CN103539882A - Production technology of ethylene propylene rubber - Google Patents
Production technology of ethylene propylene rubber Download PDFInfo
- Publication number
- CN103539882A CN103539882A CN201310454544.0A CN201310454544A CN103539882A CN 103539882 A CN103539882 A CN 103539882A CN 201310454544 A CN201310454544 A CN 201310454544A CN 103539882 A CN103539882 A CN 103539882A
- Authority
- CN
- China
- Prior art keywords
- propylene rubber
- polymerization
- solvent
- ethylene
- monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920000181 Ethylene propylene rubber Polymers 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- 238000005516 engineering process Methods 0.000 title abstract description 7
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 15
- 239000003292 glue Substances 0.000 claims abstract description 13
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 11
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000018044 dehydration Effects 0.000 claims abstract description 6
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 239000000376 reactant Substances 0.000 claims abstract description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000011084 recovery Methods 0.000 claims description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- 239000012190 activator Substances 0.000 claims description 5
- 239000005977 Ethylene Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- 238000007791 dehumidification Methods 0.000 claims description 3
- -1 di-cyclohexylperoxy dicarbonate Chemical compound 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 230000003750 conditioning effect Effects 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract description 5
- 229920001971 elastomer Polymers 0.000 abstract description 4
- 239000005060 rubber Substances 0.000 abstract description 4
- 239000007791 liquid phase Substances 0.000 abstract description 2
- 239000010865 sewage Substances 0.000 abstract description 2
- 238000009413 insulation Methods 0.000 abstract 2
- 230000015271 coagulation Effects 0.000 abstract 1
- 238000005345 coagulation Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 abstract 1
- 230000036632 reaction speed Effects 0.000 abstract 1
- 238000010792 warming Methods 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 229940032021 tetramune Drugs 0.000 description 1
- 150000003681 vanadium Chemical class 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a production technology of ethylene propylene rubber and relates to the field of rubbers. The production technology of the ethylene propylene rubber comprises five technological processes, namely polymerization, removal of a catalyst, recycling of a monomer and a solvent, coagulation as well as dehydration and drying. According to the production technology of the ethylene propylene rubber, a catalyst (described in the specification) is adopted in the polymerization process, a reaction speed is greatly increased, a full liquid phase thermal insulation reaction is adopted in the polymerization process, namely reaction heat is used for warming a polymerization kettle in a thermal insulation manner, optimal design of the polymerization kettle can meet reactant mixing requirement, a liquid-liquid filling reaction system can accurately control parameters of the polymerization technological process and product quality, concentration of a polymer glue solution is high, quantity of a cycle solvent is low, efficiency of recycled steam and recycling rate of the solvent are high, the polymerization kettle is small in volume but high in production intensity, conversion per pass is high, raw materials and a cycle monomer do not need to be refined, content of residual catalyst in the product is low, qualified rate of a product is high, consumption of the raw materials and the catalyst is low, and content of a vanadium catalyst in sewage is low. The production technology of the ethylene propylene rubber is good, high in production elasticity and low in investment.
Description
Technical field
The present invention relates to rubber materials, be specifically related to a kind of ethylene-propylene rubber(EPR) production technique.
Background technology
Ethylene-propylene rubber(EPR) is a kind of organic compound Tetramune, very important starting material in rubber item industry, there is multiple good physicochemical property, within 2003, Chinese synthetic rubber consumption reaches 1,130,000 tons of left and right, wherein terpolymer EP rubber consumption is 2.04 ten thousand tons, only account for 1.8% of synthetic rubber consumption, therefore the demand of ethylene-propylene rubber(EPR) is still more considerable, improve its production technique, produce how better product and become the duty-bound of enterprise, application number is the preparation method that CN200710193031.3 discloses a kind of ethylene-propylene rubber(EPR), take ethene and propylene as raw material, under the existence of catalyzer metallocene compound and promotor MAO, in 60-70 ℃, carry out polyreaction 1-5 hour, steaming desolventizes, obtain ethylene-propylene rubber(EPR), the method polymerization technology is simple, production cost is low, compared with prior art, reduced the pollution that vanadium series catalyst brings, be conducive to environment protection, for the production development of ethylene-propylene rubber(EPR) a new operational path, but the method catalytic effect is poor, productivity is low, the steam efficiency and the solvent recycling rate that reclaim are low.
Summary of the invention
Problem to be solved by this invention is to provide steam efficiency and the high ethylene-propylene rubber(EPR) production technique of solvent recycling rate of a kind of excellent catalytic effect, productivity, recovery.
To achieve these goals, the technical scheme that the present invention takes is: a kind of ethylene-propylene rubber(EPR) production technique, comprises following processing step:
(1) polymerization: reacting ethylene and propylene are chilled to-50 ℃ in advance through two sections, take hexane as solvent, then add catalyzer, monomer, activator, then put into polymeric kettle and carry out polyreaction, temperature of reaction is controlled at 45～55 ℃, reaction pressure is controlled at 2.0～2.5MPa, and polymerization time is controlled at 2～4min;
(2) catalyst removal: by adding alkaline vanadium removal agent, and under the effect of hot wash, make vanadium catalyst residual in polymkeric substance glue enter people's water, then through twice washing, vanadium catalyst residual in reactant is thoroughly removed;
(3) recovery of monomer and solvent: to twice vacuum flashing of unreacted polymkeric substance glue in step (2), complete the recovery to monomer and solvent;
(4) cohesion: add the auxiliary agents such as people's oxidation inhibitor, dispersion agent in the polymkeric substance glue that the concentration making is 7.5%～8.5% after step (3) reclaims, then deliver in the cohesion still of two series connection and carry out stripping and cohesion;
(5) dehydration and dry: by the draining screen laggard people's aftertreatment dehumidification system that dewaters for the buffings after step (4) cohesion, obtain product after dry through extruding-desiccation machine and expansion-exsiccation machine two-stage.
Preferably, the catalyzer, monomer and the activator that in described step (1), add are respectively VOCl
3-1/2Al
2etCl
3, di-cyclohexylperoxy dicarbonate and aminophenyl diethyl aluminum amido complex compound.
Preferably, in described step (1), in polymerization process, need to pass into hydrogen as relative molecular mass conditioning agent.
Preferably, the polymeric kettle using in described step (1) is filled reactor system for liquid-liquid, and the volume of polymeric kettle is 6m
3.
Preferably, in described step (4), stripping wet hexane solvent out recycles after dehydration and impurity processing.
Adopt technical scheme of the present invention, in described polymerization process, adopt VOCl
3-1/2Al
2etCl
3as catalyzer, catalytic efficiency is high, speed of response is greatly improved, polymerization adopts full liquid phase adiabatic reaction, be that reaction heat is for polymeric kettle adiabatic heating, the optimization design of polymeric kettle can meet reaction mass mixing requirement, liquid-liquid is filled reactor system can accurately control polymerization technique parameter and quality product, polymkeric substance glue concentration is compared with high and circulating solvent amount is few, the steam efficiency and the solvent recycling rate that reclaim are high, polymeric kettle volume is little but production intensity is high, per pass conversion is high, raw material and recycle monomer do not need to refine, in product, the content of residual catalyst is low, conforming product rate is higher, the consumption of raw material and catalyzer is low, in sewage, vanadium catalyst content is low, this processing method technique is good, production elasticity is large, invest low.
Embodiment
Embodiment 1:
(1) polymerization: reacting ethylene and propylene are chilled to-50 ℃ in advance through two sections, take hexane as solvent, then add VOCl
3-1/2Al
2etCl
3catalyzer, di-cyclohexylperoxy dicarbonate monomer, aminophenyl diethyl aluminum amido complex compound activator, and pass into hydrogen, and then to put into liquid-liquid filling reactor system and carry out polyreaction, temperature of reaction is 45 ℃, reaction pressure is 2.0MPa, and polymerization time is 2min;
(2) catalyst removal: by adding alkaline vanadium removal agent sodium hydroxide, and under the effect of hot wash, make vanadium catalyst residual in polymkeric substance glue enter people's water, then through twice washing, vanadium catalyst residual in reactant is thoroughly removed;
(3) recovery of monomer and solvent: to twice vacuum flashing of unreacted polymkeric substance glue in step (2), complete the recovery to monomer and solvent;
(4) cohesion: add the auxiliary agents such as people's oxidation inhibitor Ursol D, the loose PL-90 of dispersion agent Puli in the polymkeric substance glue that the concentration making is 7.5% after step (3) reclaims, then deliver in the cohesion still of two series connection and carry out stripping and cohesion;
(5) dehydration and dry: by the draining screen laggard people's aftertreatment dehumidification system that dewaters for the buffings after step (4) cohesion, obtain product after dry through extruding-desiccation machine and expansion-exsiccation machine two-stage.
Embodiment 2: all the other are identical with embodiment 1, and difference is that, in described step (1), temperature of reaction is 48 ℃, and reaction pressure is 2.2MPa, and polymerization time is 3min; In described step (4), polymkeric substance glue concentration gets 8.0%.
Embodiment 3: all the other are identical with embodiment 1, and difference is, in described step (1), temperature of reaction is 53 ℃, and reaction pressure is 2.5MPa, and polymerization time is 4min; In described step (4), polymkeric substance glue concentration gets 8.5%.
After above processing step, take out ethylene-propylene rubber(EPR) sample, to be measured:
From above data, the ethylene-propylene rubber(EPR) mooney viscosity of producing is high, and sizing material molecular weight is high, distribution range is wide, and ethylene content is also moderate, and the rate of recovery of monomer and solvent is high, and polymerization efficiency is more than 96%, and production efficiency is high.
Obviously specific implementation of the present invention is not subject to the restrictions described above; as long as adopted the improvement of the various unsubstantialities that method of the present invention design and technical scheme carry out; or without improving, design of the present invention and technical scheme are directly applied to other occasion, all within protection scope of the present invention.
Claims (5)
1. an ethylene-propylene rubber(EPR) production technique, comprises following processing step:
(1) polymerization: reacting ethylene and propylene are chilled to-50 ℃ in advance through two sections, take hexane as solvent, then add catalyzer, monomer, activator, then put into polymeric kettle and carry out polyreaction, temperature of reaction is controlled at 45～55 ℃, reaction pressure is controlled at 2.0～2.5MPa, and polymerization time is controlled at 2～4min;
(2) catalyst removal: by adding alkaline vanadium removal agent, and under the effect of hot wash, make vanadium catalyst residual in polymkeric substance glue enter people's water, then through twice washing, vanadium catalyst residual in reactant is thoroughly removed;
(3) recovery of monomer and solvent: to twice vacuum flashing of unreacted polymkeric substance glue in step (2), complete the recovery to monomer and solvent;
(4) cohesion: add the auxiliary agents such as people's oxidation inhibitor, dispersion agent in the polymkeric substance glue that the concentration making is 7.5%～8.5% after step (3) reclaims, then deliver in the cohesion still of two series connection and carry out stripping and cohesion;
(5) dehydration and dry: by the draining screen laggard people's aftertreatment dehumidification system that dewaters for the buffings after step (4) cohesion, obtain product after dry through extruding-desiccation machine and expansion-exsiccation machine two-stage.
2. a kind of ethylene-propylene rubber(EPR) production technique according to claim 1, is characterized in that: the catalyzer, monomer and the activator that in described step (1), add are respectively VOCl
3-1/2Al
2etCl
3, di-cyclohexylperoxy dicarbonate and aminophenyl diethyl aluminum amido complex compound.
3. a kind of ethylene-propylene rubber(EPR) production technique according to claim 1, is characterized in that: in described step (1), in polymerization process, need to pass into hydrogen as relative molecular mass conditioning agent.
4. a kind of ethylene-propylene rubber(EPR) production technique according to claim 1, is characterized in that: the polymeric kettle using in described step (1) is filled reactor system for liquid-liquid, and polymeric kettle volume is 6m
3.
5. a kind of ethylene-propylene rubber(EPR) production technique according to claim 1, is characterized in that: in described step (4), stripping wet hexane solvent out recycles after dehydration and impurity processing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310454544.0A CN103539882A (en) | 2013-09-29 | 2013-09-29 | Production technology of ethylene propylene rubber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310454544.0A CN103539882A (en) | 2013-09-29 | 2013-09-29 | Production technology of ethylene propylene rubber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103539882A true CN103539882A (en) | 2014-01-29 |
Family
ID=49963776
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310454544.0A Pending CN103539882A (en) | 2013-09-29 | 2013-09-29 | Production technology of ethylene propylene rubber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103539882A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104031196A (en) * | 2014-04-17 | 2014-09-10 | 王渊朴 | Production process for ethylene propylene rubber |
| CN105330764A (en) * | 2014-06-25 | 2016-02-17 | 中国石油化工股份有限公司 | Glue solution coacervation method of ethylene propylene rubber |
| CN106967189A (en) * | 2016-01-14 | 2017-07-21 | 中国石油化工股份有限公司 | Removal method of catalyst and EP rubbers of EP rubbers glue containing vanadium series catalyst and preparation method thereof |
| CN112940166A (en) * | 2019-12-11 | 2021-06-11 | 中国石油天然气股份有限公司 | Preparation method of ethylene propylene diene monomer for heat insulation layer |
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|---|---|---|---|---|
| CN1775820A (en) * | 2004-11-18 | 2006-05-24 | 锦湖Polychem株式会社 | Method for preparing EP(D)M elastomer, controlling its yield and recycling |
| CN101092465A (en) * | 2006-06-23 | 2007-12-26 | 中国石油天然气股份有限公司 | Ethylene propylene rubber for automobile sealing strip and preparation method thereof |
| CN101200514A (en) * | 2007-12-04 | 2008-06-18 | 河南省科学院化学研究所有限公司 | Production method of ethylene propylene rubber |
| CN103044598A (en) * | 2011-10-17 | 2013-04-17 | 中国石油天然气股份有限公司 | Method for concentrating ethylene propylene rubber liquid through flash evaporation |
-
2013
- 2013-09-29 CN CN201310454544.0A patent/CN103539882A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1775820A (en) * | 2004-11-18 | 2006-05-24 | 锦湖Polychem株式会社 | Method for preparing EP(D)M elastomer, controlling its yield and recycling |
| CN101092465A (en) * | 2006-06-23 | 2007-12-26 | 中国石油天然气股份有限公司 | Ethylene propylene rubber for automobile sealing strip and preparation method thereof |
| CN101200514A (en) * | 2007-12-04 | 2008-06-18 | 河南省科学院化学研究所有限公司 | Production method of ethylene propylene rubber |
| CN103044598A (en) * | 2011-10-17 | 2013-04-17 | 中国石油天然气股份有限公司 | Method for concentrating ethylene propylene rubber liquid through flash evaporation |
Non-Patent Citations (1)
| Title |
|---|
| 祁俊: "钒系溶液聚合法乙丙橡胶生产工艺技术分析", 《石化技术》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104031196A (en) * | 2014-04-17 | 2014-09-10 | 王渊朴 | Production process for ethylene propylene rubber |
| CN105330764A (en) * | 2014-06-25 | 2016-02-17 | 中国石油化工股份有限公司 | Glue solution coacervation method of ethylene propylene rubber |
| CN105330764B (en) * | 2014-06-25 | 2018-10-16 | 中国石油化工股份有限公司 | A kind of method of EP rubbers glue cohesion |
| CN106967189A (en) * | 2016-01-14 | 2017-07-21 | 中国石油化工股份有限公司 | Removal method of catalyst and EP rubbers of EP rubbers glue containing vanadium series catalyst and preparation method thereof |
| CN106967189B (en) * | 2016-01-14 | 2019-01-22 | 中国石油化工股份有限公司 | Removal method of catalyst and EP rubbers of EP rubbers glue containing vanadium series catalyst and preparation method thereof |
| CN112940166A (en) * | 2019-12-11 | 2021-06-11 | 中国石油天然气股份有限公司 | Preparation method of ethylene propylene diene monomer for heat insulation layer |
| CN112940166B (en) * | 2019-12-11 | 2022-10-04 | 中国石油天然气股份有限公司 | Preparation method of ethylene propylene diene monomer for heat insulation layer |
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Application publication date: 20140129 |