CN104151650A - Rubber composition containing modified rubber - Google Patents
Rubber composition containing modified rubber Download PDFInfo
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- CN104151650A CN104151650A CN201410423873.3A CN201410423873A CN104151650A CN 104151650 A CN104151650 A CN 104151650A CN 201410423873 A CN201410423873 A CN 201410423873A CN 104151650 A CN104151650 A CN 104151650A
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- rubber
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- carbon black
- coupling agent
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Abstract
The invention relates to the technical field of rubber and particularly relates to a rubber composition containing modified rubber. The composition is characterized by also including, on the basis of 100 parts by weight of the rubber composition, 50-80 parts of a mixture composed of carbon black and white carbon black at any proportion, 1-10 parts of an amino silane coupling agent, 1-10 parts of a silane coupling agent, 2.0-5.0 parts of zinc oxide, 1.0-3.0 parts of stearic acid, 1.0-4.0 parts of anti-aging agent, 1.0-2.0 parts of protective wax, 1.0-4.0 parts of sulphur and 1.0-4.0 parts of an accelerator, wherein the rubber composition comprises 0-95 parts of a mixture composed of natural rubber, butadiene rubber, and butadiene styrene rubber at any proportion and 5-100 parts of a mixture composed of modified natural rubber, modified butadiene rubber, and modified butadiene styrene at any proportion. By means of the modified rubber and the amino silane coupling agent, performances of the rubber are enhanced and compatibility of the rubber with white carbon black is improved. A rubber material is improved in processability and hysteresis loss.
Description
Technical field
The present invention relates to rubber technology field, specifically a kind of rubber combination containing modified rubber.
Background technology
In tire formulation field, the use of white carbon black is more and more extensive.Conventionally, white carbon black need to coordinate silane coupling agent to use together could to improve and the consistency of rubber and increase white carbon black and rubber between Intermolecular Forces, improve the result of use of white carbon black.The silane coupling agent that tyre industry is conventional generally contains sulphur atom.The contained sulphur sulfide linkage of such silane coupling agent at high temperature ruptures and reacts with rubber, and the siloxane groups of the other end decomposes rear and white carbon black surface formation chemical bond, therefore, such coupling agent has improved the interaction force of white carbon black and rubber greatly, has obtained large-scale application.
Modification by rubber can improve the performance of rubber and increase rubber and white carbon black between interaction force, obtain using the high-performance rubber formula of white carbon black.But, in general modified rubber and tire industry, between conventional silane coupling agent, there is not special chemical reaction.To the modification of rubber, can not promote the improvement of silane coupling agent to the improvement of bonding force between white carbon black and rubber and sizing material processing characteristics.
Summary of the invention
Object of the present invention is exactly in order to overcome above-mentioned the deficiencies in the prior art, a kind of rubber combination containing modified rubber is provided, adopt modified rubber and amino silicane coupling agent, improve rubber performance and increase the consistency with white carbon black, improve the processing characteristics of sizing material and improve the hysteresis loss of sizing material.
The technical scheme that the present invention solves the problems of the technologies described above employing is: a kind of rubber combination containing modified rubber, it is characterized in that,
The rubber combination of 100 weight parts of take is benchmark, also comprises
50～80 parts, carbon black and white carbon black arbitrary proportion mixture, 1～10 part of amino silicane coupling agent, 1～10 part of silane coupling agent, 2.0～5.0 parts, zinc oxide, 1.0～3.0 parts of stearic acid, 1.0～4.0 parts, anti-aging agent, 1.0～2.0 parts of protection waxes, 1.0～4.0 parts, sulphur, 1.0～4.0 parts of promotor;
Wherein rubber combination is 0～95 part of natural rubber, cis-1,4-polybutadiene rubber, styrene-butadiene rubber(SBR) arbitrary proportion mixture, 5～100 parts of modified natural rubbers, modification cis-1,4-polybutadiene rubber, modified styrene butadiene rubber arbitrary proportion mixture.
As preferably, the rubber combination of 100 weight parts of take is benchmark, also comprises
50～80 parts, carbon black and white carbon black arbitrary proportion mixture, 3.0～8.0 parts of amino silicane coupling agents, 1～10 part of silane coupling agent, 2.0～3.0 parts, zinc oxide, 2.0～3.0 parts of stearic acid, 2.0～3.0 parts, anti-aging agent, 1.0～2.0 parts of protection waxes, 1.0～2.0 parts, sulphur, 1.0～2.0 parts of promotor;
Wherein rubber combination is 0～95 part of natural rubber, cis-1,4-polybutadiene rubber, styrene-butadiene rubber(SBR) arbitrary proportion mixture, 5～100 parts of modified natural rubbers, modification cis-1,4-polybutadiene rubber, modified styrene butadiene rubber arbitrary proportion mixture.
The present invention also can be achieved by the following measures:
The rubber that above-mentioned modified natural rubber, modification cis-1,4-polybutadiene rubber, modified styrene butadiene rubber are is 0.05～0.7 with the epoxy content of epoxide group on rubber molecular chain.
Above-mentioned amino silicane coupling agent molecular structure is: NH2 (CH
2) xSi (OR1) yR2z. wherein, R1 and R2 are H or methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, phenyl.X is that numeral 1～20, y is that numeral 1～3, z is 3-y.
As preferably, described carbon black is selected N234 or the high hard(carbon)black of N375.
As preferably, above-mentioned promotor is selected accelerator NS.
The present invention also can be achieved by the following measures: vulcanizing agent TB710 is comprised of 90% p-tert-butylphenol disulphide polymer and 10% stearic mixture.
The invention has the beneficial effects as follows, adopt modified rubber and amino silicane coupling agent, improve rubber performance and increase the consistency with white carbon black, improve the processing characteristics of sizing material and improve the hysteresis loss of sizing material.
Embodiment
Below in conjunction with embodiment, the invention will be further described:
It is benchmark that the rubber combination of 100 weight parts is take in the present invention, also comprise 50～80 parts, carbon black and white carbon black arbitrary proportion mixture, 1～10 part of amino silicane coupling agent, 1～10 part of silane coupling agent, 2.0～5.0 parts, zinc oxide, 1.0～3.0 parts of stearic acid, 1.0～4.0 parts, anti-aging agent, 1.0～2.0 parts of protection waxes, 1.0～4.0 parts, sulphur, 1.0～4.0 parts of promotor; Wherein rubber combination is 0～95 part of natural rubber, cis-1,4-polybutadiene rubber, styrene-butadiene rubber(SBR) arbitrary proportion mixture, 5～100 parts of modified natural rubbers, modification cis-1,4-polybutadiene rubber, modified styrene butadiene rubber arbitrary proportion mixture.
The rubber that above-mentioned modified natural rubber, modification cis-1,4-polybutadiene rubber, modified styrene butadiene rubber are is 0.05～0.7 with the epoxy content of epoxide group on rubber molecular chain.
Above-mentioned amino silicane coupling agent molecular structure is: NH
2(CH
2) xSi (OR1) yR2z, wherein, R1 and R2 are H or methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, phenyl.X is that numeral 1～20, y is that numeral 1～3, z is 3-y.
As preferably, described carbon black is selected N234 or the high hard(carbon)black of N375.
As preferably, above-mentioned promotor is selected accelerator NS.
Vulcanizing agent TB710 is comprised of 90% p-tert-butylphenol disulphide polymer and 10% stearic mixture.
Adopt feed composition of the present invention and content can prepare by existing routine techniques, concrete steps are:
First paragraph is mixing: by rubber (natural rubber, cis-1,4-polybutadiene rubber, styrene-butadiene rubber(SBR) arbitrary proportion mixture 0～95 modified natural rubber, modification cis-1,4-polybutadiene rubber, modified styrene butadiene rubber arbitrary proportion mixture 5～100) be added in Banbury mixer, press bolt 10～60 seconds, by carbon black, white carbon black, amino silicane coupling agent, silane coupling agent joins Banbury mixer, press bolt 10～200 seconds, after carrying bolt, press bolt to 125 ℃ to carry bolt, again press bolt to 140～160 ℃ to keep after 10～60 seconds, add zinc oxide, stearic acid, anti-aging agent, protection wax, press bolt 10～60 seconds, after carrying bolt, press bolt to 125 ℃ to carry bolt, again press bolt to 145 ℃ to keep binder removal after 10～60 seconds, twice time sheet of thin-pass in mill.
Second segment is mixing: add one section of rubber unvulcanizate, press bolt to keep 10～60 seconds, press bolt 10～60 seconds after carrying bolt again, press bolt to 145 ℃ binder removal, twice time sheet of thin-pass in mill after carrying bolt.
Three-stage mixing: add second segment rubber unvulcanizate, and sulphur, promotor, scorch retarder, multi-functional processing aid, press bolt to keep 10～60 seconds, press bolt to 105 ℃ binder removal, twice time sheet of thin-pass in mill after carrying bolt.
Adopt identical calendering process to carry out mixing, properties of rubber test discovery to sizing material of the present invention and actual production sizing material, the present invention has obviously improved the performance of sizing material, maintaining on the basis of sizing material wear resisting property, obviously improved the hysteresis loss of sizing material, effectively improve the rolling resistance of tire.
For the reliability of proved invention effect, the present invention is contrasted with formula and the property indices of the tire tread of prior art, the results are shown in Table 1 and table 2:
As can be seen from Table 1, 2, tread mix prepared by use the present invention is than comparative example, and tensile strength obviously improves, and rebound performance significantly increases, and hysteresis loss is obviously improved.Be mainly reflected in comparative example, curing time is that the cross-linked rubber tensile strength of 30 minutes is 18.6MPa, and rebound value is that at 35,60 ℃, dissipation factor is 0.15; Invention formula curing time is that the cross-linked rubber tensile strength of 30 minutes is 20.5MPa, and rebound value is that at 42,60 ℃, dissipation factor is 0.09.Invention recipe ratio comparative example tensile strength increases by 9.5%, and rebound resilience increases by 6.8%, and hysteresis loss reduces by 26.5%.As can be seen here, use formula of the present invention can obviously improve the tensile strength of tire tread compound, improve the hysteresis loss of sizing material, improve the rolling resistance of tire.
Biao1:(Ge material content unit: weight part)
| Starting material | Comparative example | The present invention |
| Styrene-butadiene rubber(SBR) | 80 | 80 |
| Cis-1,4-polybutadiene rubber | 20 | ? |
| Modification cis-1,4-polybutadiene rubber | ? | 20 |
| Carbon black | 35 | 25 |
| White Carbon black | 30 | 30 |
| Zinc oxide | 3.0 | 3.0 |
| Stearic acid | 1.0 | 1.0 |
| Anti-aging agent | 2.0 | 2.0 |
| Silane coupling agent | 6.0 | 1.0 |
| Amino silicane coupling agent | ? | 6.0 |
| Protection wax | 1.0 | 1.0 |
| Sulphur | 1.5 | 1.5 |
| Promotor | 2.0 | 2.0 |
Note: the epoxy content of modification cis-1,4-polybutadiene rubber is 40%, the molecular formula of amino silicane coupling agent is NH
2(CH
2)
3si (OC
2h
5)
3.
Table 2: physical and mechanical properties
Embodiment (each material content unit: weight part)
| Starting material | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Natural rubber | ? | ? | ? | 20 |
| Cis-1,4-polybutadiene rubber | 20 | ? | ? | 20 |
| Styrene-butadiene rubber(SBR) | 20 | ? | ? | ? |
| Modified natural rubber | ? | ? | ? | 40 |
| Modification cis-1,4-polybutadiene rubber | 20 | ? | 20 | 20 |
| Modified styrene butadiene rubber | 40 | 100 | 80 | ? |
| Carbon black | 35 | 35 | 20 | 20 |
| White Carbon black | 30 | 30 | 35 | 40 |
| Zinc oxide | 2.0 | 4.0 | 5.0 | 3.0 |
| Stearic acid | 1.0 | 2.0 | 3.0 | 1.0 |
| Antioxidant 4020 | 1.0 | 2.0 | 3.0 | 2.0 |
| Anti-aging agent RD | 2.0 | 1.0 | 0.5 | 1.0 |
| Silane coupling agent | 2.0 | 1.0 | 1.0 | 6.0 |
| Amino silicane coupling agent | 4.0 | 5.0 | 6.0 | 2.0 |
| Protection wax | 1.0 | 1.5 | 2.0 | 1.0 |
| Sulphur | 1.0 | 2.0 | 1.6 | 1.2 |
| Promotor | 1.6 | 0.8 | 1.2 | 0.9 |
Note: in embodiment 1-4, modified natural glue epoxy content is 30%, and the epoxy content of modification cis-1,4-polybutadiene rubber is respectively 10%, 20% and 35%, and the epoxy content of modified styrene butadiene rubber is respectively 40%, 35% and 30%.The molecular formula of amino silicane coupling agent is respectively NH
2(CH
2)
4si (OCH
3)
1(C
2h
5)
2, NH
2(CH
2)
3si (OC
2h
5)
2c
2h
5, NH
2(CH
2)
3si (OC
3h
7)
3, NH
2(CH
2)
3si (OC
2h
5)
3.
The physical and mechanical properties of embodiment (150 ℃, 30 minutes) is as follows:
| Test subject | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Shao Er A type hardness tester/degree | 62 | 64 | 61 | 58 |
| Elongation rate of tensile failure/% | 441 | 437 | 456 | 513 |
| Tensile strength/Mpa | 19.3 | 18.9 | 19.4 | 22.8 |
| 300% stress at definite elongation/MPa | 12.7 | 11.5 | 11.9 | 12.8 |
| 100% stress at definite elongation/MPa | 2.9 | 2.7 | 2.9 | 3.1 |
| Rebound value/% | 43 | 41 | 42 | 50 |
| Tear strength/(KN/m) | 52 | 51 | 55 | 59 |
| Drum-type abrasion | 149 | 148 | 150 | 151 |
| tanδ（0℃） | 0.31 | 0.42 | 0.36 | 0.21 |
| tanδ（60℃） | 0.09 | 0.10 | 0.09 | 0.08 |
Claims (6)
1. the rubber combination containing modified rubber, it is characterized in that, the rubber combination of 100 weight parts of take is benchmark, also comprises 50～80 parts, carbon black and white carbon black arbitrary proportion mixture, 1～10 part of amino silicane coupling agent, 1～10 part of silane coupling agent, 2.0～5.0 parts, zinc oxide, 1.0～3.0 parts of stearic acid, 1.0～4.0 parts, anti-aging agent, 1.0～2.0 parts of protection waxes, 1.0～4.0 parts, sulphur, 1.0～4.0 parts of promotor;
Wherein rubber combination is 0～95 part of natural rubber, cis-1,4-polybutadiene rubber, styrene-butadiene rubber(SBR) arbitrary proportion mixture, 5～100 parts of modified natural rubbers, modification cis-1,4-polybutadiene rubber, modified styrene butadiene rubber arbitrary proportion mixture.
2.. contain according to claim 1 the rubber combination of modified rubber, it is characterized in that, the rubber combination of 100 weight parts of take is benchmark, also comprises 50～80 parts, carbon black and white carbon black arbitrary proportion mixture, 3.0～8.0 parts of amino silicane coupling agents, 1～10 part of silane coupling agent, 2.0～3.0 parts, zinc oxide, 2.0～3.0 parts of stearic acid, 2.0～3.0 parts, anti-aging agent, 1.0～2.0 parts of protection waxes, 1.0～2.0 parts, sulphur, 1.0～2.0 parts of promotor;
Wherein rubber combination is 0～95 part of natural rubber, cis-1,4-polybutadiene rubber, styrene-butadiene rubber(SBR) arbitrary proportion mixture, 5～100 parts of modified natural rubbers, modification cis-1,4-polybutadiene rubber, modified styrene butadiene rubber arbitrary proportion mixture.
3. according to claim 1 containing the rubber combination of modified rubber, it is characterized in that described modified natural rubber, modification cis-1,4-polybutadiene rubber, modified styrene butadiene rubber are the rubber that is 0.05～0.7 with the epoxy content of epoxide group on rubber molecular chain.
4. according to claim 1 containing the rubber combination of modified rubber, it is characterized in that described amino silicane coupling agent molecular structure is: NH
2(CH
2) xSi (OR1) yR2z, wherein, R1, R2 and R3 are H or methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, phenyl, x is that numeral 1～20, y be that digital 1～3, z is 3-y.
5. according to claim 1 containing the rubber combination of modified rubber, the carbon black described in it is characterized in that is selected N234 or the high hard(carbon)black of N375.
6. according to claim 1 containing the rubber combination of modified rubber, the promotor described in it is characterized in that is selected accelerator NS.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410423873.3A CN104151650A (en) | 2014-08-26 | 2014-08-26 | Rubber composition containing modified rubber |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410423873.3A CN104151650A (en) | 2014-08-26 | 2014-08-26 | Rubber composition containing modified rubber |
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|---|---|
| CN104151650A true CN104151650A (en) | 2014-11-19 |
Family
ID=51877290
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410423873.3A Pending CN104151650A (en) | 2014-08-26 | 2014-08-26 | Rubber composition containing modified rubber |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105131492A (en) * | 2015-08-18 | 2015-12-09 | 合肥市再德高分子材料有限公司 | Composite modified high-performance natural rubber material |
| CN107739456A (en) * | 2017-08-26 | 2018-02-27 | 南通成山高分子材料有限公司 | A kind of polymer rubber beam of service life length |
| CN109384975A (en) * | 2017-08-03 | 2019-02-26 | 中国石油化工股份有限公司 | For the rubber composition of sole and vulcanized rubber and its preparation method and application |
| CN116063759A (en) * | 2023-03-06 | 2023-05-05 | 三门县质量技术服务中心(三门县产品质量检验所、三门县计量检定测试所) | Method for preparing rubber composition and rubber obtained by same |
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| US20090105403A1 (en) * | 2007-10-23 | 2009-04-23 | Toyo Tire & Rubber Co., Ltd. | Rubber Composition For Tire Tread |
| CN101679686A (en) * | 2007-05-22 | 2010-03-24 | 住友橡胶工业株式会社 | Rubber composition for tire and pneumatic tire |
| CN101679688A (en) * | 2007-06-05 | 2010-03-24 | 住友橡胶工业株式会社 | Rubber composition for tire, tire member, rubber composition for base tread, base tread, and tire |
| US20120285601A1 (en) * | 2007-10-03 | 2012-11-15 | Tatsuya Miyazaki | Rubber composition for sidewall and tire having sidewall using thereof, and rubber composition for clinch and tire having clinch using thereof |
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2014
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1315929C (en) * | 2003-06-03 | 2007-05-16 | 住友橡胶工业株式会社 | Rubber composition for tread and pneumatic tyre using the same |
| JP2006169434A (en) * | 2004-12-17 | 2006-06-29 | Sumitomo Rubber Ind Ltd | Rubber composition and tire formed from the same |
| CN101679686A (en) * | 2007-05-22 | 2010-03-24 | 住友橡胶工业株式会社 | Rubber composition for tire and pneumatic tire |
| CN101679688A (en) * | 2007-06-05 | 2010-03-24 | 住友橡胶工业株式会社 | Rubber composition for tire, tire member, rubber composition for base tread, base tread, and tire |
| US20120285601A1 (en) * | 2007-10-03 | 2012-11-15 | Tatsuya Miyazaki | Rubber composition for sidewall and tire having sidewall using thereof, and rubber composition for clinch and tire having clinch using thereof |
| US20090105403A1 (en) * | 2007-10-23 | 2009-04-23 | Toyo Tire & Rubber Co., Ltd. | Rubber Composition For Tire Tread |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105131492A (en) * | 2015-08-18 | 2015-12-09 | 合肥市再德高分子材料有限公司 | Composite modified high-performance natural rubber material |
| CN109384975A (en) * | 2017-08-03 | 2019-02-26 | 中国石油化工股份有限公司 | For the rubber composition of sole and vulcanized rubber and its preparation method and application |
| CN107739456A (en) * | 2017-08-26 | 2018-02-27 | 南通成山高分子材料有限公司 | A kind of polymer rubber beam of service life length |
| CN116063759A (en) * | 2023-03-06 | 2023-05-05 | 三门县质量技术服务中心(三门县产品质量检验所、三门县计量检定测试所) | Method for preparing rubber composition and rubber obtained by same |
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Application publication date: 20141119 |