CN102181082B - Environment-friendly reinforced rubber and preparation method of the environment-friendly reinforced rubber - Google Patents
Environment-friendly reinforced rubber and preparation method of the environment-friendly reinforced rubber Download PDFInfo
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- CN102181082B CN102181082B CN201110080037A CN201110080037A CN102181082B CN 102181082 B CN102181082 B CN 102181082B CN 201110080037 A CN201110080037 A CN 201110080037A CN 201110080037 A CN201110080037 A CN 201110080037A CN 102181082 B CN102181082 B CN 102181082B
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- environment
- rubber
- reinforced rubber
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 24
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 12
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011787 zinc oxide Substances 0.000 claims abstract description 12
- 239000003738 black carbon Substances 0.000 claims abstract description 10
- 229920013649 Paracril Polymers 0.000 claims description 21
- 239000005864 Sulphur Substances 0.000 claims description 10
- 238000005336 cracking Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000006579 Tsuji-Trost allylation reaction Methods 0.000 claims description 7
- 239000013543 active substance Substances 0.000 claims description 6
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical group C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 claims description 5
- 150000003016 phosphoric acids Chemical class 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 abstract description 16
- 239000006229 carbon black Substances 0.000 abstract description 14
- 239000002245 particle Substances 0.000 abstract description 12
- 230000002209 hydrophobic effect Effects 0.000 abstract description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052731 fluorine Inorganic materials 0.000 abstract description 6
- 239000011737 fluorine Substances 0.000 abstract description 6
- 238000003756 stirring Methods 0.000 abstract description 5
- 230000002776 aggregation Effects 0.000 abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 abstract description 3
- 229920000459 Nitrile rubber Polymers 0.000 abstract 4
- 235000021355 Stearic acid Nutrition 0.000 abstract 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 abstract 2
- 239000008117 stearic acid Substances 0.000 abstract 2
- 239000011593 sulfur Substances 0.000 abstract 2
- 238000004220 aggregation Methods 0.000 abstract 1
- 238000000197 pyrolysis Methods 0.000 abstract 1
- 238000005507 spraying Methods 0.000 abstract 1
- 239000010920 waste tyre Substances 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 239000000470 constituent Substances 0.000 description 3
- 238000009499 grossing Methods 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000012962 cracking technique Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to environment-friendly reinforced rubber and a preparation method of the environment-friendly reinforced rubber. The environment-friendly reinforced rubber contains the following components in parts by weight: 100 parts of nitrile rubber, 51-53 parts of waste tire pyrolysis carbon black (PCB), 3.1-3.5 parts of zinc oxide, 0.8-0.9 part of stearic acid, 1.1-1.3 parts of accelerator, 1 .8-1.9 parts of sulfur and 0.1-0.3 part of fluorine-containing surfactant. Raw nitrile rubber after plastication is placed in an open mill; after roller banding, the stearic acid, the zinc oxide, the accelerator and the PCB are added (spraying fluorine-containing surfactant and conducting stirring to uniform); and finally the sulfur is added and the open mill thins and dredges for 6 times, therefore the gross nitrile rubber is obtained. The environment-friendly reinforced rubber can solve the problems that the elementary particles of the PCB are smaller than that of common commercialization black carbon and aggregation is caused due to close arrangement; in addition, the PCB is effectively and uniformly dispersed, the mechanical strength of the gross nitrile rubber is improved, and a hydrophobic, oleophobic and smooth surface is obtained, therefore the environment-friendly reinforced rubber is incomparable to the common commercialization black carbon and the comprehensive property is improved obviously.
Description
Technical field
The present invention relates to the rubber preparation field, especially relate to a kind of environment-friendly type Reinforced Rubber and preparation method thereof.
Background technology
Carbon black is the most important reinforced filling of rubber industry, is difficult to replace in the usefulness that rubber strengthens the field as traditional practical filler.But preparation carbon black not only consumes energy and raw material but also contaminate environment.The damaged tire cracking technique that low-carbon circular economy expedites the emergence of, one of its main split product is a carbon black, is used for rubber item and can saves the energy, reduces production costs simultaneously.So rubber industry utilizes damaged tire cracking black carbon (PCB) to become the concern of industry.Existing now scholar studies substruction and the modification technology of PCB, but the systematic Study how rubber item utilizes PCB still seldom, therefore demands researching and solving rubber item employing PCB enhanced production technology urgently.Because the PCB ash oontent is high, the natural characteristics that particle diameter is little makes its reinforced effects not as high-quality carbon black N330; So study intensively PCB Reinforced Rubber technology, make it to bring into play the little strong point of particle diameter, overcome clustering phenomena again; Dwindle the gap with high-quality carbon black N330 reinforced effects, even some performance surmounts to some extent as far as possible, for example obtain hydrophobic, hate oil; Level and smooth surface obviously is a challenging gordian technique.
Summary of the invention
The object of the invention is exactly to provide a kind of PCB of making to be uniformly dispersed for the defective that overcomes above-mentioned prior art existence; Thereby effectively improve the mechanical property of rubber unvulcanizate; Obtain hydrophobic simultaneously, hate oil, surface smoothing, environment-friendly type Reinforced Rubber that over-all properties is high and preparation method thereof.
The object of the invention can be realized through following technical scheme:
A kind of environment-friendly type Reinforced Rubber is characterized in that, this Reinforced Rubber comprises following component and weight part content:
Described promotor is N cyclohexyl 2 benzothiazole sulfenamide, and molecular formula is C
13H
16N
2S
2
Described tensio-active agent is a fluorochemical surfactant.
Described fluorochemical surfactant is a perfluor allylic alkylation phosphoric acid salt, and molecular formula is C
18F
17H
11NO
7PSNa
2Or perfluor allylic alkylation ammonium sulphonate, molecular formula is C
15F
17H
8NO
4S.
A kind of preparation method of environment-friendly type Reinforced Rubber is characterized in that, this method may further comprise the steps:
(1) get the raw materials ready according to following component and weight part content:
(2) will hope the paracril rubber after the refining put into mill; The damaged tire cracking black carbon that adds Triple Pressed Stearic Acid, zinc oxide, promotor successively and sprayed tensio-active agent and stirred behind the bag roller; Add sulphur at last, following sheet promptly obtained the paracril rubber unvulcanizate after mill approached logical 6 times.
Compared with prior art; Advantage of the present invention is to add to have high surface, high heat-resistant stability, high chemical stability, the lipophobic again fluorochemical surfactant of hydrophobic; Overcome PCB particle accumulation phenomenon, the PCB that can effectively be uniformly dispersed, the physical strength of raising paracril rubber unvulcanizate; Obtain hydrophobic simultaneously, hate oil, level and smooth surface; Paracril rubber unvulcanizate over-all properties is obviously improved, and especially hydrophobicity performance improves and low coefficient of friction surfaces can suppress friction process and produces the electrostatic possibility, and is most important to mining Plastic-sheathed Cable.Also can be widely used in other rubber item higher, realize that PCB is used for the purpose of important rubber item, renewable resource are appreciated, and environmental protection be energy-conservation again performance requriements.
Embodiment
Below in conjunction with specific embodiment the present invention is elaborated.
Research shows; The PCB ultimate particle is spherical; Commercialization carbon black particle commonly used is littler, arranges closelyr, and the Van der Waals force between the particle causes the particle agglomeration size to be about 10 μ m; Obvious size (being about 2 μ m), particle agglomeration distribution of sizes broad simultaneously greater than convenience goods carbon black N774 aggregate.Learn that through analyzing C content is more than 85% in the PCB main chemical compositions, also contain O, Si, three kinds of non-metallic elements of S and Al, Ni, Cu, four kinds of metallic elements of Zn, for the PCB particle that is uniformly dispersed, it is little to bring into play its particle diameter, more effectively the effect of Reinforced Rubber.Consider that from being convenient to tissue production adopt and add table and the method for promoting agent, the present invention adopts fluorochemical surfactant; To solve the clustering phenomena of PCB ultimate particle, make it to be dispersed in the rubber unvulcanizate, reach the purpose of the mechanical property of effective raising paracril rubber unvulcanizate; Obtain hydrophobic simultaneously, hate oil, the effect of surface smoothing; Paracril rubber unvulcanizate over-all properties is obviously improved, thereby get into the row of important rubber item, broadened application scope.
Embodiment 1
A kind of preparation method of environment-friendly type Reinforced Rubber, this method may further comprise the steps:
The content unit of constituent is weight (kg)
Getting paracril is 100, and PCB is 51, and zinc oxide is 3.1; Triple Pressed Stearic Acid is 0.8, and promotor is 1.1, and sulphur is 1.8; Fluorochemical surfactant is 0.2 (Shanghai City organic fluorine Research Institute), and wherein PCB is the damaged tire cracking black carbon, and promotor is N cyclohexyl 2 benzothiazole sulfenamide; Fluorochemical surfactant is a perfluor allylic alkylation phosphoric acid salt, and molecular formula is C
18F
17H
11NO
7PSNa
2Paracril rubber after plasticating is put into mill; The bag roller after successively to wherein adding Triple Pressed Stearic Acid, zinc oxide, promotor and PCB; The PCB that adds must spray fluorochemical surfactant and stir, and adds sulphur at last, following sheet after mill approaches logical 6 times; Obtain the paracril rubber unvulcanizate, as rubber item.
Embodiment 2
A kind of preparation method of environment-friendly type Reinforced Rubber, this method may further comprise the steps:
The content unit of constituent is weight (kg)
Getting paracril is 100, and PCB is 52, and zinc oxide is 3.3; Triple Pressed Stearic Acid is 0.85, and promotor is 1.2, and sulphur is 1.85; Fluorochemical surfactant is 0.1 (Shanghai City organic fluorine Research Institute), and wherein PCB is the damaged tire cracking black carbon, and promotor is N cyclohexyl 2 benzothiazole sulfenamide; Fluorochemical surfactant is a perfluor allylic alkylation ammonium sulphonate, and molecular formula is C
15F
17H
8NO
4S.Paracril rubber after plasticating is put into mill; The bag roller after successively to wherein adding Triple Pressed Stearic Acid, zinc oxide, promotor and PCB; The PCB that adds must spray fluorine-containing table and promoting agent and stirring, and adds sulphur at last, sheet down after thin logical 6 times of the mill; Obtain the paracril rubber unvulcanizate, as rubber item.
Embodiment 3
A kind of preparation method of environment-friendly type Reinforced Rubber, this method may further comprise the steps:
The content unit of constituent is weight (kg)
Getting paracril is 100, and PCB is 53, and zinc oxide is 3.5; Triple Pressed Stearic Acid is 0.9, and promotor is 1.3, and sulphur is 1.9; Fluorochemical surfactant is 0.3 (Shanghai City organic fluorine Research Institute), and wherein PCB is the damaged tire cracking black carbon, and promotor is N cyclohexyl 2 benzothiazole sulfenamide; Fluorochemical surfactant is a perfluor allylic alkylation phosphoric acid salt, and molecular formula is C
18F
17H
11NO
7PSNa
2Paracril rubber after plasticating is put into mill; The bag roller after successively to wherein adding Triple Pressed Stearic Acid, zinc oxide, promotor and PCB; The PCB that adds must spray fluorochemical surfactant and stir, and adds sulphur at last, following sheet after mill approaches logical 6 times; Obtain the paracril rubber unvulcanizate, as rubber item.
The tensile strength of the prepared paracril rubber unvulcanizate of the foregoing description can reach 15.3MPa, and tear strength can reach 45.6kN/m.With regard to physical strength; The a little higher than commodity carbon black of its reinforced effects N660 enhanced paracril rubber unvulcanizate; Slightly inferior to carbon black N330 enhanced rubber, Mooney viscosity is near carbon black N330 enhanced rubber, and maximum torque, time of scorch, sulfurizing time are also near carbon black N330 enhanced rubber; But be to use present embodiment production, cost can reduce greatly.Practicality shows, adds fluorochemical surfactant and sprays the PCB enhancing paracril rubber unvulcanizate that stirs, and not only physical strength satisfies important rubber item requirement; And the surperficial hydrophobic of its goods, hate oil, surface smoothing; Non-common carbon black Reinforced Rubber can be reached, and from the over-all properties discussion, the PCB that adds fluorochemical surfactant strengthens the paracril rubber unvulcanizate can rival commodities carbon black Reinforced Rubber; The realization renewable resource are appreciated, and environmental protection is energy-conservation again.
Claims (3)
1. an environment-friendly type Reinforced Rubber is characterized in that, this Reinforced Rubber comprises following component and weight part content:
Paracril 100;
Damaged tire cracking black carbon 51～53;
Zinc oxide 3.1～3.5;
Triple Pressed Stearic Acid 0.8～0.9;
Promotor 1.1～1.3;
Sulphur 1.8～1.9;
Tensio-active agent 0.1～0.3;
Described tensio-active agent is a perfluor allylic alkylation phosphoric acid salt, and molecular formula is C
18F
17H
11NO
7PSNa
2, or perfluor allylic alkylation ammonium sulphonate, molecular formula is C
15F
17H
8NO
4S.
2. a kind of environment-friendly type Reinforced Rubber according to claim 1 is characterized in that described promotor is N cyclohexyl 2 benzothiazole sulfenamide, and molecular formula is C
13H
16N
2S
2
3. the preparation method of an environment-friendly type Reinforced Rubber as claimed in claim 1 is characterized in that, this method may further comprise the steps:
(1) get the raw materials ready according to following component and weight part content:
Paracril 100,
Damaged tire cracking black carbon 51～53,
Zinc oxide 3.1～3.5,
Triple Pressed Stearic Acid 0.8～0.9,
Promotor 1.1～1.3,
Sulphur 1.8～1.9,
Tensio-active agent 0.1～0.3;
(2) the paracril rubber after will plasticating is put into mill; The damaged tire cracking black carbon that adds Triple Pressed Stearic Acid, zinc oxide, promotor successively and sprayed tensio-active agent and stirred behind the bag roller; Add sulphur at last, following sheet promptly obtained the paracril rubber unvulcanizate after mill approached logical 6 times.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110080037A CN102181082B (en) | 2011-03-31 | 2011-03-31 | Environment-friendly reinforced rubber and preparation method of the environment-friendly reinforced rubber |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110080037A CN102181082B (en) | 2011-03-31 | 2011-03-31 | Environment-friendly reinforced rubber and preparation method of the environment-friendly reinforced rubber |
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| Publication Number | Publication Date |
|---|---|
| CN102181082A CN102181082A (en) | 2011-09-14 |
| CN102181082B true CN102181082B (en) | 2012-09-05 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103897231B (en) * | 2014-03-01 | 2016-05-18 | 安徽省定兴电缆有限公司 | Aging cable sheath material of a kind of heat-resistant and preparation method thereof |
| CN107383419A (en) * | 2017-08-28 | 2017-11-24 | 中创奕龙科技股份有限公司 | A kind of CNT and cracking black carbon composite material and preparation method thereof |
| CN107459682A (en) * | 2017-09-25 | 2017-12-12 | 芜湖凯奥尔环保科技有限公司 | A kind of preparation method of fibre reinforced rubber composite |
| CN110561633A (en) * | 2019-09-17 | 2019-12-13 | 安徽电缆股份有限公司 | rubber cable material open milling processing technology |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7250451B2 (en) * | 2004-03-09 | 2007-07-31 | American Rubber Technologies, Inc. | Recycled rubber processing and performance enhancement |
| CN101089124A (en) * | 2006-06-15 | 2007-12-19 | 任丽娟 | Waste tyre cracking process and apparatus |
| CN101643596A (en) * | 2008-08-07 | 2010-02-10 | 上海中路实业有限公司 | Granulation processing device for pyrolytic carbon black of waste tyre and granulation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ATE362958T1 (en) * | 2001-01-02 | 2007-06-15 | Michelin Soc Tech | RUBBER MIXTURE BASED ON A DIENE ELASTOMER AND A REINFORCEMENT SILICON CARBIDE |
-
2011
- 2011-03-31 CN CN201110080037A patent/CN102181082B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7250451B2 (en) * | 2004-03-09 | 2007-07-31 | American Rubber Technologies, Inc. | Recycled rubber processing and performance enhancement |
| CN101089124A (en) * | 2006-06-15 | 2007-12-19 | 任丽娟 | Waste tyre cracking process and apparatus |
| CN101643596A (en) * | 2008-08-07 | 2010-02-10 | 上海中路实业有限公司 | Granulation processing device for pyrolytic carbon black of waste tyre and granulation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| JP特表2004-517183A 2004.06.10 |
| 彭小芹等.废轮胎裂解炭黑的深加工及应用.《高分子材料科学与工程》.2004,第20卷(第4期),142-145页. * |
| 杜爱华等.废轮胎裂解炭黑的基本性质及其在丁苯橡胶种的应用.《合成橡胶工业》.2008,第31卷(第6期),446-449页. * |
| 肖国良等.废轮胎裂解炭黑的超细粉碎和表面改性及在NR中的应用.《橡胶工业》.2004,第51卷(第2期),78-82页. * |
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