CN102553471B - Raw material premixing method for preparing rare earth isoprene rubber - Google Patents
Raw material premixing method for preparing rare earth isoprene rubber Download PDFInfo
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- CN102553471B CN102553471B CN201010594908.1A CN201010594908A CN102553471B CN 102553471 B CN102553471 B CN 102553471B CN 201010594908 A CN201010594908 A CN 201010594908A CN 102553471 B CN102553471 B CN 102553471B
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Abstract
The invention relates to a raw material premixing method for preparing rare earth isoprene rubber. The method comprises the steps of introducing precooled polymerization reactants into a ring tube mixer, and under the action of an axial-flow pump, subjecting the polymerization reactants to quick circularly flowing in the ring tube mixer, thereby violently mixing under a turbulent flow condition to form highly uniform polymerization reaction materials. By utilizing the method of the invention, since the highly uniform polymerization reaction material can be formed, the cis-1,4-polyisoprene rubber configuration content, the number-average molecular weight and the polydispersity index of the rare earth isoprene rubber product can be correspondingly improved, i.e., the quality of the obtained rare earth isoprene rubber product can be significantly improved.
Description
Technical field
The present invention relates to a kind of raw material premixing method of preparing rare-earth isoprene rubber, particularly, relate to a kind of method of utilizing endless tube blender to carry out rare-earth isoprene rubber raw material premix.
Background technology
Rare-earth isoprene rubber is the isoprene monomer polymer taking cis-Isosorbide-5-Nitrae construction unit as master that polymerisation in solution generates under rare earth catalyst effect.Because physical property is all similar to natural rubber (NR) with mechanical performance, rare-earth isoprene rubber is also referred to as " natural man-made rubber ".Particularly, rare-earth isoprene rubber has good elasticity, sealing, creep resistant, wearability, heat resistance and tear resistance, and tensile strength and percentage elongation also approach natural rubber, therefore can be used as in some cases the substitute of natural rubber, also can be used in combination with natural rubber (NR) or other synthetic rubber.Therefore, rare-earth isoprene rubber is widely used in the rubber processings such as tire, adhesive tape, sebific duct.
In the solution polymerization process of preparing rare-earth isoprene rubber, the premix state of polymerisation material (comprising isoprene monomer, solvent and catalyst) will directly affect cis-configuration content, the molecular weight and molecualr weight distribution of speed, catalyst amount and gained rubber product of subsequent polymerisation reaction.Therefore, before carrying out isoprene monomer solution polymerization, need to create a good mass transfer environment, polymerisation material can fully be mixed, the uniform mixture of height of formation.
In the prior art, for the solution polymerization process of preparing rare-earth isoprene rubber, conventional raw material premix process adopts static mixer to carry out more, but because static mixer exists fluid stagnant area conventionally in exit, therefore, material flow skewness, disturbance effect is poor, causes mixed effect not ideal enough.
In addition, in the prior art, for the solution polymerization process of preparing rare-earth isoprene rubber; conventionally also adopt the stirring autoclave blender of structure relative complex as raw material premixed device; wherein, under the effect of paddle, material turbulent extent strengthens, and causes mixed effect to be strengthened.But due to the characteristic of paddle, near material suffered shearing force blade is larger, less at the still wall away from blade and liquid level place shearing force, therefore easily form dead band in these regions, cause the interior local mixing effect of stirred tank not ideal enough.If improve this undesirable mixed effect, often need to arrange inner member, the structure in stirred tank is inevitable more complicated like this, and energy consumption is corresponding increase also, adds the existence of rotatable parts, and whole plant maintenance is got up more difficult.
US005397179A discloses a kind of device mixing for fluid, and described device is the tubular type turbulent flow mixing arrangement with diffusion-contraction section.2003, Russian Kauchuk company built up first set ton rare-earth isoprene rubber process units in the world, wherein just adopts the tubular type turbulent flow mixing arrangement in above-mentioned United States Patent (USP) to carry out raw material premix.This class mixing arrangement is in fact suitable with static mixer, and just wherein material experiences diffusion and contraction causes turbulent diffusivity to improve repeatedly, and the mixing between material is strengthened, and then mixes more even.But the shortcoming of this fluid mixer is to be difficult for processing and manufacturing.
CN201415984Y discloses a kind of premixing device for rare-earth isoprene rubber production, comprising the pipeline super mixer being in series and premix still.For the solution polymerization process of preparing rare-earth isoprene rubber, before entering polymeric kettle, the microcosmic that polymerisation material can reach height after this pre-mixing apparatus premix evenly mixes, thereby improve the catalytic efficiency of catalyst, and reduce the degree of branching of product, make molecular weight distribution more even, finally improved the product quality of isoprene rubber.But the shortcoming of this pre-mixing apparatus is, the long period that the mean residence time of material in premix still is 20-30min, then, after the polymerization reaction kettle reaction of many series connection, final conversion ratio can only reach 85-90wt%, and therefore production capacity is lower.
Therefore, for the solution polymerization process of preparing rare-earth isoprene rubber, require further improvement the premix process of polymerisation material, thereby further improve the quality of gained rare-earth isoprene rubber product, improve production capacity simultaneously and reduce energy consumption.
Summary of the invention
For the above-mentioned problems in the prior art, the invention provides a kind of raw material premixing method of preparing rare-earth isoprene rubber, for the premix of rare-earth isoprene rubber preparation process polymerisation material (comprising isoprene monomer, catalysts and solvents).
Particularly, the invention provides a kind of raw material premixing method of preparing rare-earth isoprene rubber, endless tube blender introduced by the polymerisation material of cooling mistake in advance by the method, wherein under axial-flow pump effect, polymerisation material Rapid Circulation in described endless tube blender is flowed, thereby under turbulent-flow conditions, be acutely mixed to form polymerisation material highly uniformly.
In the raw material premixing method of preparing rare-earth isoprene rubber of the present invention, wherein said endless tube blender has at least two straight lengths, the ratio of height to diameter of described straight length is 2-100, be preferably 3-50, more preferably 4-20, described straight length interconnects to form endless tube at two ends by elbow, and described endless tube blender is provided with import and outlet in bottom, is respectively used to introduce and discharge polymerisation material.
In the raw material premixing method of preparing rare-earth isoprene rubber of the present invention, each component in polymerisation material does not preferably enter described endless tube blender with the form of mixture together, isoprene monomer at least wherein and catalyst need to enter described endless tube blender from different imports, solvent can enter separately, also can enter described endless tube blender with together with any among the above two.The object of operation is the generation in order to avoid better prepolymerization reaction like this, thereby is conducive to follow-up married operation and follow-up solution polymerization.
Therefore, in the raw material premixing method of preparing rare-earth isoprene rubber of the present invention, wherein said endless tube blender is preferably provided with three imports to introduce respectively isoprene monomer, catalysts and solvents in bottom, more preferably be provided with two imports to introduce respectively isoprene monomer and catalyst, now consider that the inlet amount of isoprene monomer and solvent in solution polymerization process is all far above the inlet amount of catalyst, most preferred solvent is introduced together with catalyst.
In the raw material premixing method of preparing rare-earth isoprene rubber of the present invention, wherein said endless tube blender is connected with described axial-flow pump in bottom, and wherein controls the circular flow Q of polymerisation material in described endless tube internal mixer
rwith the rate of discharge Q that flows out described endless tube blender
outratio Q
r/ Q
outfor 100-140, be preferably 120-130.
In the raw material premixing method of preparing rare-earth isoprene rubber of the present invention, described axial-flow pump can be any axial-flow pump usually used in this field, and those skilled in the art can correspondingly select according to the circular flow scope in the desired endless tube blender of process.
In the raw material premixing method of preparing rare-earth isoprene rubber of the present invention, due to the large flow effect of axial-flow pump, polymerisation material Rapid Circulation in described endless tube blender is flowed, in blender, substantially do not have dead band, all reaction masses can fully mix with the uniform mixture of height of formation under turbulent-flow conditions.
In the raw material premixing method of preparing rare-earth isoprene rubber of the present invention, can determine according to production scale inlet flow rate and the rate of discharge of polymerisation material, and can be accordingly correspondingly determine that the size of described endless tube blender for example determines the ratio of height to diameter of the straight length part of described endless tube blender, thereby making the mean residence time of polymerisation material in described endless tube blender is 0.5-5min, is preferably 2-4min.
In the raw material premixing method of preparing rare-earth isoprene rubber of the present invention, in order to avoid better the generation of prepolymerization reaction in described endless tube blender, control better the reaction temperature of subsequent solution polymerization, general by described polymerisation material in advance in cooler is cooled to certain low temperature range, at the temperature of be specifically cooled to-30-20 DEG C, preferably be cooled to-20-10 DEG C, be more preferably cooled to-10-0 DEG C.
In addition, in the raw material premixing method of preparing rare-earth isoprene rubber of the present invention, be similar to above for described in difference charging in endless tube blender, isoprene monomer and catalyst are preferably cooled to corresponding low temperature range through different coolers respectively in advance, solvent can be cooling separately, or cooling with together with any among the above two.
Correspondingly, in the raw material premixing method of preparing rare-earth isoprene rubber of the present invention, wherein preferably use three coolers with the cooling isoprene monomer of difference, catalysts and solvents, more preferably use two coolers with the cooling isoprene monomer of difference and catalyst, now consider that the inlet amount of isoprene monomer and solvent in solution polymerization process is all far above the inlet amount of catalyst, most preferred solvent is cooling together with catalyst.
In the raw material premixing method of preparing rare-earth isoprene rubber of the present invention, described cooler can be the conventional cooler in this area, for example, can be plate type heat exchanger, and cooling medium wherein can be water at low temperature and chilled brine, is preferably chilled brine.
In the raw material premixing method of preparing rare-earth isoprene rubber of the present invention, isoprene monomer will carry out solution polymerization under rare earth catalyst effect.Therefore, described isoprene monomer is generally polymer grade, can be commercially available, and described rare earth catalyst can be any suitable catalyst conventional in this area, for example neodymium series catalysts, and described solvent is generally inert hydrocarbon solvent.
The formerly patent application that described neodymium series catalysts is applicant, the Chinese patent application that can be specifically 200910244026.X referring to application number, this patent application is introduced by reference to full text at this.
More specifically, mainly to comprise conjugated diene, carboxylic acid neodymium compound, general formula be AlR to described neodymium series catalysts
3alkyl aluminum or general formula be AlHR
2alkyl aluminium hydride or the two mixture (wherein R is C
1-C
6straight or branched alkyl) and halogen contained compound, wherein taking every moles of carboxylic acids neodymium compound as benchmark, the content of described conjugated diene is about 20-100 mole, be preferably about 25-80 mole, more preferably about 30-70 mole, the content of described alkyl aluminum or alkyl aluminium hydride or the two mixture is about 5-30 mole, is preferably about 6-25 mole, with the content of described halogen contained compound be about 2-10 mole, be preferably about 2-4 mole.
'inertia' in described " inert hydrocarbon solvent " taking not negative interference mixing and course of reaction and/or not with material component and reaction as principle.Particularly, the example of described inert hydrocarbon solvent can be selected from pentane, isopentane, hexane, cyclohexane, hexahydrotoluene, heptane, octane, benzene,toluene,xylene and isopropylbenzene.
In the raw material premixing method of preparing rare-earth isoprene rubber of the present invention, in polymerisation material, the inlet amount of each component can be determined according to the requirement of subsequent solution polymerisation.Particularly, the isoprene monomer concentration in polymerisation material can be 10-20wt%, is preferably 13-17wt%, taking the gross weight of whole polymerisation material as benchmark; The consumption of described catalyst should the principle based on industrial economy suitably be selected, can not be too small or excessive, and for example, taking neodymium series catalysts as example, taking every mole of isoprene monomer as benchmark, the consumption of described neodymium series catalysts can be 1 × 10 conventionally
-5-4 × 10
-4molNd, is preferably 1.5 × 10
-5-2.5 × 10
-4molNd.
In the raw material premixing method of preparing rare-earth isoprene rubber of the present invention, owing to adopting endless tube blender to carry out the premix of polymerisation material, can obtain mixture highly uniformly, make catalyst in mixture, obtain high degree of dispersion, and then improve catalytic efficiency.
In the time utilizing the polymerisation material obtaining by the inventive method to carry out the solution polymerization of isoprene monomer, total polymeric reaction temperature is-30-80 DEG C, be preferably 0-70 DEG C, more preferably 10-60 DEG C, with total polymerization reaction time be 20-300 minute, be preferably 100-200 minute, the rare-earth isoprene rubber product obtaining can have relatively high cis-1,4-configuration content, relatively high number-average molecular weight and relatively low molecular weight distribution coefficient, the rare-earth isoprene rubber product quality obtaining with respect to prior art can have obvious improvement.
More specifically, when the polymerisation material that utilizes the inventive method to obtain carries out the solution polymerization of isoprene monomer, cis-1 of the rare-earth isoprene rubber obtaining, 4-configuration content can reach 98wt%, number-average molecular weight can reach 400,000, can reach below 3 with molecular weight distribution coefficient, for example, be 2.7-2.9.
As cis-Isosorbide-5-Nitrae-configuration content, number-average molecular weight and molecular weight distribution coefficient, can adopt oneself any appropriate method of knowing of this area to measure for the mass parameter of described rare-earth isoprene rubber product.
Particularly, in the present invention, the microstructure of the rare-earth isoprene rubber product of synthesized adopts German Bruker Tensor 27 mid-infrared light spectrometers and German Bruker 400MHz nmr determination, and solvent is deuterochloroform; Molecular weight and molecualr weight distribution adopts Shimadzu LC-10AT type gel permeation chromatograph (GPC) to measure, and THF is mobile phase, and Narrow distribution polystyrene is standard specimen, and temperature is 25 DEG C; Wherein in sample preparation process: it is to carry out mixing 70 ± 5 times in roller temperature that rubber adopts mill; Curing temperature is 145 DEG C, and cure time is 20min; In sulfuration basic components, rubber 100g; Carbon black 45g; Sulphur 2g; Accelerant CZ (N-cyclohexyl 2-phenylpropyl alcohol thiazolesulfenamide) 0.9g; Stearic acid 4g; Zinc oxide 5g; And vulcanizating glue physical performance adopts the Taiwan high ferro tester GT-7012-D of company type abrasion machine to measure.
Brief description of the drawings
Further describe with reference to the accompanying drawings the present invention, wherein:
Fig. 1 is the schematic diagram of applied endless tube blender in the inventive method, and wherein said endless tube blender has two straight lengths.In Fig. 1, the implication of each Reference numeral is as follows: 1-endless tube blender; 2-axial-flow pump; 3,4-blender material inlet; 5-blender material outlet; With
Fig. 2 utilizes the polymerisation material of the inventive method acquisition to carry out the schematic flow sheet of isoprene monomer solution polymerization, after wherein said endless tube blender, connect the equal-volume reactor of three series connection, and each reactor all carries out isothermal operation by chuck temperature control.
Detailed description of the invention
The present invention is described in further detail by the following examples, but these embodiment should not think limitation of the scope of the invention.
Embodiment 1
At normal temperatures and pressures, first by the isoprene monomer (23.5kg/h in the polymerisation material for the preparation of rare-earth isoprene rubber, polymer grade, commercially available), solvent (152kg/h, solvent as used herein is cyclohexane, commercially available) and neodymium series catalysts (4.5kg/h, concentration is 6 × 10
-6molNd/ml, solvent is cyclohexane, the concrete composition of neodymium series catalysts as used herein is isoprene by the molar ratio computing of each component: neodymium caprate: triisobutyl aluminium: aluminium diethyl monochloride=50: 1: 10: 3, this catalyst is prepared voluntarily by applicant and the neodymium series catalysts cyclohexane preparing is diluted to above-mentioned concentration) in traditional heat exchanger, carry out precooling, precooling temperature is-5 DEG C.Wherein, after catalysts and solvents is pre-mixed, again through heat exchanger precooling, isoprene monomer is precooling in independent heat exchanger.At this, the sodium chloride chilled brine that the cooling medium using is 3wt%.
Then, each component of the polymerisation material after precooling is incorporated into respectively and in endless tube blender, carries out premix, wherein said isoprene monomer is introduced in endless tube blender through material inlet 3 after outflow heat exchanger, and described catalysts and solvents is introduced in endless tube blender through material inlet 4 after outflow heat exchanger.
Under axial-flow pump effect, polymerisation material is Rapid Circulation in described endless tube blender, wherein makes the circular flow Q of polymerisation material in described endless tube blender
rwith the rate of discharge Q that flows out described endless tube blender
outratio Q
r/ Q
outbe 100, and to make the mean residence time of polymerisation material in described endless tube blender be 1.5min.
Next, carry out the solution polymerization operation of isoprene monomer according to flow process shown in Fig. 2.The uniform polymerisation material forming after described endless tube blender premix enters successively in each reactor and reacts, be 30min with the mean residence time in each reactor, wherein the reaction temperature of each reactor inside is controlled at 30 DEG C, 40 DEG C and 50 DEG C successively.
According to this embodiment, the final conversion ratio of isoprene monomer is 95wt%.
Finally, cis-Isosorbide-5-Nitrae-configuration content, number-average molecular weight and the molecular weight distribution coefficient of the rare-earth isoprene rubber product that this embodiment of Analysis deterrmination obtains, the results are shown in following table 1.
Embodiment 2:
Substantially repeat embodiment 1, just wherein make the Q of described endless tube blender
r/ Q
outbe 125.
According to this embodiment, the final conversion ratio of isoprene monomer is 96wt%.
The quality analysis of having reacted rear obtained rare-earth isoprene rubber product the results are shown in following table 1.
Embodiment 3
Substantially repeat embodiment 1, just wherein make the Q of described endless tube blender
r/ Q
outbe 140.
According to this embodiment, the final conversion ratio of isoprene monomer is 96.3wt%.
The quality analysis of having reacted rear obtained rare-earth isoprene rubber product the results are shown in following table 1.
Embodiment 4:
Substantially repeat embodiment 1, just wherein make the Q of described endless tube blender
r/ Q
outbe 125, and reduce the inlet amount of total polymerisation material, and the maintenance isoprene monomer identical with embodiment 1, the mass ratio of catalysts and solvents, making the mean residence time of polymerisation material in described endless tube blender is 2.5min.
According to this embodiment, the final conversion ratio of isoprene monomer is 96.8wt%.
The quality analysis of having reacted rear obtained rare-earth isoprene rubber product the results are shown in following table 1.
Embodiment 5:
Substantially repeat embodiment 1, just wherein make the Q of described endless tube blender
r/ Q
outbe 125, and reduce the inlet amount of total polymerisation material, and the maintenance isoprene monomer identical with embodiment 1, the mass ratio of catalysts and solvents, making the mean residence time of polymerisation material in described endless tube blender is 4min.
According to this embodiment, the final conversion ratio of isoprene monomer is 97.2wt%.
The quality analysis of having reacted rear obtained rare-earth isoprene rubber product the results are shown in following table 1.
Comparative example 1:
The basic embodiment 1 that repeats, just wherein the each component of polymerisation material after precooling, without the premix stage of endless tube blender, is reacted but be fed directly in each reactor of polymerization stage.
According to this comparative example, the final conversion ratio of isoprene monomer is 90wt%.
The quality analysis of having reacted rear obtained rare-earth isoprene rubber product the results are shown in following table 1.
Comparative example 2:
The basic comparative example 1 that repeats, just rises to original twice by the consumption of catalyst wherein.
According to this comparative example, the final conversion ratio of isoprene monomer is 95wt%.
The quality analysis of having reacted rear obtained rare-earth isoprene rubber product the results are shown in following table 1.
Table 1
Can be found out by table 1 column data, according to the present invention, when polymerisation material after utilizing endless tube blender to precooling carries out premix production rare-earth isoprene rubber, owing to can obtaining polymerisation material highly uniformly, make cis-1 of obtained isoprene rubber product, 4-configuration content obviously higher, number-average molecular weight is larger and molecular weight distribution coefficient is less, and the isoprene rubber product quality that obtained is better.
Claims (10)
1. prepare the raw material premixing method of rare-earth isoprene rubber for one kind, endless tube blender introduced by the polymerisation material of cooling mistake in advance by the method, wherein under axial-flow pump effect, polymerisation material Rapid Circulation in described endless tube blender is flowed, wherein control the circular flow Q of polymerisation material in described endless tube internal mixer
rwith the rate of discharge Q that flows out described endless tube blender
outratio Q
r/ Q
outfor 100-140, and to make the mean residence time of described polymerisation material in described endless tube blender be 0.5-5min, thereby under turbulent-flow conditions, be acutely mixed to form polymerisation material highly uniformly.
2. the method for claim 1, wherein said endless tube blender has at least two straight lengths, the ratio of height to diameter of described straight length is 2-100, described straight length interconnects to form endless tube at two ends by elbow, be provided with import and outlet in bottom with described endless tube blender, be respectively used to introduce and discharge polymerisation material.
3. the method for claim 2, the ratio of height to diameter of the straight length of wherein said endless tube blender is 3-50.
4. the method for claim 3, the ratio of height to diameter of the straight length of wherein said endless tube blender is 4-20.
5. the method for claim 2-4 any one, wherein said endless tube blender is provided with two imports in bottom, and one for introducing the isoprene monomer of polymerisation material, and another is for introducing the catalysts and solvents of polymerisation material.
6. the method for claim 1-4 any one, wherein said endless tube blender is connected with described axial-flow pump in bottom, and wherein controls the circular flow Q of polymerisation material in described endless tube internal mixer
rwith the rate of discharge Q that flows out described endless tube blender
outratio Q
r/ Q
outfor 120-130.
7. the method for claim 1-4 any one, the mean residence time of wherein said polymerisation material in described endless tube blender is 2-4min.
8. the method for claim 1-4 any one, wherein apply two coolers, an isoprene monomer for cooling polymerisation material, and another is for the catalysts and solvents of cooling polymerisation material, be-30-20 DEG C of the target temperature of each cooling down operation.
9. the method for claim 8, be wherein-20-10 DEG C of the target temperature of each cooling down operation.
10. the method for claim 8, be wherein-10-0 DEG C of the target temperature of each cooling down operation.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010594908.1A CN102553471B (en) | 2010-12-09 | 2010-12-09 | Raw material premixing method for preparing rare earth isoprene rubber |
| PCT/CN2011/083777 WO2012075964A1 (en) | 2010-12-09 | 2011-12-09 | Neodymium based homogeneous phase rare earth catalyst and use thereof |
| BR112013014478-5A BR112013014478B1 (en) | 2010-12-09 | 2011-12-09 | CATALYST OF RARE LANDS WITH A HOMOGENEAL PHASE BASED ON NEODYME AND PROCESS TO PREPARE A POLYMER OF CONJUGATED DIENO |
| EP11846459.3A EP2650313B1 (en) | 2010-12-09 | 2011-12-09 | Neodymium based homogeneous phase rare earth catalyst and use thereof |
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|---|---|---|---|
| CN201010594908.1A CN102553471B (en) | 2010-12-09 | 2010-12-09 | Raw material premixing method for preparing rare earth isoprene rubber |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1172817A (en) * | 1996-07-19 | 1998-02-11 | 蒙岱尔北美股份有限公司 | Process for producing polyolefin grafted copolymers |
| CN201415984Y (en) * | 2009-05-06 | 2010-03-03 | 淄博齐鲁乙烯鲁华化工有限公司 | Premixing device for rare-earth isoprene rubber production |
-
2010
- 2010-12-09 CN CN201010594908.1A patent/CN102553471B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1172817A (en) * | 1996-07-19 | 1998-02-11 | 蒙岱尔北美股份有限公司 | Process for producing polyolefin grafted copolymers |
| CN201415984Y (en) * | 2009-05-06 | 2010-03-03 | 淄博齐鲁乙烯鲁华化工有限公司 | Premixing device for rare-earth isoprene rubber production |
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| Title |
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| 王定松.环管反应器在顺丁橡胶生产中的应用前景.《合成橡胶工业》.1995,第18卷(第4期),208. |
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