CN102485756B - Adiabatic polymerization method of rare-earth isoprene rubber - Google Patents
Adiabatic polymerization method of rare-earth isoprene rubber Download PDFInfo
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- CN102485756B CN102485756B CN201010580720.1A CN201010580720A CN102485756B CN 102485756 B CN102485756 B CN 102485756B CN 201010580720 A CN201010580720 A CN 201010580720A CN 102485756 B CN102485756 B CN 102485756B
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Abstract
The invention relates to an adiabatic polymerization method of rare-earth isoprene rubber, comprising the following steps: letting an isoprene monomer and organic solvent enter a first polymerization reactor of three polymerization reactors in series at a room temperature, simultaneously adding a rare earth catalyst, reacting for 1-6h, after the reaction, adding a hexane solution containing 0.5 % of antioxidant 2,6-di-tert-butyl-para-methyl phenol to terminate the reaction, wherein 5-20g of the isoprene monomer is in every 100 mL of hexane, the ratio of the Nd mole number of the catalyst to the gram number of the monomer is 1*10<-7>-1*10<-6>:1. According to the method, the energy consumption in the production of the rare-earth isoprene rubber can be greatly reduced, the energy consumption is reduced by about 50-60 %, thus the production cost of the rare-earth isoprene rubber is greatly reduced; and the molecular weight distribution of the produced rare-earth isoprene rubber is unimodal, and the cis content is larger than 97 wt%.
Description
Technical field:
The present invention relates to a kind of adiabatic polymerization method of rare-earth isoprene rubber.
Background technology:
Natural rubber is the most important raw material that tire is manufactured, and is and national economy and the closely-related valuable cargo of national security.China's natural rubber inadequate resource, development space is extremely limited.Simultaneously China is again natural rubber consumption big country, and the degree of self-sufficiency is serious, therefore greatly develops that natural synthetic rubber---the necessity and urgency of polyisoprene rubber need not be put speech.
Polyisoprene rubber is that the important component of take in ethylene project by-product carbon five resources---isoprene is monomer, by the high-cis polyisoprene rubber of tactic polymerization synthetic.In world's polyisoprene rubber industrial production, poly-unit, solvent and monomer etc. need to be preheated to the polymerization temperature of setting on the one hand, consume certain energy; On the other hand, in polymerization process, because monomer polymerization produces a large amount of heat of polymerizations, for making poly-unit keep the polymerization temperature of setting, prevent the rising of polymerization system temperature, avoid the change of catalyst catalytic performance, thereby affect polymer architecture parameter, affect polymer performance, poly-unit needs cooling, thereby expends large energy.
Polyisoprene rubber is still immature in China's domestic industry technology at present, also only has solution polymerization technique to produce for rare-earth isoprene rubber abroad, and how to reduce energy consumption and production costs and there is not yet report under solution polymerization condition.
Because rare-earth catalysis system has polymerization activity and micmstructure of polymer temperature influence in the wider scope little feature that fluctuates, this may for producing under adiabatic condition that rare-earth isoprene rubber provides.Adiabatic polymerisation technology is owing to having saved heating in polymerization process or cooling mode, thereby can save a large amount of energy, significantly reduces the production cost of rare-earth isoprene rubber.
US6871752B2 discloses high along 1, the polyisoprene of 4 structural contents (>=96%) and narrow molecular weight distributions (dispersion index < 3.0) has excellent performance, being better than titanium is polyisoprene rubber, close to natural rubber, even at some aspect of performance, be also better than natural rubber.
Chinese Academy of Sciences Changchun should change patent CN85102250 the mass polymerization of isoprene under rare earth catalyst effect disclosed.Isoprene is under rare earth catalyst effect, catalyzer used is neodymium (or pr-nd enriched product) compound-chlorination aluminum alkyls-aluminum alkyls (or alkyl aluminium hydride) system and neodymium trichloride (or pr-nd enriched product)-ol-trialkylaluminium system, relatively can energy efficient.
The patent CN 86103812 of Italy Enichem Elastomeri S.r.l. disclose by under a kind of rare earth catalyst system exists and the method for carrying out polymerization when solvent-free manufacture isoprene copolymer and multipolymer.
Chinese Academy of Sciences Changchun should change patent CN101045768A disclose a kind of synthetic high along Isosorbide-5-Nitrae polymerizing rare earth catalyst with prepare the method for polyisoprene rubber with rare-earth catalysis system.Its polymerization technique is prepared with 5L batch still, its preparation technology is first preheating to temperature of reaction by still, and there is the hot merit of removing energy, do not belong to adiabatic polymerisation reaction, its reaction adopts the ethanolic soln that contains 2,6 one di-tert-butyl methyl phenols to stop, take unnecessary component ethanol to aftertreatment recovery system and cause burden to production, catalyst levels is large in addition, causes product ash content high, and Financial cost is too high.
But above technology still belongs to testing laboratory's technology, not yet embody pilot scale technology, and all have the problem of cis Isosorbide-5-Nitrae structural content (infrared analysis 95-96% left and right) on the low side.
The patent CN1544492A of Jinzhou discloses by the synthetic cis-1,4-polybutadiene rubber adiabatic polymerisation production technology of rare-earth catalysis system, Energy Intensity Reduction 30-40%, although divinyl and isoprene structural similitude, but polymeric reaction condition is different, polymeric articles characteristic is different, cis-1,4-polybutadiene rubber is different with polyisoprene rubber production technique, utilizes polybutadiene rubber equipment to be redesigned and just may be produced polyisoprene rubber by transformation and part unit.
CN101880344A has proposed a kind of adiabatic polymerisation method of rare-earth isoprene rubber, but its catalyst system is to take rare earth superphosphate or rare earth carboxylate, as Nd (P
204)
3or Nd (P
507)
3.Its technique exist catalyst system Primary Catalysts (rare earth) and promotor aluminum alkyls consumption large, this causes product ash content high, and end reaction temperature is over 80 ℃, to quality product, brings problem, reactor number of units more (7 still), long reaction time (8-24 hour).
Summary of the invention:
The object of this invention is to provide the adiabatic polymerisation technique of a kind of isoprene under rare earth catalyst effect.Under higher polymerization temperature, cause isoprene polymerization, obtain the high polyisoprene rubber along Isosorbide-5-Nitrae structural content (>=97%) and narrow molecular weight distributions (< 3.0).
Preparation method of the present invention is as follows:
Isoprene monomer and organic solvent enter 3 the first polymeric kettles in series connection polymeric kettle at normal temperatures, add rare earth catalyst simultaneously, rely on self-polymerization reaction heat reaction 1～6h, after polymerization completes, add and contain 0.5% anti-aging agent hexane solution and carry out termination reaction, then enter storage glue tank, through cohesion, extruding, dry, obtain product again.
The composition of the present invention's rare-earth catalysis system used is:
The composition of rare earth catalyst is:
A. isopropoxy neodymium or isobutoxy neodymium;
B. the mixture of one or two or more kinds in triisobutyl aluminium, ADEH;
C. tert-butyl chloride or sesquialter aluminium triethyl;
Its mol ratio is: A: B: C=1: 5～20: 1-5.
The concentration of isoprene monomer is 5～20g/100mL.
The mole number of the Nd of this catalyzer is 1 * 10 with the grams of isoprene monomer ratio
-7～1 * 10
-6: 1.
The present invention's organic solvent used is saturated fatty compounds of group and composition thereof, preferred hexane, heptane or isoparaffin, and add-on and isoprene monomer add-on mass ratio are 4～20: 1.
Containing 0.5% anti-aging agent hexane solution add-on is 0.1 quality %～5 quality % of isoprene monomer add-on.
Anti-aging agent is 2,6,4 (BHT), i.e. BHTs.
Adiabatic polymerisation involved in the present invention is applicable to single polymeric kettle device, is also applicable to poly and closes kettle device; Applicable to successive polymerization mode, be also applicable to batchwise polymerization mode.
Isoprene monomer of the present invention, solvent and rare earth catalyst feeding temperature are controlled at normal temperature 20-25 ℃.
This invents polymeric kettle used without any heating or refrigerating unit.
The present invention can significantly reduce the energy consumption of rare-earth isoprene rubber in producing, Energy Intensity Reduction 50-60% left and right, thus significantly reduce the production cost of rare-earth isoprene rubber.
Embodiment:
In test tank, isoprene monomer and solvent enter the first polymeric kettle from bottom, and catalyzer enters the first polymeric kettle bottom through test tank simultaneously.Polymeric kettle is without any heating or refrigerating unit.After polymerization completes, glue enters termination still.Add the hexane solution that contains anti-aging agent the double terminator of doing to carry out termination reaction, then enter storage glue tank, enter treatment and finishing section condense, push, dry and pack.
The molecular weight of polymkeric substance and molecular weight distribution: adopt Waters gel permeation chromatograph to measure, probe temperature is 30 ℃, and solvent is tetrahydrofuran (THF), is inside designated as polystyrene.
Microtexture: adopt dithiocarbonic anhydride coating method, test on PE SPECTRUM-1000 type infrared spectrometer.
Performance test: adopt the MV2-90E type mooney viscosity instrument that Wuxi Li Garden electronic chemical equipment company limited produces to press GB/T1232.1-2000 mensuration mooney viscosity at 100 ℃.
Embodiment 1
Poly-unit adopts batchwise polymerization device, and polymeric kettle volume is 10L, and the inlet amount of rare earth catalyst is:
Isopropoxy neodymium neodymium hexane solution: 3.1mol/L, 3ml;
The hexane solution of triisobutyl aluminium: 3.96mol/L, 0.6ml;
The hexane solution of sesquialter aluminium triethyl: 0.6mol/L, 0.9ml.
Under nitrogen protection, to the hexane solvent that adds 6824mL in the polymeric kettle of the dry deoxygenation of 10L, the isoprene of 1176mL (800g monomer, now monomer concentration is 10g/100mL).Feeding temperature is 20 ℃ of normal temperature, then adds the above-mentioned catalyzer preparing, and the mole number of catalyst n d is 1.0 * 10 with adding the grams ratio of monomer
-7: 1.React after 2 hours, add the double terminator of doing of hexane solution 60mL containing 0.5% anti-aging agent to stop polymerization, after the cohesion of cohesion still, carry out extruding stem dry, obtain isoprene polymerization product 7200g.Polymer yield is 90%.Through infrared spectra, recording along Isosorbide-5-Nitrae structural content is 97.8%, and mooney viscosity is 75 (ML
1+4?
100 ℃).Test products indices is qualified.
Embodiment 2
Poly-unit adopts batchwise polymerization device, and polymeric kettle volume is 400L, identical with example 1 catalyst system.Under nitrogen protection, to 400L, be dried the 170L hexane solvent adding in the polymeric kettle of deoxygenation, the isoprene of 29.4L (20kg monomer, now monomer concentration is 10g/100mL).Feeding temperature is 20 ℃ of normal temperature, then adds the above-mentioned catalyzer preparing, and the mole number of catalyst n d is 1.0 * 10 with adding the grams ratio of monomer
-7mol/g.React after 2 hours, the double terminator of doing of hexane solution 1500mL that reaction adds containing 0.5% anti-aging agent stops polymerization, carries out extruding stem dry after the cohesion of cohesion still, obtains isoprene polymerization product 18.4kg.Polymer yield is 92%.Through infrared spectra, recording along Isosorbide-5-Nitrae structural content is 97.3%, and mooney viscosity is 81 (ML
1+4 100 ℃).Test products indices is qualified.Estimation energy consumption cost is 720 yuan/ton.
Embodiment 3
Poly-unit adopts continuous polymerization unit, and polymeric kettle volume is 20L, is 3 polymeric kettle continuous polymerization units, and is furnished with glue tank, termination still and after-treatment device (comprising the unit such as cohesion, aftertreatment are reclaimed, extruding is dry).Isoprene inlet amount is 3.0L/h, and the inlet amount of solvent hexane is 17L/h.After mixing, isoprene and hexane enter the first polymeric kettle with rare earth catalyst at 20 ℃ of room temperatures simultaneously.The inlet amount of rare earth catalyst is:
Isopropoxy neodymium hexane solution: 0.31mol/L, 1.92mmol/h, 6.20ml/h;
The hexane solution of triisobutyl aluminium: 3.96mol/L, 48.0mmol/h, 12.12ml/h;
The hexane solution of sesquialter aluminium triethyl: 0.6mol/L, 11.16mmol/h, 18.6ml/h.
Successive polymerization enters termination tank after 2 hours, the double terminator of doing of hexane solution 153ml/h adding containing 0.5% anti-aging agent stops polymerization, then enters continuously storage glue tank, through condensing, push, pack and to obtain rare-earth isoprene rubber product.Turnout is 1.83Kg/ hour.Through infrared spectra, recording along Isosorbide-5-Nitrae structural content is 97.1%, and mooney viscosity is 79 (ML
1+4 100 ℃).Test products indices is qualified.Estimation energy consumption cost is 700 yuan/ton.
Embodiment 4
With embodiment 3, in catalyst system, isobutoxy neodymium replaces isopropoxy neodymium.The inlet amount of rare earth catalyst and operational condition are with embodiment 3, successive polymerization enters termination tank after 2 hours, the double terminator of doing of hexane solution adding containing 0.5% anti-aging agent stops polymerization, then enters continuously storage glue tank, through condensing, push, pack and to obtain rare-earth isoprene rubber product.Turnout is 1.93Kg/ hour.Through infrared spectra, recording along Isosorbide-5-Nitrae structural content is 97.2%, and mooney viscosity is 83 (ML
1+4?
100 ℃).Test products indices is qualified.Estimation energy consumption cost is 750 yuan/ton.
Embodiment 5
With embodiment 3, in catalyst system, in catalyst system, ADEH replaces triisobutyl aluminium, the inlet amount of rare earth catalyst and operational condition are with embodiment 3, successive polymerization enters termination tank after 2 hours, the double terminator of doing of hexane solution adding containing 0.5% anti-aging agent stops polymerization, then enters continuously storage glue tank, through condensing, push, pack and to obtain rare-earth isoprene rubber product.Turnout is 1.85Kg/ hour.Through infrared spectra, recording along Isosorbide-5-Nitrae structural content is 97.0%, and mooney viscosity is 88 (ML
1+4 100 ℃).Test products indices is qualified.Estimation energy consumption cost is 720 yuan/ton.
Embodiment 6
With embodiment 3, in catalyst system, tert-butyl chloride replaces sesquialter aluminium triethyl, and the inlet amount of rare earth catalyst and operational condition are with embodiment 3, and successive polymerization enters termination tank after 2 hours, add containing 0.5%.
Claims (1)
1. an adiabatic polymerization method of rare-earth isoprene rubber, is characterized in that: poly-unit adopts batchwise polymerization device, and polymeric kettle volume is 10L, and the inlet amount of rare earth catalyst is:
Isopropoxy neodymium hexane solution: 0.31mol/L, 3ml;
The hexane solution of triisobutyl aluminium: 3.96mol/L, 0.6ml;
The hexane solution of sesquialter aluminium triethyl: 0.6mol/L, 0.9ml;
Under nitrogen protection, to the hexane solvent that adds 6824mL in the polymeric kettle of the dry deoxygenation of 10L, the isoprene solution containing 800g monomer of 1176mL, now monomer concentration is 10g/100mL; Feeding temperature is 20 ℃ of normal temperature, then adds the above-mentioned catalyzer preparing, and the mole number of catalyst n d is 1.0 * 10 with adding the grams ratio of monomer
-7: 1, react after 2 hours, add the double terminator of doing of hexane solution 60mL containing 0.5% anti-aging agent to stop polymerization, after the cohesion of cohesion still, carry out extruding stem dry, obtain isoprene polymerization product 7200g, polymer yield is 90%, through infrared spectra, records along 1,4 structural contents are 97.8%, and mooney viscosity is 75ML
1+4 100 ℃, test products indices is qualified.
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|---|---|---|---|---|
| CN101880344A (en) * | 2009-05-06 | 2010-11-10 | 淄博鲁华泓锦化工股份有限公司 | Heat insulation method for rare-earth isoprene rubber solution polymerization |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101880344A (en) * | 2009-05-06 | 2010-11-10 | 淄博鲁华泓锦化工股份有限公司 | Heat insulation method for rare-earth isoprene rubber solution polymerization |
Non-Patent Citations (2)
| Title |
|---|
| 史雨田 等.异丙氧基稀土催化合成聚异戊二烯的活性.《青岛化工学院学报》.1989,第10卷(第2期), |
| 异丙氧基稀土催化合成聚异戊二烯的活性;史雨田 等;《青岛化工学院学报》;19890702;第10卷(第2期);第27-33页 * |
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