CN115772331A - Rubber processing aid and preparation method thereof and tire rubber composition - Google Patents
Rubber processing aid and preparation method thereof and tire rubber composition Download PDFInfo
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Abstract
The invention discloses a rubber processing aid, a preparation method thereof and a tire rubber composition. The preparation method of the rubber processing aid obtains the block polymer by continuous dynamic coupling reaction of rubber compounds with different functional groups, realizes different functionalized rubber combinations, and prepares the rubber processing aid. When the rubber processing aid is compounded with rubber for use, the compatibility and the bonding force of polymer-polymer and rubber-filler of the rubber can be improved, so that the interface looseness of the polymer-polymer and polymer-filler is effectively reduced, the interface acting force is enhanced, the stability of a filler network and a polymer dispersion system is improved, and the performance of a target rubber product is improved. The tire rubber composition disclosed by the invention contains rubber and the rubber processing aid in a compounding manner, has the advantages of uniform rubber dispersion, strong filler binding force, good processing performance, high strength and the like, and can reduce the rolling resistance of a tire when being applied to an automobile tire.
Description
Technical Field
The invention relates to the technical field of tire rubber, in particular to a rubber processing aid, a preparation method thereof and a tire rubber composition.
Background
The new energy automobile uses the battery as a power source and has the advantages of energy conservation, environmental protection and the like. However, due to reasons such as battery energy storage density, the cruising ability is a main factor restricting the development of the new energy automobile industry, and the improvement of the cruising ability of the new energy automobile is beneficial to the development of the new energy automobile industry. During the running of the automobile, energy is consumed by various resistances, and the rolling resistance of the tire, which is the only ground-contacting part of the automobile, consumes about 20% of power. The energy consumption in this respect can be reduced by using green tyres, which increase the endurance mileage of the vehicle, and the rolling resistance can be reduced by 22-35% compared with tyres of the same specification, and thus the fuel consumption of the vehicle can be reduced by 3-8%. Similarly, the green low-rolling-resistance tire can reduce the power consumption of the new energy automobile battery and promote the development of the new energy automobile industry.
As the only part contacting the ground of an automobile, the tire is mainly prepared by compounding rubber, fiber and other materials, the rolling resistance of the tire mainly comes from energy loss caused by tire deformation, and the principle of the tire is rubber entanglement network slippage deformation, imperfect network (suspension chain) relaxation and filler network damage. The reduction of the rolling resistance of rubber composites requires a reduction in the losses of rubber or rubber mixtures (loss of bulk chain motion and interfacial losses) and an increase in the dispersion of fillers to reduce the energy consumption caused by network damage.
At present, the low rolling resistance tire is mainly prepared by a rubber/white carbon black composite material and combining rubber and a filler through a silanization reaction. Although the technology increases the combination effect of the polymer and the filler and improves the rolling resistance of the tire to a certain extent, the polymer generally uses composite rubber, the compatibility among different polymers is poor, the binding force is weak, and the relaxation loss of the rubber is not improved; in addition, white carbon black is required to be used in the system, the silanization reaction process requirement is high, the processing is difficult, and the batch uniformity of the product is poor.
The binding force between rubber and filler can be improved through rubber functionalization reaction, such as a terminal modified SSBR (solution polymerized styrene butadiene rubber) material, but the rubber has larger molecular weight, and the functionalized material has high binding glue content, so that the viscosity of a rubber system is overlarge, the later molding processing is difficult, and the application and development of the functionalized rubber are seriously limited. And the above method merely increases the interaction between the polymer and the filler, and cannot increase the polymer-polymer or polymer-filler binding force at the same time, resulting in that the material properties cannot be optimized.
Disclosure of Invention
The invention aims to solve the problems that polymers in a low rolling resistance tire manufactured by a traditional preparation method have poor compatibility, weak bonding force and poor filler dispersibility, the bonding force of polymer-polymer and polymer-filler cannot be increased simultaneously through rubber functionalization, and the rubber processing aid is difficult to mold and process. The rubber processing aid can be used in the preparation of tire rubber compositions, is used in a composite way with rubber, and improves the compatibility and the bonding force between polymers in the rubber and between the polymers and fillers.
The invention also aims to provide a preparation method of the rubber processing aid, the method can prepare the rubber processing aid which has excellent performance and can effectively improve the compatibility and the bonding force between polymers and between polymer and filler in the rubber composition, and the prepared rubber processing aid is convenient to use.
The invention also aims to provide a tire rubber composition which is prepared by adopting the rubber processing aid, has high compatibility and bonding force among polymers and between the polymers and fillers in the rubber composition, and has excellent mechanical property.
The purpose of the invention is realized by the following technical scheme.
A preparation method of a rubber processing aid comprises the following steps: carrying out banburying mixing on the polymer I and the polymer II for 3-10 minutes at 120-180 ℃ by using a banbury mixer, uniformly mixing the obtained reaction product with the polymer III, the antioxidant and the lubricant, and carrying out extrusion granulation by using a double-screw extruder to obtain the rubber processing aid;
the polymer I is a maleic anhydride or epoxy group graft modified monofunctional or polyfunctional polymer compound; the polymer II is a monofunctional high molecular compound with hydroxyl, amino or carboxyl graft modification; the polymer III is polymer resin or thermoplastic elastomer.
In a preferred embodiment, the raw materials comprise the following components in parts by weight: 30-60 parts of polymer I, 30-60 parts of polymer II, 0-30 parts of polymer III, 0.1-0.5 part of antioxidant and 0.3-3 parts of lubricant.
In preferred embodiments, the polymer I comprises maleic anhydride grafted ethylene propylene rubber, epoxy modified 1,2-polymerized butadiene, epoxidized natural rubber or epoxidized modified butyl rubber.
In a preferred embodiment, the polymer II comprises a terminal carboxyl-modified styrene-butadiene rubber, a terminal amino-modified butadiene rubber or a terminal hydroxyl-modified styrene-butadiene rubber.
In a preferred embodiment, the polymer I and the polymer II are mixed and kneaded homogeneously at 150 ℃.
In a preferred embodiment, the polymer iii comprises a polyethylene resin or a styrenic thermoplastic elastomer (SBS).
In a preferred embodiment, the antioxidant is one or more of a hindered phenol antioxidant, a hindered amine antioxidant, and a phosphite antioxidant.
In a preferred embodiment, the lubricant is one or more of polyethylene wax, polypropylene wax, oxidized paraffin wax, calcium stearate, barium stearate and zinc stearate.
In a preferred embodiment, the molar ratio of the functionalized groups of said polymer I and said polymer II is between 0.5 and 2:1.
in a preferred embodiment, said polymer i and said polymer ii have a mooney viscosity of less than 5MU.
In a preferred embodiment, the rubber processing aid of any one of the above items, in terms of mass percentage of the rubber processing aid, further includes: 0.5 to 3 percent of separant; the obtained rubber processing aid and the separant are uniformly mixed to prevent adhesion, so that the rubber processing aid is convenient to use.
In a further preferred embodiment, the isolating agent accounts for 1-3% of the rubber processing aid by mass.
In a further preferred embodiment, the release agent is mineral powder, including talc powder or nano calcium carbonate.
A rubber processing aid prepared by any one of the above methods.
A rubber composition for a tire comprising a rubber and the rubber processing aid of any of the above.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the preparation method of the rubber processing aid disclosed by the invention has the advantages that the rubber with different functional groups is coupled through continuous dynamic coupling reaction to obtain the block polymer, different blocks of the polymer and different rubbers have good affinity and molecular entanglement, the block polymer is dispersed on interfaces of different types of rubbers in the processing process, the rubber dispersion is accelerated under the action of shearing force, and the block polymer has the effect of stabilizing the interfaces and generates smaller rubber dispersion size. Thereby obtaining the rubber processing aid capable of enhancing the compatibility and the bonding force among polymers in the rubber and between the polymers and the filler.
The rubber processing aid is a granular mixture prepared by the method, has the characteristics of convenience in use, excellent performance and the like, and can improve the compatibility and the bonding force of a polymer-polymer and a rubber-filler of rubber when a small amount of the rubber processing aid is added and compounded with rubber for use, so that the relaxation of polymer-polymer and polymer-filler interfaces is effectively reduced, the interface acting force is enhanced, the stability of a filler network and a polymer dispersion system is improved, and the performance of a target rubber product is improved.
The tire rubber composition disclosed by the invention contains rubber and the rubber processing aid in a compounding manner, has the advantages of uniform rubber dispersion, strong filler binding force, good processing performance, high strength and the like, and can reduce the rolling resistance of the tire when being applied to the automobile tire so as to further reduce the energy consumption.
Drawings
FIG. 1 is a flow chart illustrating the preparation of a rubber processing aid according to the present invention in a specific example;
FIG. 2 is a schematic diagram of the terminal graft coupling between the functionalized groups of Polymer I and Polymer II;
FIG. 3 is a schematic diagram of the side-chain graft coupling between the functionalized groups of Polymer I and Polymer II.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following specific examples, but the scope and implementation of the present invention are not limited thereto. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Also, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
It should be understood that as used herein, singular forms, such as "a", "an", include plural references unless the context clearly dictates otherwise. Furthermore, the terms "comprising," "including," and "having" are intended to be open-ended, i.e., to include but not exclude the presence of other elements as well as certain aspects of the invention. In other words, the term also includes "consisting essentially of …," or "consisting of ….
In addition, "and a combination thereof" in the specification refers to any combination of all items listed. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as is standard in the art to which the claimed subject matter belongs. In case there are multiple definitions for a term, the definitions herein control.
Unless otherwise indicated, the present invention employs standard nomenclature for analytical chemistry, organic synthetic chemistry, and optics, and standard laboratory procedures and techniques.
The above preferred conditions can be arbitrarily combined to obtain preferred embodiments of the present invention without departing from the common general knowledge in the art.
The technical solution of the present invention is described in detail below with reference to specific examples.
In the following specific examples, some of the raw materials and sources thereof specifically used are as follows:
maleic anhydride-grafted ethylene-propylene rubber, alvarez (brazil) ltd, no. keltan 0500R, mooney viscosity 5MU.
Maleic anhydride-grafted ethylene-propylene rubber, allan New Co., ltd (Brazil), under the designation keltan1500R, mooney viscosity of 15MU.
The maleic anhydride modified 1,2-polymerized butadiene, self-made, the Mooney viscosity is 4.0MU.
The terminal amino modified styrene butadiene rubber is self-made, and the Mooney viscosity is 4.8MU.
The terminal epoxy modified styrene butadiene rubber is self-made, and the Mooney viscosity is 4.5MU.
KH-550, JUSICA CHEMICAL CO., hangzhou.
Silane coupling agent A-187, miyao high-tech materials group.
1,2-polymerized butadiene, JSR, japan, trade name RB-840, mooney viscosity of 4.7MU.
Styrene-based thermoplastic elastomer (SBS), koteng Polymer Co., ltd. D1164, mooney viscosity MFR 12 g/10min.
Antioxidant, basf (china) ltd, antioxidant 1010, antioxidant 168.
Lubricants, friendly and auxiliaries ltd, calcium stearate.
Talc powder, liaoning Ai Hai Talc Co., ltd., mark AHCP-250.
Nano calcium carbonate, trade of english porcelain (shanghai) ltd, trade mark Imercarb 130.
Natural rubber, malaysia SMR5.
Styrene butadiene rubber, aluraniki ltd, under the designation Buna SE1500, mooney viscosity 52MU.
Ethylene propylene diene monomer, achromenib chemical Co., ltd., EPDM 4608, mooney viscosity 62MU.
Chlorinated butyl rubber, alvarnetic, ltd, under the designation CIIR 1240, mooney viscosity 38MU.
Carbon black, cabot (china) investment limited, under the designation N660.
Accelerator, shandong Shanshun chemical Co., ltd., trade name DM.
Vulcanizing agent, guangzhou Qia developing chemicals, inc., under the designation VULTAC5.
The maleic anhydride modified 1,2-polymerized butadiene, the terminal amino modified butadiene rubber, the terminal hydroxyl modified butadiene styrene rubber and the like are laboratory products, and the preparation method comprises the following steps:
1. the preparation method of the maleic anhydride modified 1,2-polymerized butadiene comprises the following steps: selecting JSR product RB840, performing extrusion reaction on the JSR product RB840, 1wt% of maleic anhydride and 0.1wt% of DCP (dicumyl peroxide) at 160 ℃ by using a double-screw extruder under the vacuum conditions of 400rpm and-0.09 MPa, and then cooling and dicing to obtain the maleic anhydride modified 1,2-polymerized butadiene.
2. Polymers such as terminal carboxyl modified styrene butadiene rubber, terminal hydroxyl modified styrene butadiene rubber and the like are prepared by polymerization in the laboratory, and the process is as follows: using n-butyl lithium (1 g) as an initiator, adjusting the material temperature to 30-40 ℃ under the condition of anion initiation reaction, contacting 200g of styrene and 600g of butadiene in 4000g of solvent S (wherein the mass percentages of toluene and tetrahydrofuran are 85wt% and 15wt% in sequence) with 50g of n-butyl lithium hexane solution (the mass percentage of n-butyl lithium is 5 wt%), carrying out initiation reaction, keeping the kettle pressure at 0.4MPa, stirring at the speed of 100rpm, keeping the temperature to 60-80 ℃, and carrying out polymerization reaction for 2 hours to obtain the solution of linear solution polymerized styrene-butadiene rubber. The reaction was terminated after 30 minutes of adding hexamethylcyclotrisiloxane. Then 4g of silane coupling agent KH-550 and 4g of silane coupling agent A-187 are respectively added to react for 30 minutes at 40 ℃, and the styrene-butadiene rubber with modified amino at the tail end and the styrene-butadiene rubber with modified epoxy at the tail end can be respectively obtained.
In a specific embodiment, the process of the preparation method of the rubber processing aid provided by the invention is shown in fig. 1, and comprises the following steps:
s1, mixing a polymer I and a polymer II uniformly at 150 ℃ for 5-10 minutes by using an internal mixer to obtain a block polymer with grafted and modified tail end or branched side chain;
wherein, the reaction principle of the end graft coupling is shown in figure 2, the end of the polymer I and the front end of the polymer II are graft-modified to obtain the end graft-modified block polymer; the reaction principle of side chain branching coupling is shown in figure 3, and the side chain of the polymer I is grafted and coupled with the polymer II to obtain the side chain branched block polymer.
S2, uniformly mixing the obtained block polymer with the polymer III, the antioxidant and the lubricant, and extruding and granulating by using a double-screw extruder to obtain corresponding rubber processing aid polymer particles.
In the preferred embodiment, the raw materials comprise the following components in parts by weight: 30-60 parts of polymer I, 30-60 parts of polymer II, 0-30 parts of polymer III, 0.1-0.5 part of antioxidant and 0.3-3 parts of lubricant.
And S3, uniformly mixing the rubber processing aid polymer particles of S2 with 0.5-3% of a release agent to prevent the particles from being bonded, and obtaining a final product which is convenient to use.
The raw material compositions of the rubber processing aids of examples 1-6 are shown in Table 1 below.
TABLE 1 raw Material compositions (parts by weight, PHR) of the rubber processing aids of examples 1-6
| Starting materials | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| Maleic anhydride grafted ethylene-propylene rubber (keltan 0500R) | 45 | 45 | 40 | 30 | ||
| Maleic anhydride modified 1,2-polymerized butadiene | 60 | 40 | ||||
| Terminal amino modified styrene-butadiene rubber | 40 | 35 | 40 | |||
| Terminal epoxy modified styrene-butadiene rubber | 30 | 40 | 60 | |||
| 1,2-polymerization of butadiene (RB-840) | 20 | 30 | ||||
| Styrene thermoplastic elastomer (SBS) | 25 | 20 | ||||
| Antioxidant 1010 | 0.1 | 0.05 | 0.3 | 0.1 | 0.2 | 0.15 |
| Antioxidant 168 | 0.1 | 0.05 | 0.2 | 0.2 | 0.3 | 0.2 |
| Lubricant (calcium stearate) | 0.5 | 0.3 | 1 | 3 | 2 | 0.5 |
Example 1:
the rubber processing aid of this example was prepared by the following steps:
according to the raw material composition of the rubber processing aid of example 1 in table 1, maleic anhydride-modified 1,2-polymerized butadiene and terminal amino-modified styrene-butadiene rubber (molar ratio of maleic anhydride functional group to amino functional group is 1:2) were mixed by an internal mixer at 120 ℃ for 5 minutes, and then an antioxidant and a lubricant were added, and extrusion granulation was performed using a twin-screw extruder; the polymer particles obtained by granulation were uniformly mixed with 0.5% talc to prevent the polymer from sticking, and the rubber processing aid of the present example was obtained.
Example 2:
the rubber processing aid of this example was prepared by the following steps:
according to the raw material composition of the rubber processing aid in example 2 in table 1, maleic anhydride grafted ethylene propylene rubber and terminal epoxy modified styrene-butadiene rubber (the molar ratio of maleic anhydride functional groups to epoxy functional groups is 2:1) are mixed by an internal mixer at 180 ℃ for 3 minutes, added with SBS and mixed uniformly, then added with antioxidant and lubricant and extruded by an extruder for granulation; the polymer particles obtained by granulation were uniformly mixed with 1% of nano calcium carbonate to prevent the polymer from sticking, and the rubber processing aid of the present example was obtained.
Example 3
The rubber processing aid of this example was prepared by the following steps:
according to the raw material composition of the rubber processing aid in example 3 in table 1, maleic anhydride grafted ethylene propylene rubber and terminal amino modified styrene-butadiene rubber (the molar ratio of maleic anhydride functional groups to amino functional groups is 1.5; the polymer particles obtained by granulation and 2% of nano calcium carbonate are uniformly mixed to prevent the polymer from bonding, and the rubber processing aid of the embodiment can be obtained.
Example 4
The rubber processing aid of this example was prepared by the following steps:
according to the raw material composition of the rubber processing aid of example 4 in table 1, maleic anhydride grafted ethylene propylene rubber and terminal epoxy modified styrene-butadiene rubber (the molar ratio of maleic anhydride functional groups to epoxy functional groups is 1.5) are mixed by an internal mixer at 160 ℃ for 5 minutes, then low-density polyethylene is added and mixed uniformly, and then antioxidant and lubricant are added and extrusion granulation is carried out by an extruder; the polymer particles obtained by granulation were uniformly mixed with 2% talc to prevent the polymer from sticking, and the rubber processing aid of the present example was obtained.
Example 5
The rubber processing aid of this example was prepared by the following steps:
according to the raw material composition of the rubber processing aid in example 5 in table 1, maleic anhydride grafted ethylene propylene rubber and terminal amino modified styrene-butadiene rubber (molar ratio of maleic anhydride functional group to amino functional group is 1:1) are mixed by an internal mixer at 150 ℃ for 8 minutes, then low-density polyethylene is added and mixed uniformly, and then antioxidant and lubricant are added and extrusion granulation is carried out by an extruder; the polymer particles obtained by granulation were uniformly mixed with 3% talc to prevent the polymer from sticking, and the rubber processing aid of the present example was obtained.
Example 6
The rubber processing aid of this example was prepared by the following steps:
according to the raw material composition of the rubber processing aid of example 6 in table 1, maleic anhydride modified 1,2-polymerized butadiene and terminal epoxy modified styrene-butadiene rubber (molar ratio of maleic anhydride functional group to epoxy functional group is 1:1) were mixed by an internal mixer at 150 ℃ for 5 minutes, and then antioxidant and lubricant were added and extrusion granulation was performed using a twin-screw extruder; the polymer particles obtained by granulation were uniformly mixed with 0.5% talc to prevent the polymer from sticking, and the rubber processing aid of the present example was obtained.
Comparative example 1
According to the formula requirement of example 1 in Table 1, maleic anhydride epoxy modified 1,2-polymerized butadiene and terminal amino modified butadiene styrene rubber (the molar ratio of epoxy maleic anhydride functional group to amino functional group is 1:2) are mixed for 5 minutes at 100 ℃ by an internal mixer, then the rest auxiliary agents are added, and a double-screw extruder is used for extrusion granulation; the polymer particles obtained by granulation and 0.5% of talcum powder are mixed uniformly to prevent the polymer from bonding, thus obtaining the rubber processing aid of the comparative example.
Comparative example 2
The rubber processing aid of this example was prepared by the following steps:
according to the formula requirements of example 2 in table 1, maleic anhydride grafted ethylene propylene rubber and terminal epoxy carboxyl modified butadiene styrene rubber (the molar ratio of epoxy maleic anhydride functional group to carboxyl epoxy functional group is 3:1) are mixed by an internal mixer at 180 ℃ for 3 minutes, then SBS is added and mixed uniformly, then the rest of auxiliary agents are added and extruded by an extruder for granulation; the polymer particles obtained by granulation and 1% of nano calcium carbonate are uniformly mixed to prevent the polymer from bonding, thus obtaining the rubber processing aid of the comparative example.
Comparative example 3
The rubber processing aid of this example was prepared by the following steps:
according to the raw material composition of the rubber processing aid in example 3 in table 1, maleic anhydride grafted ethylene propylene rubber and terminal amino modified styrene-butadiene rubber (the molar ratio of maleic anhydride functional groups to amino functional groups is 0.3; the polymer particles obtained by granulation and 2% of nano calcium carbonate are uniformly mixed to prevent the polymer from bonding, thus obtaining the rubber processing aid of the comparative example.
Comparative example 4
The rubber processing aid of this comparative example was prepared according to the raw material composition of example 3 in table 1, in which the maleic anhydride grafted ethylene-propylene rubber keltan 0500R was replaced with the same amount of maleic anhydride grafted ethylene-propylene rubber keltan1500R, and using the same process as example 3.
Comparative example 5
According to the raw material composition of the rubber processing aid of example 6 in table 1, wherein the ratio of polymer i and polymer ii was adjusted, 20 parts of maleic anhydride-modified 1,2-polymerized butadiene and 80 parts of terminal epoxy-modified styrene-butadiene rubber (molar ratio of maleic anhydride functional group to epoxy functional group was 1:1) were mixed by an internal mixer at 150 ℃ for 5 minutes, and then an antioxidant and a lubricant were added, and extrusion granulation was performed using a twin-screw extruder; the polymer particles obtained by granulation and 0.5% of talc powder are uniformly mixed to prevent the polymer from bonding, and the rubber processing aid of the comparative example can be obtained.
1. Preparation of tire sidewall rubber
The raw materials comprise: 5 parts of natural rubber SMR, 1500 parts of butadiene styrene rubber Buna SE, 30 parts of ethylene propylene diene monomer EPDM 4608 parts, 1240 parts of chlorinated butyl rubber CIIR, 3 parts of zinc oxide, 2 parts of stearic acid, 60 parts of carbon black N660, 30 parts of paraffin oil, 0.8 part of accelerator DM, 0.8 part of sulfur, 1.5 parts of vulcanizing agent VULTAC and 10 parts of rubber processing aid.
The preparation method comprises the following steps: butadiene styrene rubber Buna SE1500, ethylene propylene diene monomer EPDM 4608 and rubber processing aid are added into an internal mixer together, mixed for 1 minute at 60rpm and 60 ℃, then added with natural rubber SMR5 and chlorinated butyl rubber CIIR 1240, and mixed for 3 minutes. Then adding half of the carbon black N660 and half of the paraffin oil, mixing for 30s, adding the rest carbon black N660 and paraffin oil, stearic acid and zinc oxide, continuously mixing for 3 minutes, and discharging. Then an open mill is used, and the accelerator DM, the sulfur and the vulcanizing agent are added and uniformly mixed to obtain the required rubber composite material.
Wherein, the rubber processing aids of examples 1-6 and comparative examples 1-5 are respectively adopted to correspondingly prepare corresponding tire side wall rubber products.
Further, a blank comparative example 6 was provided, and no rubber processing aid was added to the tire side rubber of the blank comparative example 6.
2. Tire sidewall rubber Performance testing
Tire side rubbers prepared using the respective rubber processing aids of examples 1 to 6 and comparative examples 1 to 6 were subjected to performance tests including filler dispersion grade (reference GB/T6030), tear strength (unit MPa, reference GB/T529), 60 ℃ loss factor (reference ISO 4664), flexural strength (reference GB/T13934) and heat generation temperature (reference GB/T1687), and the test results are shown in Table 2.
TABLE 2 results of testing the properties of tire sidewall rubbers prepared using the rubber processing aids of examples 1-6 and comparative examples 1-6
| Test sample | Filler dispersion grade | Tear Strength (MPa) | Loss factor at 60 DEG C | Flex strength (thousands times) | Heat Generation temperature (. Degree. C.) |
| Example 1 | Grade 9 | 26.8 | 0.189 | 160 | 20.8 |
| Example 2 | Grade 9 | 24.5 | 0.178 | 184 | 20.6 |
| Example 3 | Grade 9 | 25 | 0.171 | 180 | 20.2 |
| Example 4 | Stage 8 | 23.8 | 0.182 | 175 | 20.1 |
| Example 5 | Stage 8 | 26.5 | 0.192 | 172 | 21.2 |
| Example 6 | Grade 9 | 25.8 | 0.191 | 175 | 20.6 |
| Comparative example 1 | Grade 5 | 19.8 | 0.208 | 120 | 24.1 |
| Comparative example 2 | Stage 7 | 20.1 | 0.205 | 100 | 26.5 |
| Comparative example 3 | Grade 6 | 18.7 | 0.215 | 110 | 24.7 |
| Comparative example 4 | Grade 6 | 21.1 | 0.201 | 130 | 23.6 |
| Comparative example 5 | 7.5 grade | 21.8 | 0.199 | 130 | 23.4 |
| Comparative example 6 | Stage 7 | 18 | 0.225 | 95 | 26.2 |
From the test results in table 2, it can be seen that, compared with the tire side wall rubber prepared by using the rubber composite additive obtained by adopting other preparation process conditions based on the comparative examples 1-2 and the other rubber processing additives of the comparative examples 3-6, the rubber composite additive obtained by the preparation process of the invention based on the examples 1-6 can greatly improve the filler dispersion degree of the tire side wall rubber produced by processing, from 6-7 level to 8-9 level, and simultaneously improve the tear strength and fatigue resistance, reduce the loss factor and the heat generated by compression, so that the tire side wall rubber material produced by corresponding processing has better comprehensive performance.
All the technical features of the above embodiments can be arbitrarily combined, and for the sake of brevity, all the possible combinations of the technical features in the above embodiments are not described in this specification. However, as long as there is no contradiction between combinations of these technical features, the scope of the present specification should be considered as being described. Furthermore, the above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention.
It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The preparation method of the rubber processing aid is characterized by comprising the following steps of:
banburying and mixing the polymer I and the polymer II at 120-180 ℃ for 3-10 minutes, uniformly mixing the obtained reaction product, the polymer III, the antioxidant and the lubricant, extruding and granulating, and uniformly mixing the obtained reaction product with the separant to obtain the rubber processing aid;
the rubber processing aid comprises the following raw material components in parts by weight: 30-60 parts of polymer I, 30-60 parts of polymer II, 0-30 parts of polymer III, 0.1-0.5 part of antioxidant and 0.3-3 parts of lubricant;
the polymer I is a maleic anhydride or epoxy group graft modified monofunctional or polyfunctional compound; the polymer II is a monofunctional compound with hydroxyl, amino or carboxyl graft modification; the polymer III is polymer resin or thermoplastic elastomer.
2. The method of claim 1, wherein said polymer i comprises a maleic anhydride grafted ethylene propylene rubber or an epoxy modified 1,2-polymerized butadiene rubber.
3. The method of claim 1, wherein the polymer II comprises a terminal carboxyl-modified styrene-butadiene rubber, a terminal amino-modified butadiene rubber, or a terminal hydroxyl-modified styrene-butadiene rubber.
4. The method of claim 1, wherein polymer iii comprises a polyethylene resin or a styrenic thermoplastic elastomer.
5. The method of claim 1, wherein the antioxidant is one or more of a hindered phenol antioxidant, a hindered amine antioxidant, and a phosphite antioxidant;
and/or the lubricant is one or more of polyethylene wax, polypropylene wax, oxidized paraffin wax, calcium stearate, barium stearate and zinc stearate.
6. The method of claim 1, wherein the molar ratio of the functionalized groups of polymer i to polymer ii is from 0.5 to 2:1.
7. the method of claim 1, wherein said polymer I and said polymer II have Mooney viscosities of less than 5MU.
8. The method for preparing a rubber processing aid according to any one of claims 1 to 7, further comprising, in mass percent based on the rubber processing aid: 0.5 to 3 percent of separant; uniformly mixing the obtained rubber processing aid and the separant;
the separant is mineral powder and comprises talcum powder or nano calcium carbonate.
9. A rubber processing aid prepared by the method of any one of claims 1 to 8.
10. A tire rubber composition comprising a rubber and the rubber processing aid according to claim 9.
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| CN202310104515.5A CN115772331B (en) | 2023-02-13 | 2023-02-13 | Rubber processing aid, preparation method thereof and tire rubber composition |
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| CN1465614A (en) * | 2002-06-11 | 2004-01-07 | 毅 邵 | Composite polyolefine thermoplastic vulcanizate |
| US20100308495A1 (en) * | 2009-06-05 | 2010-12-09 | Pillai Chandrasekaran R | Process for the manufacture of reactive rubber process aids |
| CN108003540A (en) * | 2017-12-19 | 2018-05-08 | 江苏通用科技股份有限公司 | Improve ethylene propylene diene rubber and the composite material of chlorinated polyethylene rubber compatibility and preparation method thereof |
| US20190144647A1 (en) * | 2017-11-16 | 2019-05-16 | Toyo Tire & Rubber Co., Ltd. | Rubber composition for tires, and pneumatic tire using the same |
| CN110713640A (en) * | 2018-07-13 | 2020-01-21 | 杭州星庐科技有限公司 | Rubber composition and processing method, and rubber product and production method using same |
| CN114716619A (en) * | 2021-01-06 | 2022-07-08 | 中国石油天然气股份有限公司 | Preparation method of maleic anhydride grafted styrene-butadiene rubber compatibilizer |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1465614A (en) * | 2002-06-11 | 2004-01-07 | 毅 邵 | Composite polyolefine thermoplastic vulcanizate |
| US20100308495A1 (en) * | 2009-06-05 | 2010-12-09 | Pillai Chandrasekaran R | Process for the manufacture of reactive rubber process aids |
| US20190144647A1 (en) * | 2017-11-16 | 2019-05-16 | Toyo Tire & Rubber Co., Ltd. | Rubber composition for tires, and pneumatic tire using the same |
| CN108003540A (en) * | 2017-12-19 | 2018-05-08 | 江苏通用科技股份有限公司 | Improve ethylene propylene diene rubber and the composite material of chlorinated polyethylene rubber compatibility and preparation method thereof |
| CN110713640A (en) * | 2018-07-13 | 2020-01-21 | 杭州星庐科技有限公司 | Rubber composition and processing method, and rubber product and production method using same |
| CN114716619A (en) * | 2021-01-06 | 2022-07-08 | 中国石油天然气股份有限公司 | Preparation method of maleic anhydride grafted styrene-butadiene rubber compatibilizer |
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| CN115772331B (en) | 2023-04-25 |
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