the vulcanized rubber, relative to 100 parts by weight of the rubber matrix, the white carbon black is used in an amount of 20-120 parts by weight, the activating agent is used in an amount of 1-15 parts by weight, the anti-aging agent is used in an amount of 0.5-10 parts by weight, the softening agent is used in an amount of 5-30 parts by weight, the carbon black is used in an amount of 0-30 parts by weight, the accelerator is used in an amount of 0.5-10 parts by weight, and the vulcanizing agent is used in an amount of 0.1-5 parts by weight.
More preferably, in the method for preparing vulcanized rubber, the white carbon black is used in an amount of 50 to 100 parts by weight, the activating agent is used in an amount of 3 to 8 parts by weight, the antioxidant is used in an amount of 1 to 6 parts by weight, the softening agent is used in an amount of 10 to 20 parts by weight, the carbon black is used in an amount of 0 to 20 parts by weight, the accelerator is used in an amount of 1 to 6 parts by weight, and the vulcanizing agent is used in an amount of 0.5 to 3 parts by weight, based on 100 parts by weight of the rubber matrix.
In fact, in the process for producing a vulcanized rubber, the amounts of the respective components involved in the production of the vulcanized rubber may be the same as the amounts of the respective components in the rubber composition involved in the second aspect of the present invention, and therefore, in the third aspect of the present invention, the amounts of the respective components involved in the production of the vulcanized rubber are not individually listed in order to avoid repetition.
Preferably, in the method for producing a vulcanized rubber, the rubber matrix is selected from at least one of solution-polymerized styrene-butadiene rubber, butadiene rubber and natural rubber.
Preferably, in the method for producing a vulcanized rubber, the solution-polymerized styrene-butadiene rubber has a styrene structural unit content of 15 to 30% by mass, a vinyl group content of 35 to 70% by mass, an oil-containing component of 0 to 30% by mass, and a Mooney viscosity of 45 to 70.
Preferably, in the production method of a vulcanized rubber, the cis content in the cis-butadiene rubber is 90 to 99 mass%.
Preferably, in the preparation method of the vulcanized rubber, the rubber matrix is solution polymerized styrene-butadiene rubber or a mixture of solution polymerized styrene-butadiene rubber and butadiene rubber. More preferably, the content of the solution-polymerized styrene-butadiene rubber in the rubber matrix is 60 to 100 parts by weight and the content of the butadiene rubber is 0 to 40 parts by weight with respect to 100 parts by weight of the rubber matrix. The cis-butadiene rubber content is 0-40 parts by weight, and represents: when the rubber matrix does not contain butadiene rubber, the content of the butadiene rubber is 0 part by weight; when the rubber matrix contains butadiene rubber, the content of the butadiene rubber is more than 0 part by weight and less than or equal to 40 parts by weight.
Preferably, in the method for producing a vulcanized rubber, the conditions for the first mixing include: the temperature is 130-; more preferably, the conditions of the first mixing include: the temperature is 140 ℃ and 150 ℃, and the time is 5-8 min. And the first kneading in the production method of a vulcanized rubber is the same as the first kneading in the first aspect of the invention.
Preferably, in the method for producing a vulcanized rubber, the conditions for the second mixing include: the temperature is 100-150 ℃, and the time is 3-10 min; more preferably, the conditions of the second mixing include: the temperature is 110-120 ℃, and the time is 5-7 min.
Preferably, in the method for producing a vulcanized rubber, the conditions for the third mixing include: the temperature is 80-140 deg.C, and the time is 3-12 min; more preferably, the third mixing conditions include: the temperature is 110 ℃ and 130 ℃, and the time is 3-5 min.
Preferably, in the method for producing a vulcanized rubber, the conditions for the fourth mixing include: the temperature is not more than 130 deg.C, and the time is 5-7 min. More preferably, the temperature of the fourth mixing is 110-130 ℃.
Preferably, the anti-aging agent is at least one of amine anti-aging agents, quinoline anti-aging agents and benzimidazole anti-aging agents. For example, the antioxidant is antioxidant 4020.
Preferably, the softening agent is at least one of aromatic oil, paraffin oil, naphthenic oil, petroleum resin, and polyethylene glycol. Wherein the weight average molecular weight of the polyethylene glycol is 3000-5000. And the polyethylene glycol with the weight-average molecular weight within the range of 3000-. The aromatic oil may be, for example, aromatic oil TDAE V500, and the polyethylene glycol may be, for example, polyethylene glycol PEG 4000.
Preferably, the activator is a combination of a metal oxide and a fatty acid or a fatty acid metal soap salt. The metal oxide is preferably zinc oxide and/or magnesium oxide; the fatty acid is preferably stearic acid; the fatty acid metal soap salt is zinc stearate and/or zinc borate.
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 N-tert-butyl-2-benzothiazolesulfenamide (TBBS), diphenylguanidine (accelerator D).
Preferably, the vulcanizing agent is sulfur and/or 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.
According to the present invention, preferably, the white carbon black is silica; more preferably, the white carbon blackThe nitrogen adsorption specific surface area is 10-200m2(ii) in terms of/g. For example, the white carbon black is 115GR (Rodiya, France) and/or 165GR (Rodiya, France).
Preferably, when carbon black is contained, the carbon black has a CTAB adsorption specific surface area of 10 to 300m2(ii) in terms of/g. For example, the carbon black is N330 (Zideli chemical technologies, Inc. of Dongguan) and/or N220 (Zideli chemical technologies, Inc. of Dongguan).
Preferably, the conditions of the vulcanization include: the temperature is 150 ℃ and 170 ℃, the pressure is 10-20MPa, and the time is 30-50 min.
In a fourth aspect, the present invention provides a vulcanizate prepared by the above-described method.
The pressures used in the present invention are gage pressures.
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:
solution polymerized styrene-butadiene rubber: 2535E, Yanshan petrochemical (wherein the styrene structural unit content is 23 mass%, the vinyl content is 63 mass%, the oil content is 27 mass%, and the Mooney viscosity is 60);
butadiene rubber: BR9000, a yanshan petrochemical (wherein, the cis content is 97.8 mass%);
white carbon black: 165GR, Rodiya, France, nitrogen adsorption specific surface area 170m2/g；
Carbon black: n330, Zideli chemical technology Co., Ltd, Dongguan, CTAB adsorption specific surface area of 75m2/g；
Matrix modifier: maleic anhydride (Jessie Ka chemical Co., Ltd., Hangzhou), diethyl maleate (Jinnan Zi Anhua chemical Co., Ltd.), maleic acid (Bailingwei science and technology Co., Ltd.), diisopropyl maleate (Shaanxi Baoyu Jade chemical Co., Ltd.);
softening agent: environmental aromatic oil TDAE V500 (TDAE for short), xindayang (ningbo) limited;
activating agent: zinc oxide, stearic acid, Weifang Heng Feng chemical Limited;
an anti-aging agent: n- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine (antioxidant 4020), 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer (antioxidant RD), saint ao chemical technology ltd, jiang su;
vulcanizing agent: sulfur, Heicheng Hechenghuai chemical Limited;
accelerator (b): n-tert-butyl-2-benzothiazolesulfenamide (TBBS), diphenylguanidine (accelerator D), tetramethylthiuram disulfide (TMTD), Shanghai Yongyan chemical science and technology Co., Ltd;
PEG 4000: huaihean petrochemical plant.
The components in the following examples and comparative examples were used in parts by weight, each representing 1 g.
Examples 1 to 6 are intended to illustrate the rubber composition, the vulcanized rubber and the process for producing 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
| Serial number | Test items | Model of the test apparatus | Manufacturer of the product |
| 1 | Tensile strength | Universal tensile machine, SHIMADZU, AG-20KNG | Shimadzu Japan Ltd |
| 2 | Rebound resilience | ZWICK 5109 | ZWICK, Germany |
| 3 | DIN abrasion | GT-7012-A | High speed railway instrumentation Co Ltd |
| 4 | Dynamic viscoelastometer | EPLEXOR 500N | German Gaobao Co |
| 5 | Rubber processing analyzer | RPA2000 | Alpha company of USA |
| 6 | Dynamic compression fatigue heating | Compression thermogenesis experimental machine Y3000E | Beijing Youth deep electronics Instrument Co Ltd |
TABLE 3
Example 1
The rubber composition formula comprises: 60 parts of solution polymerized styrene-butadiene rubber, 40 parts of butadiene rubber, 50 parts of white carbon black, 20 parts of carbon black, 10 parts of diethyl maleate (matrix modifier), 17 parts of TDAE (softening agent), 3 parts of PEG4000 (softening agent), 5 parts of zinc oxide (activator), 1 part of stearic acid (activator), 0.5 part of sulfur (vulcanizing agent), 4 parts of TBBS (accelerator), 2 parts of accelerator D (accelerator) and 1 part of antioxidant 4020 (antioxidant).
The preparation process of the vulcanized rubber comprises the following steps:
(1) carrying out first mixing on a rubber matrix and a matrix modifier to obtain a section of master batch; specifically, adding solution polymerized styrene-butadiene rubber and butadiene rubber into an internal mixer, setting the rotating speed to be 80rpm, the plasticating temperature to be 80 ℃, and the raw rubber plasticating time to be 0.5min to obtain a rubber matrix; adding a matrix modifier into the internal mixer for mixing at the mixing temperature of 140 ℃ for 5min to obtain a section of master batch;
(2) carrying out second mixing on the first-stage masterbatch and white carbon black to obtain second-stage masterbatch; specifically, adding the primary masterbatch and white carbon black into an internal mixer for secondary mixing at the mixing temperature of 110 ℃ for 5min to obtain secondary masterbatch;
(3) carrying out third mixing on the second-stage masterbatch, an activating agent, an anti-aging agent, a softening agent and carbon black to obtain third-stage masterbatch; specifically, adding carbon black, TDAE, zinc oxide, stearic acid, an anti-aging agent 4020 and PEG4000 into an internal mixer, carrying out third mixing with the second-stage masterbatch, wherein the mixing time is 3min, the rubber discharge temperature is 110 ℃, discharging and standing for 4 hours to obtain a third-stage masterbatch;
(4) carrying out fourth mixing on the three sections of master batch, an accelerant and a vulcanizing agent to obtain final rubber; specifically, setting the rotation speed of an internal mixer to be 80rpm, plasticating the three sections of master batch to be 40 ℃, adding a vulcanizing agent and an accelerant to carry out fourth mixing after plasticating the three sections of master batch for 1min, wherein the mixing temperature is 130 ℃, the mixing time is 5min, and discharging to obtain final mixed rubber;
(5) 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: 75 parts of solution polymerized styrene-butadiene rubber, 25 parts of butadiene rubber, 77 parts of white carbon black, 8 parts of carbon black, 5 parts of maleic anhydride (matrix modifier), 8 parts of TDAE (softener), 6 parts of PEG4000 (softener), 5 parts of zinc oxide (activator), 3 parts of stearic acid (activator), 1.7 parts of sulfur (vulcanizing agent), 1.7 parts of TBBS (accelerator), 1.9 parts of accelerator D (accelerator) and 2 parts of antioxidant 4020 (antioxidant).
The preparation process of the vulcanized rubber comprises the following steps:
(1) adding solution polymerized styrene-butadiene rubber and butadiene rubber into an internal mixer, setting the rotating speed at 80rpm, the plasticating temperature at 80 ℃ and the raw rubber plasticating time at 0.5min to obtain a rubber matrix; adding a matrix modifier into the internal mixer for mixing at the mixing temperature of 150 ℃ for 7min to obtain a section of master batch;
(2) adding the primary masterbatch and the white carbon black into an internal mixer for secondary mixing, wherein the mixing temperature is 115 ℃, and the mixing time is 6min, so as to obtain secondary masterbatch;
(3) adding carbon black, TDAE, zinc oxide, stearic acid, an anti-aging agent 4020 and PEG4000 into an internal mixer, carrying out third mixing with the second-section masterbatch, wherein the mixing time is 4min, the rubber discharge temperature is 120 ℃, discharging and standing for 4 hours to obtain a third-section masterbatch;
(4) setting the rotation speed of an internal mixer to be 80rpm, plasticating the three sections of master batch at 40 ℃, adding a vulcanizing agent and an accelerant to carry out fourth mixing after plasticating the three sections of master batch for 1min, wherein the mixing temperature is 110 ℃, the mixing time is 7min, and discharging to obtain final mixed rubber;
(5) 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 solution polymerized styrene butadiene rubber, 100 parts of white carbon black, 2.5 parts of maleic anhydride (matrix modifier), 5.5 parts of diethyl maleate (matrix modifier) 4 parts, 8 parts of TDAE (softening agent), 2 parts of PEG4000 (softening agent), 2 parts of zinc oxide (activating agent), 1 part of stearic acid (activating agent), 3 parts of sulfur (vulcanizing agent), 0.5 part of TBBS (accelerating agent), 0.5 part of accelerating agent D (accelerating agent) and 6 parts of anti-aging agent RD (anti-aging agent).
The preparation process of the vulcanized rubber comprises the following steps:
(1) adding solution polymerized styrene-butadiene rubber into an internal mixer, setting the rotating speed at 80rpm, the plasticating temperature at 80 ℃ and the raw rubber plasticating time at 0.5min to obtain a rubber matrix; adding a matrix modifier into the internal mixer for mixing at 145 ℃ for 8min to obtain a section of master batch;
(2) adding the primary masterbatch and the white carbon black into an internal mixer for secondary mixing, wherein the mixing temperature is 120 ℃, and the mixing time is 7min, so as to obtain secondary masterbatch;
(3) adding TDAE, zinc oxide, stearic acid, an anti-aging agent RD and PEG4000 into an internal mixer, carrying out third mixing with the second-stage masterbatch for 5min at the rubber discharge temperature of 130 ℃, discharging and standing for 4 hours to obtain a third-stage masterbatch;
(4) setting the rotation speed of an internal mixer to be 80rpm, plasticating the three sections of master batch at 40 ℃, adding a vulcanizing agent and an accelerant to carry out fourth mixing after plasticating the three sections of master batch for 1min, wherein the mixing temperature is 120 ℃, the mixing time is 6min, and discharging to obtain the final mixed rubber.
(5) 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
The rubber composition formula comprises: 100 parts of solution polymerized styrene butadiene rubber, 100 parts of white carbon black, 8 parts of maleic anhydride (matrix modifier), 14 parts of TDAE (softening agent), 5 parts of PEG4000 (softening agent), 5 parts of zinc oxide (activating agent), 3 parts of stearic acid (activating agent), 3 parts of sulfur (vulcanizing agent), 0.5 part of TMTD (promoter), 0.5 part of promoter D (promoter) and 6 parts of anti-aging agent 4020 (anti-aging agent).
The procedure for the preparation of the vulcanizates was similar to that in example 3, except that:
in the process of preparing the first-stage masterbatch, the temperature of first mixing is 160 ℃, and the time is 10 min;
in the process of preparing the second-stage masterbatch, the temperature of second mixing is 150 ℃ and the time is 9 min;
in the process of preparing the three-section master batch, the third mixing time is 7min, and the rubber discharge temperature is 105 ℃.
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
This example was a rubber composition formulation and process similar to example 1 except that the same parts by weight of maleic acid were used in place of the diethyl maleate in example 1 to prepare a vulcanizate S5, which was otherwise the same as in example 1.
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 was a rubber composition formulation and process similar to example 2 except that the same parts by weight of diisopropyl maleate was used in place of maleic anhydride in example 2 to prepare vulcanized rubber S6, which 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.
Comparative example 1
The formulation of the rubber composition of this comparative example was the same as in example 2, specifically: 75 parts of solution polymerized styrene-butadiene rubber, 25 parts of butadiene rubber, 77 parts of white carbon black, 8 parts of carbon black, 5 parts of maleic anhydride (matrix modifier), 8 parts of TDAE (softening agent), 5 parts of zinc oxide, 3 parts of stearic acid, 1.7 parts of sulfur (vulcanizing agent), 1.7 parts of TBBS (promoter), 1.9 parts of promoter D (promoter), 2 parts of anti-aging agent 4020 (anti-aging agent) and 6 parts of PEG4000 (softening agent).
The preparation process of the vulcanized rubber comprises the following steps:
adding solution polymerized styrene-butadiene rubber into an internal mixer, setting the rotating speed at 80rpm, the plasticating temperature at 80 ℃, and the raw rubber plasticating time at 0.5 min; adding butadiene rubber, white carbon black, a matrix modifier, carbon black, TDAE, zinc oxide, stearic acid, an anti-aging agent 4020 and PEG4000 into an internal mixer for mixing for 10min, discharging at 175 ℃, and standing for 4 hours to prepare master batch;
setting the rotating speed of an internal mixer at 80rpm, setting the initial mixing temperature at 40 ℃, plasticating the master batch for 1min, adding a vulcanizing agent and an accelerant for mixing, setting the mixing temperature at 110 ℃, setting the mixing time at 7min, and discharging to obtain final mixed rubber;
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 DS1 is prepared.
The cured rubber article DS1 was subjected to the performance test, and the results are shown in Table 4.
Comparative example 2
The formulation of the rubber composition of this comparative example was the same as in example 2, specifically: 75 parts of solution polymerized styrene-butadiene rubber, 25 parts of butadiene rubber, 77 parts of white carbon black, 8 parts of carbon black, 5 parts of maleic anhydride (matrix modifier), 8 parts of TDAE (softening agent), 5 parts of zinc oxide, 3 parts of stearic acid, 1.7 parts of sulfur (vulcanizing agent), 1.7 parts of TBBS (promoter), 1.9 parts of promoter D (promoter), 2 parts of anti-aging agent 4020 (anti-aging agent) and 6 parts of PEG4000 (softening agent).
A vulcanized rubber was prepared according to the compounding process of example 1 of CN103881161A, specifically:
a rubber mixing process:
the carbon black masterbatch process comprises the following steps: adding solution polymerized styrene-butadiene rubber into an internal mixer with the rotating speed of 45rpm, plasticating for 60 seconds, then lifting a top plug, adding carbon black, mixing for 60 seconds, then lifting the top plug, cleaning, mixing for 60 seconds, and then discharging rubber; the pressurizing and mixing time is 180 seconds, and the rubber discharging temperature is 165 ℃;
white carbon black masterbatch process: adding solution polymerized styrene-butadiene rubber into an internal mixer with the rotating speed of 45rpm, mixing for 30 seconds, then lifting a top plug, adding butadiene rubber, white carbon black and a matrix modifier, mixing for 60 seconds, then lifting the top plug, mixing for 30 seconds, lifting the top plug, and then mixing for 60 seconds to remove rubber; the pressure mixing time is 210 seconds, and the rubber discharging temperature is 160 ℃.
The two-stage mixing process comprises the following steps:
adding carbon black master batch and white carbon black master batch into an internal mixer with the rotating speed of 40rpm, mixing for 80 seconds, lifting a top bolt, adding zinc oxide, stearic acid, an anti-aging agent 4020, TDAE and PEG4000, mixing for 70 seconds, cleaning, mixing for 30 seconds, discharging rubber, pressurizing and mixing for 180 seconds, and discharging the rubber at the temperature of 155 ℃ to obtain the second-stage mixed master batch.
And (3) final rubber mixing process:
adding two-stage mixing master batch into an internal mixer with the rotation speed of 20rpm, mixing for 30 seconds, lifting a top bolt, adding an accelerant and a vulcanizing agent, mixing for 60 seconds, cleaning, mixing for 30 seconds, and discharging rubber, wherein the pressurizing mixing time is 120 seconds, and the discharging temperature is 105 ℃; and obtaining final rubber compound.
The preparation process of the vulcanized rubber comprises the following steps:
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 DS2 is prepared.
The cured rubber sample DS2 was subjected to performance testing and the results are shown in Table 4.
Comparative example 3
This comparative example was carried out in a similar manner to example 2, except that:
the matrix modifier used in this comparative example was fumaric acid, i.e., the maleic anhydride in example 2 was replaced with this fumaric acid.
The rest is the same as in example 2. A vulcanizate sample DS3 was prepared.
The cured rubber sample DS3 was subjected to performance testing and the results are shown in Table 4.
TABLE 4
From the above results, it can be seen that the use of the process for producing a vulcanized rubber according to the present invention enables better dispersibility of each component for producing a vulcanized rubber in a rubber composition, thereby enabling further improvement in the strength of the resultant vulcanized rubber, reduction in heat generation, and improvement in wet skid resistance.
Further, it can be seen from the results of comparing comparative example 1 and comparative example 2 with example 2 that, when the same rubber composition formulation as in example 2 was employed but a different vulcanized rubber production process was employed, the vulcanized rubbers DS1 and DS2 obtained in comparative example 1 and comparative example 2, respectively, were inferior in properties to the vulcanized rubber S2 obtained in example 2, specifically, the vulcanized rubbers DS1 and DS2 of comparative example 1 and comparative example 2 were lower in tear strength than S2, higher in compression temperature than S2, lower in rebound resilience than S2, and higher in DIN abrasion than S2; the dynamic mechanical properties of the vulcanizate S2 prepared in example 2 showed less rolling resistance and better wet skid resistance, and the Peltier effect data also show that the dispersion of carbon black in the vulcanizate S2 prepared in example 2 is better than the vulcanizates of comparative examples 1 and 2.
The preparation method provided by the invention can enable the obtained vulcanized rubber to have better performance, so that when the vulcanized rubber is applied to the tread of an automobile tire, the durability of the tire can be improved, the fuel economy of the automobile can be improved, and the safety of the automobile can be improved.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (24)
1. A method of preparing a vulcanized rubber, the method comprising:
(1) carrying out first mixing on a rubber matrix and a matrix modifier to obtain a section of master batch;
(2) carrying out second mixing on the first-stage masterbatch and white carbon black to obtain second-stage masterbatch;
(3) carrying out third mixing on the second-stage masterbatch, an activating agent, an anti-aging agent, a softening agent and optional carbon black to obtain third-stage masterbatch;
(4) carrying out fourth mixing on the three sections of master batch, an accelerant and a vulcanizing agent to obtain final rubber;
(5) vulcanizing the final rubber;
wherein the matrix modifier is a maleic acid monomer, the maleic acid monomer is at least one selected from the group consisting of maleic acid, maleic anhydride and dialkyl maleate, and the number of carbons of an alkyl group in the dialkyl maleate is 1 to 6.
2. The method according to claim 1, wherein the maleic acid-based monomer is at least one selected from the group consisting of maleic acid, maleic anhydride, dimethyl maleate, diethyl maleate, dibutyl maleate, dipropyl maleate and diisopropyl maleate.
3. The method according to claim 1 or 2, wherein the matrix modifier is used in an amount of 2 to 20 parts by weight with respect to 100 parts by weight of the rubber matrix.
4. The method according to claim 1 or 2, wherein the matrix modifier is used in an amount of 5 to 10 parts by weight with respect to 100 parts by weight of the rubber matrix.
5. The method according to claim 1 or 2, wherein the white carbon is used in an amount of 20 to 120 parts by weight, the activator is used in an amount of 1 to 15 parts by weight, the anti-aging agent is used in an amount of 0.5 to 10 parts by weight, the softener is used in an amount of 5 to 30 parts by weight, the carbon black is used in an amount of 0 to 30 parts by weight, the accelerator is used in an amount of 0.5 to 10 parts by weight, and the vulcanizing agent is used in an amount of 0.1 to 5 parts by weight, relative to 100 parts by weight of the rubber matrix.
6. The method according to claim 5, wherein the white carbon black is used in an amount of 50 to 100 parts by weight, the activator is used in an amount of 3 to 8 parts by weight, the antioxidant is used in an amount of 1 to 6 parts by weight, the softener is used in an amount of 10 to 20 parts by weight, the carbon black is used in an amount of 0 to 20 parts by weight, the accelerator is used in an amount of 1 to 6 parts by weight, and the vulcanizing agent is used in an amount of 0.5 to 3 parts by weight, relative to 100 parts by weight of the rubber matrix.
7. The method of claim 1 or 2, wherein the rubber matrix is selected from at least one of solution-polymerized styrene-butadiene rubber, and natural rubber.
8. The method according to claim 7, wherein the solution-polymerized styrene-butadiene rubber has a styrene structural unit content of 15 to 30 mass%, a vinyl group content of 35 to 70 mass%, an oil-containing component of 0 to 30 mass%, and a Mooney viscosity of 45 to 70;
the cis content in the butadiene rubber is 90 to 99 mass%.
9. The method of claim 1 or 2, wherein the rubber matrix is solution polymerized styrene butadiene rubber or a mixture of solution polymerized styrene butadiene rubber and butadiene rubber; relative to 100 parts by weight of the rubber matrix, the amount of the solution polymerized styrene-butadiene rubber in the rubber matrix is 60-100 parts by weight, and the amount of the butadiene rubber is 0-40 parts by weight.
10. A method according to claim 1 or 2, wherein the conditions of the first mixing comprise: the temperature is 130-170 ℃ and the time is 3-10 min.
11. The method of claim 10, wherein the conditions of the first mixing comprise: the temperature is 140 ℃ and 150 ℃, and the time is 5-8 min.
12. The method of claim 1 or 2, wherein the conditions of the second mixing comprise: the temperature is 100 ℃ and 150 ℃, and the time is 3-10 min.
13. The method of claim 12, wherein the conditions of the second mixing comprise: the temperature is 110-120 ℃, and the time is 5-7 min.
14. The method of claim 1 or 2, wherein the conditions of the third mixing comprise: the temperature is 80-140 deg.C, and the time is 3-12 min.
15. The method of claim 14, wherein the conditions of the third mixing comprise: the temperature is 110 ℃ and 130 ℃, and the time is 3-5 min.
16. The method of claim 1 or 2, wherein the conditions of the fourth mixing comprise: the temperature is not more than 130 deg.C, and the time is 5-7 min.
17. The process according to claim 1 or 2, wherein the conditions of the vulcanization comprise: the temperature is 150 ℃ and 170 ℃, the pressure is 10-20MPa, and the time is 30-50 min.
18. The method according to claim 1 or 2, wherein the silica has a nitrogen adsorption specific surface area of 10 to 200m2(ii)/g; the carbon black has a CTAB adsorption specific surface area of 10-300m2/g。
19. The method according to claim 1 or 2, wherein the antioxidant is at least one of an amine antioxidant, a quinoline antioxidant, and a benzimidazole antioxidant.
20. The method according to claim 1 or 2, wherein the softening agent is at least one of aromatic oil, paraffin oil, naphthenic oil, petroleum resin, and polyethylene glycol.
21. A process according to claim 1 or 2, wherein the activator is a combination of a metal oxide and a fatty acid or a fatty acid metal soap salt.
22. A process according to claim 1 or 2, wherein the accelerator is at least one of a sulfenamide accelerator, a thiazole accelerator, a thiuram accelerator and a guanidine accelerator.
23. The method according to claim 1 or 2, wherein the vulcanizing agent is sulphur and/or a sulphur donor.
24. A vulcanized rubber produced by the process of any one of claims 1-23.
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| CN110551236A (en) * | 2018-05-30 | 2019-12-10 | 中国石油化工股份有限公司 | Modified styrene-butadiene rubber and preparation method thereof, rubber composition, vulcanized rubber and preparation method and application thereof |
| CN110551239A (en) * | 2018-06-01 | 2019-12-10 | 中国石油化工股份有限公司 | modified styrene-butadiene rubber and preparation method thereof, rubber composition, vulcanized rubber and preparation method and application thereof |
| CN110551237A (en) * | 2018-06-01 | 2019-12-10 | 中国石油化工股份有限公司 | modified styrene-butadiene rubber and preparation method thereof, rubber composition, vulcanized rubber and preparation method and application thereof |
| CN110564020A (en) * | 2018-06-05 | 2019-12-13 | 中国石油化工股份有限公司 | modified main rubber and preparation method thereof, rubber composition, vulcanized rubber and preparation method and application thereof |
| CN110484165B (en) * | 2019-07-18 | 2021-09-24 | 南京利德东方橡塑科技有限公司 | High-temperature-resistant and low-temperature-resistant environment-friendly chloroprene rubber adhesive and preparation method thereof |
| CN112239573B (en) * | 2019-07-19 | 2022-08-19 | 中国石油化工股份有限公司 | Rubber composition for wear-resistant sole, vulcanized rubber, and preparation method and application thereof |
| CN114149627B (en) * | 2020-09-07 | 2023-05-12 | 中国石油化工股份有限公司 | Rubber composition for light tire tread, application of rubber composition, vulcanized rubber, preparation method of vulcanized rubber and application of vulcanized rubber |
| CN114149623B (en) * | 2020-09-07 | 2023-05-12 | 中国石油化工股份有限公司 | Rubber composition for shoe soles and application thereof, vulcanized rubber and preparation method and application thereof |
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