CN102120835B - A kind of processing method of high molecular weight rare earth butadiene rubber - Google Patents
A kind of processing method of high molecular weight rare earth butadiene rubber Download PDFInfo
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- CN102120835B CN102120835B CN2010106040150A CN201010604015A CN102120835B CN 102120835 B CN102120835 B CN 102120835B CN 2010106040150 A CN2010106040150 A CN 2010106040150A CN 201010604015 A CN201010604015 A CN 201010604015A CN 102120835 B CN102120835 B CN 102120835B
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Abstract
本发明提供一种高分子量稀土顺丁橡胶的加工方法，把高分子量稀土顺丁橡胶、双环戊二烯石油树脂、硬脂酸、氧化锌、硫黄、硫化促进剂、防老剂和炭黑按配比依次投入到混炼设备中混合均匀得到混炼胶，将混炼胶在平板硫化机上硫化制得硫化胶。选用成本低廉的双环戊二烯石油树脂加到橡胶中能显著降低橡胶的成本。本发明的加工方法可显著减少混炼胶的塑炼时间，降低混炼加工能耗。本发明的加工方法能显著提高高分子量稀土顺丁橡胶硫化胶的拉伸强度、断裂伸长率在410-702％之间、拉伸强度可提高7～26％，最高可达27MPa以上，撕裂强度在40～106KN·m-1之间。The invention provides a processing method of high molecular weight rare earth butadiene rubber, comprising high molecular weight rare earth butadiene rubber, dicyclopentadiene petroleum resin, stearic acid, zinc oxide, sulfur, vulcanization accelerator, anti-aging agent and carbon black according to the proportion Sequentially put into the mixing equipment and mix evenly to obtain mixed rubber, and vulcanize the mixed rubber on a flat vulcanizing machine to obtain vulcanized rubber. Adding low-cost dicyclopentadiene petroleum resin to rubber can significantly reduce the cost of rubber. The processing method of the invention can significantly reduce the plasticating time of the compounded rubber and reduce the energy consumption of the compounding process. The processing method of the present invention can significantly improve the tensile strength of the high molecular weight rare earth butadiene rubber vulcanizate, the elongation at break is between 410-702%, the tensile strength can be increased by 7-26%, and the maximum can reach more than 27MPa. The cracking strength is between 40 and 106KN·m -1 .
Description
Technical field
The present invention relates to a kind of working method of high-molecular-weight rare earth butadiene, belong to the Rubber processing technology, be specifically related to the working method of a kind of dicyclopentadiene petroleum resin as the toughener of high-molecular-weight rare earth butadiene.
Background technology
High-molecular-weight rare earth butadiene normally with respect to the nickel polymerized BR BR9000 of common molecular weight, its weight-average molecular weight
Usually 5 * 10
5More than g/mol.The high-molecular-weight rare earth butadiene material has extraordinary physical and mechanical properties and ageing-resistant performance, yet processing and difficult forming, often need plasticate to destroy macromolecular chain or improve processing characteristics by oil-filled method, but also lost physical and mechanical properties simultaneously.(the dry nickel catalyst system of Wu Xin is along production and the performance [J] of fourth oil-extended rubber. China Synthetic Rubber Industry .1984,7 (4): 260～263).
Dicyclopentadiene petroleum resin is C
5A kind of fine chemical product that dicyclopentadiene in product separation is polymerized through free radical reaction.Dicyclopentadiene petroleum resin has good affinity, thermostability and good solubility, is widely used in the industries such as paint, printing ink, tackiness agent, rubber.(Li Shujie. ethylene unit by-product C
5The test [J] of synthetic DCPD petroleum resin. Heilungkiang chemical industry .1998,4:16～18).
In high-molecular-weight rare earth butadiene, add dicyclopentadiene petroleum resin, purpose is that to solve high-molecular-weight rare earth butadiene time of plasticating long, the shortcomings such as poor processability.The present invention's technical scheme is not indicated in document.
Summary of the invention
The present invention adds dicyclopentadiene petroleum resin in high-molecular-weight rare earth butadiene, purpose is that to solve high-molecular-weight rare earth butadiene time of plasticating long, the shortcomings such as poor processability.Add vulcanization of rubber glue tensile strength, elongation at break, tear strength after dicyclopentadiene petroleum resin all to be significantly improved.
High-molecular-weight rare earth butadiene normally with respect to the nickel polymerized BR BR9000 of common molecular weight, its weight-average molecular weight
Usually 5 * 10
5More than g/mol.
The invention provides a kind of working method of high-molecular-weight rare earth butadiene, its step and condition are as follows:
(a) according to high-molecular-weight rare earth butadiene: dicyclopentadiene petroleum resin: stearic acid: zinc oxide: Sulfur: vulcanization accelerator: anti-aging agent: the mass ratio of carbon black is 100: 5～30: 2: 3: 2～4: 0.9: 1: 50～60, put into successively high-molecular-weight rare earth butadiene, dicyclopentadiene petroleum resin, stearic acid, zinc oxide, Sulfur, vulcanization accelerator, anti-aging agent and carbon black in mixing facilities, mix rear taking-up, obtain rubber unvulcanizate;
The high-molecular-weight rare earth butadiene adopted is patented product (China Patent No. 01128289.4), its weight-average molecular weight
Scope is 6～17.5 * 10
5Between g/mol, molecular weight distribution
Scope is 3～14, and cis-Isosorbide-5-Nitrae content (cis-1,4) is 87～99%;
The dicyclopentadiene petroleum resin adopted is Shandong Province of China Jade Emperor chemical industry company limited product, and softening temperature is 120～150 ℃;
(b) by rubber unvulcanizate under 150 ℃, 10MPa condition, press the sulfuration of sulfurizing point time, make cross-linked rubber.
Beneficial effect: the 1) working method of a kind of high-molecular-weight rare earth butadiene provided by the invention, in high-molecular-weight rare earth butadiene, add dicyclopentadiene petroleum resin with low cost, be added to the cost that can significantly reduce rubber in rubber.2) working method provided by the invention can significantly reduce plasticating the time of rubber unvulcanizate, reduces the mixed refining process energy consumption.3) working method provided by the invention has significantly improved the tensile strength of cis-1,4-polybutadiene rubber cross-linked rubber, and elongation at break is between 410-702%, and the tensile strength of its cross-linked rubber can improve 7～26%, and more than reaching as high as 27Mpa, tear strength is at 40～106KNm
-1Between.
Embodiment
Embodiment 1
The working method of a kind of high-molecular-weight rare earth butadiene provided by the invention, its step and condition are as follows:
(a) according to high-molecular-weight rare earth butadiene: dicyclopentadiene petroleum resin: stearic acid: zinc oxide: Sulfur: vulcanization accelerator: anti-aging agent: the mass ratio of carbon black is 100: 20: 2: 3: 3: 0.9: 1: 60, put into successively high-molecular-weight rare earth butadiene, dicyclopentadiene petroleum resin, stearic acid, zinc oxide, Sulfur, vulcanization accelerator, anti-aging agent and carbon black in mixing facilities, mix rear taking-up, obtain rubber unvulcanizate; Described high-molecular-weight rare earth butadiene
Cis-1,4 content=98.8%, the softening temperature of described dicyclopentadiene petroleum resin are 134 ℃;
(b) by rubber unvulcanizate under 150 ℃, 10MPa condition, by the sulfurizing point time, vulcanize on vulcanizing press, make cross-linked rubber.The stretching tear resistance of cross-linked rubber is in Table 1.
Comparative Examples 1
In the formula of rubber unvulcanizate, do not add dicyclopentadiene petroleum resin, high-molecular-weight rare earth butadiene: the Sulfur mass ratio is 100: 1.5, and other step and formula and embodiment 1 are same.The stretching tear resistance of cross-linked rubber is in Table 1.
Embodiment 2
The working method of a kind of high-molecular-weight rare earth butadiene provided by the invention, its step and condition are as follows:
(a) according to high-molecular-weight rare earth butadiene: dicyclopentadiene petroleum resin: stearic acid: zinc oxide: Sulfur: vulcanization accelerator: anti-aging agent: the mass ratio of carbon black is 100: 20: 2: 3: 3: 0.9: 1: 60, put into successively high-molecular-weight rare earth butadiene, dicyclopentadiene petroleum resin, stearic acid, zinc oxide, Sulfur, vulcanization accelerator, anti-aging agent and carbon black in mixing facilities, mix rear taking-up, obtain rubber unvulcanizate; Described high-molecular-weight rare earth butadiene
Cis-1,4 content=98.8%, the softening temperature of dicyclopentadiene petroleum resin are 134 ℃;
(b) by rubber unvulcanizate under 150 ℃, 10MPa condition, by the sulfurizing point time, vulcanize on vulcanizing press, make cross-linked rubber.The stretching tear resistance of cross-linked rubber is in Table 1.
Comparative Examples 2
In the formula of the rubber unvulcanizate of step (a), do not add dicyclopentadiene petroleum resin, high component rare earth polybutadiene rubber: the Sulfur mass ratio is 100: 1.5, and other step and formula and embodiment 2 are same.The stretching tear resistance of cross-linked rubber is in Table 1.
Embodiment 3
The working method of a kind of high-molecular-weight rare earth butadiene provided by the invention, its step and condition are as follows:
(a) according to high-molecular-weight rare earth butadiene: dicyclopentadiene petroleum resin: stearic acid: zinc oxide: Sulfur: vulcanization accelerator: anti-aging agent: the mass ratio of carbon black is 100: 20: 2: 3: 3: 0.9: 1: 60, by high-molecular-weight rare earth butadiene: dicyclopentadiene petroleum resin, stearic acid, zinc oxide, Sulfur, vulcanization accelerator, anti-aging agent and carbon black are put in mixing facilities successively, mix rear taking-up, obtain rubber unvulcanizate; Described high-molecular-weight rare earth butadiene
Cis-1,4 content=87%, the softening temperature of dicyclopentadiene petroleum resin are 134 ℃;
(b) by rubber unvulcanizate under 150 ℃, 10MPa condition, by the sulfurizing point time, vulcanize on vulcanizing press, make cross-linked rubber.The stretching tear resistance of cross-linked rubber is in Table 1.
Embodiment 4
The working method of a kind of high-molecular-weight rare earth butadiene provided by the invention, its step and condition are as follows:
(a) according to high-molecular-weight rare earth butadiene: dicyclopentadiene petroleum resin: stearic acid: zinc oxide: Sulfur: vulcanization accelerator: anti-aging agent: the mass ratio of carbon black is 100: 20: 2: 3: 3: 0.9: 1: 55, put into successively high-molecular-weight rare earth butadiene, dicyclopentadiene petroleum resin, stearic acid, zinc oxide, Sulfur, vulcanization accelerator, anti-aging agent and carbon black in mixing facilities, mix rear taking-up, obtain rubber unvulcanizate; Described high-molecular-weight rare earth butadiene
Cis-1,4 content=98.2%, the softening temperature of dicyclopentadiene petroleum resin are 120 ℃;
(b) by rubber unvulcanizate under 150 ℃, 10MPa condition, by the sulfurizing point time, vulcanize on vulcanizing press, make cross-linked rubber.The stretching tear resistance of cross-linked rubber is in Table 1.
Embodiment 5
The working method of a kind of high-molecular-weight rare earth butadiene provided by the invention, its step and condition are as follows:
(a) according to high-molecular-weight rare earth butadiene: dicyclopentadiene petroleum resin: stearic acid: zinc oxide: Sulfur: vulcanization accelerator: anti-aging agent: the mass ratio of carbon black is 100: 5: 2: 3: 2: 0.9: successively put into mixing rubber master batch, stearic acid, zinc oxide, Sulfur, vulcanization accelerator, anti-aging agent and carbon black in mixing facilities at 1: 60, mix rear taking-up, obtain rubber unvulcanizate; Described high-molecular-weight rare earth butadiene
Cis-1,4=98.8%, the softening temperature of dicyclopentadiene petroleum resin are 150 ℃;
(b) by rubber unvulcanizate under 150 ℃, 10MPa condition, by the sulfurizing point time, vulcanize on vulcanizing press, make cross-linked rubber.The stretching tear resistance of cross-linked rubber is in Table 1.
Embodiment 6
The working method of a kind of high-molecular-weight rare earth butadiene provided by the invention, its step and condition are as follows:
(a) according to high-molecular-weight rare earth butadiene: dicyclopentadiene petroleum resin: stearic acid: zinc oxide: Sulfur: vulcanization accelerator: anti-aging agent: the mass ratio of carbon black is 100: 30: 2: 3: 4: 0.9: 1: 50, put into successively high-molecular-weight rare earth butadiene, dicyclopentadiene petroleum resin, stearic acid, zinc oxide, Sulfur, vulcanization accelerator, anti-aging agent and carbon black in mixing facilities, mix rear taking-up, obtain rubber unvulcanizate; Described high-molecular-weight rare earth butadiene
Cis-1,4=98.8%, the softening temperature of dicyclopentadiene petroleum resin are 140 ℃;
(b) by rubber unvulcanizate under 150 ℃, 10MPa condition, by the sulfurizing point time, vulcanize and make cross-linked rubber on vulcanizing press.The stretching tear resistance of cross-linked rubber is in Table 1.
Under table 1 different condition, obtain the physical and mechanical properties table of cross-linked rubber
Claims (5)
1. the working method of a high-molecular-weight rare earth butadiene is characterized in that step and condition are as follows:
The weight-average molecular weight of the high-molecular-weight rare earth butadiene adopted
Scope is 6～17.5 * 10
5Between, molecular weight distribution
Scope is 3～14, and cis-Isosorbide-5-Nitrae content is 87～99%;
The softening temperature of the dicyclopentadiene petroleum resin adopted is 120～150 ℃;
(a) according to high-molecular-weight rare earth butadiene: dicyclopentadiene petroleum resin: stearic acid: zinc oxide: Sulfur: vulcanization accelerator: anti-aging agent: the mass ratio of carbon black is 100: 5～30: 2: 3: 2～4: 0.9: 1: 50～60, put into successively high-molecular-weight rare earth butadiene, dicyclopentadiene petroleum resin, stearic acid, zinc oxide, Sulfur, vulcanization accelerator, anti-aging agent and carbon black in mixing facilities, mix rear taking-up, obtain rubber unvulcanizate;
(b) by rubber unvulcanizate at 150 ℃, under the 10MPa condition, press sulfurizing point time sulfuration, make cross-linked rubber.
2. the working method of a kind of high-molecular-weight rare earth butadiene as claimed in claim 1, is characterized in that, its step and condition are as follows:
(a) according to high-molecular-weight rare earth butadiene: dicyclopentadiene petroleum resin: stearic acid: zinc oxide: Sulfur: vulcanization accelerator: anti-aging agent: the mass ratio of carbon black is 100: 20: 2: 3: 3: 0.9: 1: 60, put into successively high-molecular-weight rare earth butadiene, dicyclopentadiene petroleum resin, stearic acid, zinc oxide, Sulfur, vulcanization accelerator, anti-aging agent and carbon black in mixing facilities, mix rear taking-up, obtain rubber unvulcanizate; Described high-molecular-weight rare earth butadiene
Cis-Isosorbide-5-Nitrae content is 98.8%, and the softening temperature of described dicyclopentadiene petroleum resin is 134 ℃;
(b) by rubber unvulcanizate at 150 ℃, under the 10MPa condition, vulcanize on vulcanizing press by the sulfurizing point time, make cross-linked rubber.
3. the working method of a kind of high-molecular-weight rare earth butadiene as claimed in claim 1, is characterized in that, its step and condition are as follows:
(a) according to high-molecular-weight rare earth butadiene: dicyclopentadiene petroleum resin: stearic acid: zinc oxide: Sulfur: vulcanization accelerator: anti-aging agent: the mass ratio of carbon black is 100: 20: 2: 3: 3: 0.9: 1: 55, put into successively high-molecular-weight rare earth butadiene, dicyclopentadiene petroleum resin, stearic acid, zinc oxide, Sulfur, vulcanization accelerator, anti-aging agent and carbon black in mixing facilities, mix rear taking-up, obtain rubber unvulcanizate; Described high-molecular-weight rare earth butadiene
Cis-Isosorbide-5-Nitrae content is 98.2%, and the softening temperature of dicyclopentadiene petroleum resin is 120 ℃;
(b) by rubber unvulcanizate at 150 ℃, under the 10MPa condition, vulcanize on vulcanizing press by the sulfurizing point time, make cross-linked rubber.
4. the working method of a kind of high-molecular-weight rare earth butadiene as claimed in claim 1, is characterized in that, its step and condition are as follows:
(a) according to high-molecular-weight rare earth butadiene: dicyclopentadiene petroleum resin: stearic acid: zinc oxide: Sulfur: vulcanization accelerator: anti-aging agent: the mass ratio of carbon black is 100: 5: 2: 3: 2: 0.9: successively put into high-molecular-weight rare earth butadiene, dicyclopentadiene petroleum resin, stearic acid, zinc oxide, Sulfur, vulcanization accelerator, anti-aging agent and carbon black in mixing facilities at 1: 60, mix rear taking-up, obtain rubber unvulcanizate; Described high-molecular-weight rare earth butadiene
, cis-Isosorbide-5-Nitrae content is 98.8%, the softening temperature of dicyclopentadiene petroleum resin is 150 ℃;
(b) by rubber unvulcanizate at 150 ℃, under the 10MPa condition, vulcanize on vulcanizing press by the sulfurizing point time, make cross-linked rubber.
5. the working method of a kind of high-molecular-weight rare earth butadiene as claimed in claim 1, is characterized in that, its step and condition are as follows:
(a) according to high-molecular-weight rare earth butadiene: dicyclopentadiene petroleum resin: stearic acid: zinc oxide: Sulfur: vulcanization accelerator: anti-aging agent: the mass ratio of carbon black is 100: 30: 2: 3: 4: 0.9: 1: 50, put into successively high-molecular-weight rare earth butadiene, dicyclopentadiene petroleum resin, stearic acid, zinc oxide, Sulfur, vulcanization accelerator, anti-aging agent and carbon black in mixing facilities, mix rear taking-up, obtain rubber unvulcanizate; Described high-molecular-weight rare earth butadiene
Cis-Isosorbide-5-Nitrae content is 98.8%, and the softening temperature of dicyclopentadiene petroleum resin is 140 ℃;
(b) by rubber unvulcanizate under 150 ℃, 10MPa condition, by the sulfurizing point time, vulcanize and make cross-linked rubber on vulcanizing press.
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| CN2010106040150A CN102120835B (en) | 2010-12-24 | 2010-12-24 | A kind of processing method of high molecular weight rare earth butadiene rubber |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102964646B (en) * | 2012-12-12 | 2014-10-29 | 中国科学院长春应用化学研究所 | Method for preparing dicyclopentadiene petroleum resin modified rubber |
| CN103289145B (en) * | 2013-06-24 | 2015-05-20 | 苏州新区佳合塑胶有限公司 | Impact-resistant high-temperature-resistant plastic comprising bicyclopentadiene |
| CN110016151B (en) * | 2018-01-08 | 2022-06-03 | 中国石油天然气股份有限公司 | Modified butadiene rubber and preparation method and application thereof |
| JP7346158B2 (en) * | 2019-08-22 | 2023-09-19 | Ｅｎｅｏｓ株式会社 | Sulfur-containing unsaturated hydrocarbon polymer and its production method, rubber additive, rubber composition, and tire |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1342719A (en) * | 2001-10-12 | 2002-04-03 | 中国科学院长春应用化学研究所 | Rare-earth catalyst system and its catalytic bis polymerizing process for butadiene |
| CN1356346A (en) * | 2001-12-14 | 2002-07-03 | 耿朝华 | Process for synthesizing petroleum resin by thermal polymerization method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1342719A (en) * | 2001-10-12 | 2002-04-03 | 中国科学院长春应用化学研究所 | Rare-earth catalyst system and its catalytic bis polymerizing process for butadiene |
| CN1356346A (en) * | 2001-12-14 | 2002-07-03 | 耿朝华 | Process for synthesizing petroleum resin by thermal polymerization method |
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