CN102898565A - Cooling method for isoprene rubber polymerization reaction - Google Patents
Cooling method for isoprene rubber polymerization reaction Download PDFInfo
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- CN102898565A CN102898565A CN2011102169631A CN201110216963A CN102898565A CN 102898565 A CN102898565 A CN 102898565A CN 2011102169631 A CN2011102169631 A CN 2011102169631A CN 201110216963 A CN201110216963 A CN 201110216963A CN 102898565 A CN102898565 A CN 102898565A
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Abstract
The invention relates to a cooling method for an isoprene rubber polymerization reaction. In a polymerization reaction kettle with a double helical ribbon agitator, a plurality of radial push type scrapers closely matched with a kettle wall are added between ribbons on external sides of double helical ribbon agitator blades; a frictioning direction of the radial push type scrapers and a stirring tangent direction form an angle of 30-60 DEG; adjacent radial pushing type scrapers are uniformly distributed in 30-180 DEG; the radial pushing type scrapers are fixed on a fixed bracket; and the fixed bracket is fixed on an agitating shaft between the ribbons of the double helical ribbon agitator blades, and can rotate coaxially with the double helical ribbon agitator blades. When isoprene is subjected to a continuous polymerization reaction under effect of rare earth catalyst, and a conversion rate reaches 50%, the push type scrapers are used to clean high-viscosity glue attached to the polymerization reaction kettle wall in the polymerization process, so as to control a polymerization reaction temperature at 44-46 DEG C. The method reduces thermal resistance at the kettle wall, improves mass transfer and heat transfer of a high viscosity system in later stage of the polymerization reaction and realizes a smooth and controllable temperature.
Description
Technical field:
The present invention relates to the thermal means of removing of the high sticking system of a kind of rare-earth isoprene rubber polymerization reaction late stage.
Background technology
Polyisoprene rubber is high-cis (suitable-Isosorbide-5-Nitrae content is 95%～98%) synthetic rubber that is made by isoprene, and its structure is similar to natural rubber with performance, and the natural synthetic rubber that is otherwise known as can replace natural rubber to be used for tire manufacturing and field of medicaments.
The isoprene solution polymerization prepares polyisoprene rubber and belongs to thermopositive reaction, and along with the viscosity of carrying out reaction mass of polyreaction is increasing, reaction mass is high viscosity systems during to polymerization reaction late stage.Therefore, the reaction heat that how to shift out fast in the high sticking system of polyisoprene rubber is the gordian technique that guarantees production equipment smooth running and quality product.At present, in order to solve the problem that shifts out of isoprene polymerization heat, adopt many still series connection to carry out polyreaction, strengthen heat transfer area, generally adopt 3～4 polymeric kettle series connection; Adopt and to add interchanger in the mode of reaction mass still outer circulation and the still and carry out polyreaction and remove heat; Fill cold solvent in the polyreaction different steps, utilize reaction heat heats cold solvent and the solvent latent heat of vaporization to take away reaction heat; Improve the polymeric kettle stirring pattern, as: the agitator that periodical operation is adopted has general energy formula, maximum blade formula, super blades formula and combined impeller etc.; Operate continuously adopts band to scrape the stirring of wall mechanism, reaches the effect that shifts out heat of polymerization thereby improve heat transfer efficiency.
Prior art is when isoprene polymerization initial reaction stage and mid-term, can effectively reaction heat be shifted out, the assurance temperature-stable is controlled, but the increasing along with the polymeric gel fluid viscosity, it is also more and more difficult to shift out reaction heat from polymeric kettle, particularly polymerization later stage glue belongs to high sticking system, can not shift out timely and effectively reaction heat, is difficult to polymerization temperature is controlled at set(ting)value.Quantity that can be by increasing the series connection still and adopt the still outer circulation increases heat transfer area, but can increase power consumption, and is unfavorable to scale production, and the rare-earth isoprene rubber polymerization reaction late stage belongs to high sticking system, is difficult to realize that the still outer circulation removes heat.Filling cold solvent can effectively reach and remove hot purpose, but experiment finds that rare-earth isoprene rubber polymerization later stage gelatin viscosity is too large, and cold solvent can not well mix with glue, removes on the one hand the thermal effect variation, cause on the other hand the temperature difference large, temperature distributing disproportionation affects polyreaction.Can also improve heat and mass effect in the still by changing stirring pattern, a lot of about the research of cis-1,4-polybutadiene rubber in this respect.Cis-1,4-polybutadiene rubber belongs to adiabatic reaction, and main purpose is more to be tending towards rationally not needing to control lower polymeric reaction temperature in order to reach temperature distribution, and cis-1,4-polybutadiene rubber end still temperature of reaction can reach 95 ℃, and the temperature height is insensitive on the quality product impact.The rare-earth isoprene rubber polyreaction needs strict control temperature of reaction, temperature of reaction should not be above 50 ℃, polymeric reaction temperature is to affect rare-earth isoprene rubber 1, the principal element of 4-cis-structure content, along with the rising of temperature of reaction 1,4-cis-structure content, therefore effectively shifting out isoprene polymerization reaction heat is the key that guarantees the rare-earth isoprene rubber quality product.
Summary of the invention
The present invention seeks to improve polyisoprene rubber polymerization reaction kettle blade structure and modes of emplacement, a kind of method that the high sticking system of rare-earth isoprene rubber polymerization reaction late stage is removed heat that is suitable for is provided.
A kind of polyisoprene rubber polyreaction of the present invention is removed thermal means: in the polymerization reaction kettle with two helical ribbon agitators, between the ribbon in the two ribbon stirring rakes outside, set up several and the close-fitting radially pusher scraper plate of still wall, radially pusher scraper plate frictioning direction is 30～60 degree with stirring the tangential direction angle, adjacent radially pusher scraper plate is 30～180 degree and evenly distributes, radially pusher scraper plate is fixed on the fixed support, fixed support is fixed on the stir shaft between two ribbon stirring rake ribbons, can be with two ribbon stirring rake coaxial rotatings, can be free to remove and replace, when isoprene carries out the successive polymerization reaction under the rare earth catalyst effect, when transformation efficiency reaches 50%, adopt the high viscosity glue that is attached in the pusher drag flight descaling polymerization process on the polymerization reaction kettle wall, make polymeric reaction temperature be controlled at 44～46 ℃.
When isoprene carries out the successive polymerization reaction under the rare earth catalyst effect, polymerization reaction kettle adopted pusher scraper plate to solve the heat problem of removing of high sticking system when transformation efficiency reached 50%, gained rare-earth isoprene rubber Isosorbide-5-Nitrae-cis-content 〉=96%, molecular weight distribution are 2.0～3.0.
The present invention compared with prior art has following significant progress and positive effect:
1. solved the difficult control problem of rare-earth isoprene rubber polymerization temperature, blade structure and modes of emplacement have been improved, adopt radially pusher scraper plate can reduce still wall place thermal resistance, reaction heat is in time taken away by the cryogen in the chuck by the still wall, make temperature of reaction steadily controlled reasonable with distribution, guarantee that rare-earth isoprene rubber Isosorbide-5-Nitrae-cis-structure content reaches more than 96%.
2. solved rare-earth isoprene rubber polymeric kettle still wall hanging glue problem, scraper plate can closely cooperate with the still wall all the time, guarantees the polyreaction long-period stable operation.
3. effectively improve mass transfer and the heat transfer of the high sticking system of polymerization reaction late stage, improve high viscose mixed effect, avoid local reaction strong, reduce gel content and stable molecule amount and distribute.
Embodiment
Embodiment 1
On the continuous polymerization unit of three series connection polymeric kettles, isoprene is under the rare earth catalyst effect, and take hexane as solvent, monomer concentration is 100g/L, and polymeric reaction temperature is controlled between 40～50 ℃, carries out polyreaction.
Be attached to the high viscosity glue on the still wall in the pusher drag flight descaling polymerization process of the interior employing of end still still, scraper plate is placed between the ribbon of two ribbon stirring arms in the still, and its frictioning direction is spent with stirring tangential direction angle 30, and closely cooperates all the time with the still wall.
Move continuously by long period, last still polymeric reaction temperature basic controlling is at 44～46 ℃, temperature do not occur with the reaction times phenomenon rambunctious that raises gradually, and temperature is steadily controlled.Products obtained therefrom Isosorbide-5-Nitrae-cis-content 96.8%, molecular weight distribution are 2.4, and mooney viscosity is 95.
Embodiment 2
On the continuous polymerization unit of three series connection polymeric kettles, isoprene is under the rare earth catalyst effect, and take hexane as solvent, monomer concentration is 120g/L, and polymeric reaction temperature is controlled between 40～50 ℃, carries out polyreaction.
Be attached to the high viscosity glue on the still wall in the last still still in the pusher drag flight descaling polymerization process of employing, scraper plate is placed between the ribbon of the interior two ribbons stirrings of still, and its frictioning direction is spent with stirring tangential direction angle 60, and closely cooperates all the time with the still wall.
Move continuously by long period, last still polymeric reaction temperature basic controlling is at 48～50 ℃, temperature do not occur with the reaction times phenomenon rambunctious that raises gradually, and temperature is steadily controlled.Products obtained therefrom Isosorbide-5-Nitrae-cis-content 96.1%, molecular weight distribution are 2.6, mooney viscosity 93.
Comparative example 1
On the continuous polymerization unit of three series connection polymeric kettles, isoprene is under the rare earth catalyst effect, and take hexane as solvent, monomer concentration is 100g/L, and polymeric reaction temperature is controlled between 40～50 ℃, carries out polyreaction.Polymerization reaction late stage, last still adopts the reactor that contains chuck, is provided with two ribbons in the still and stirs, and removes heat by the chuck cryogen.
By continuous operation, last still polymeric reaction temperature fluctuation is large, is difficult to be controlled at below 50 ℃, and the polymerization conversion fluctuation is large, and the violent phenomenon of local reaction is arranged, and glue transfer pressure between still falls greatly, is difficult to guarantee long-period stable operation.Products obtained therefrom Isosorbide-5-Nitrae-cis-content 93.8%, molecular weight distribution are 2.7, mooney viscosity 91.
Claims (1)
1. a polyisoprene rubber polyreaction is removed thermal means, it is characterized in that: in the polymerization reaction kettle with two helical ribbon agitators, between the ribbon in the two ribbon stirring rakes outside, set up several and the close-fitting radially pusher scraper plate of still wall, radially pusher scraper plate frictioning direction is 30～60 degree with stirring the tangential direction angle, adjacent radially pusher scraper plate is 30～180 degree and evenly distributes, radially pusher scraper plate is fixed on the fixed support, fixed support is fixed on the stir shaft between two ribbon stirring rake ribbons, can be with two ribbon stirring rake coaxial rotatings, when isoprene carries out the successive polymerization reaction under the rare earth catalyst effect, when transformation efficiency reaches 50%, adopt the high viscosity glue that is attached in the pusher drag flight descaling polymerization process on the polymerization reaction kettle wall, make polymeric reaction temperature be controlled at 44～46 ℃.
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| CN2011102169631A CN102898565A (en) | 2011-07-29 | 2011-07-29 | Cooling method for isoprene rubber polymerization reaction |
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| CN2011102169631A CN102898565A (en) | 2011-07-29 | 2011-07-29 | Cooling method for isoprene rubber polymerization reaction |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104650265A (en) * | 2013-11-19 | 2015-05-27 | 中国石油天然气股份有限公司 | Heat-removal method in polymerization reaction of synthetic rubber through solution polymerization |
| CN110088144A (en) * | 2016-12-26 | 2019-08-02 | 东亚合成株式会社 | The manufacturing method of polymer particles |
Citations (3)
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| CN101091901A (en) * | 2007-04-13 | 2007-12-26 | 青岛伊科思新材料股份有限公司 | Helix stirred reactor with cryogen gong through inside, application, and technical method of polyreaction |
| CN101234309A (en) * | 2007-11-16 | 2008-08-06 | 中国石油大学(北京) | Double helical ribbon multi-layer oar blade scraping cutter type stirrer |
| CN101492514A (en) * | 2009-03-05 | 2009-07-29 | 中国科学院长春应用化学研究所 | High cis-, low-molecular weight narrow-molecular weight distribution polyisoprene and method for preparing the same |
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2011
- 2011-07-29 CN CN2011102169631A patent/CN102898565A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101091901A (en) * | 2007-04-13 | 2007-12-26 | 青岛伊科思新材料股份有限公司 | Helix stirred reactor with cryogen gong through inside, application, and technical method of polyreaction |
| CN101234309A (en) * | 2007-11-16 | 2008-08-06 | 中国石油大学(北京) | Double helical ribbon multi-layer oar blade scraping cutter type stirrer |
| CN101492514A (en) * | 2009-03-05 | 2009-07-29 | 中国科学院长春应用化学研究所 | High cis-, low-molecular weight narrow-molecular weight distribution polyisoprene and method for preparing the same |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104650265A (en) * | 2013-11-19 | 2015-05-27 | 中国石油天然气股份有限公司 | Heat-removal method in polymerization reaction of synthetic rubber through solution polymerization |
| CN104650265B (en) * | 2013-11-19 | 2017-01-04 | 中国石油天然气股份有限公司 | A kind of solution polymerization process synthetic rubber polyreaction removes by the use of thermal means |
| CN110088144A (en) * | 2016-12-26 | 2019-08-02 | 东亚合成株式会社 | The manufacturing method of polymer particles |
| US11208508B2 (en) | 2016-12-26 | 2021-12-28 | Toagosei Co. Ltd. | Polymer fine particles manufacturing method |
| CN110088144B (en) * | 2016-12-26 | 2022-02-08 | 东亚合成株式会社 | Method for producing polymer microparticles |
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Application publication date: 20130130 |