Production system and process of vinyl polyolefin elastomer
By using a three-stage reactor system and a static mixer to premix the catalyst, protect the bed to purify the raw materials, and use an online filter to remove impurities, the problems of insufficient catalyst activation efficiency and system blockage in EPOE production have been solved, achieving efficient and stable continuous EPOE production.
Patent Information
- Application Number
- CN202511932431.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-19
- Publication Date
- 2026-02-24
AI Technical Summary
In current industrial production of EPOE, insufficient catalyst activation efficiency and uneven distribution lead to easy poisoning of the system, resulting in high production costs. Furthermore, oligomers and impurities cause system blockage, affecting yield and stability.
A three-stage reactor system is adopted, which combines a static mixer to premix the catalyst, a protective bed to purify the raw materials, and an online filter to remove impurities, thus constructing a continuous production system. The static mixer achieves catalyst premixing, the protective bed to purify the raw materials, and the online filter to remove impurities, avoiding catalyst poisoning and system blockage.
It improves catalyst activation efficiency, uniformity, and production stability, reduces oligomer formation, avoids system blockage, and enables efficient and stable continuous production of EPOE, meeting the requirements for product performance uniformity.
Smart Images
Figure CN121554630A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of olefin polymerization technology, and in particular to a production system and process for vinyl polyolefin elastomers. Background Technology
[0002] The information disclosed in the background section of this invention is intended only to enhance the understanding of the overall background of the invention and is not necessarily to be construed as an admission or in any way implying that such information constitutes prior art known to those skilled in the art.
[0003] Vinyl polyolefin elastomers (EPOEs) are a class of polymeric materials with ethylene as the main chain and flexible segments introduced through copolymerization. They combine the processing properties of polyethylene with the elasticity of rubber and are widely used in high-end packaging, medical products, and automotive lightweighting.
[0004] However, existing industrial-scale EPOE production technologies still face the following technical bottlenecks. In traditional processes, the main catalyst and co-catalyst are directly mixed in the reactor. Uneven mixing leads to insufficient activation efficiency and uneven distribution of active catalyst sites, requiring excessive catalyst addition to maintain the reaction rate. However, excessive co-catalyst can easily cause poisoning and deactivation due to trace amounts of water and oxygen within the system, significantly increasing production costs. Oligomers generated during the polymerization reaction and residual impurities in the equipment can easily cause system blockage, forcing frequent shutdowns for cleaning, resulting in low operating loads and limited production output. Therefore, developing an efficient and stable continuous EPOE production technology has become a critical issue urgently needing to be addressed in this field. Summary of the Invention
[0005] To overcome the above problems, the present invention provides a production system and process for vinyl polyolefin elastomers.
[0006] In a first aspect, the present invention provides a production system for vinyl polyolefin elastomers, comprising a first polymerization reactor, a second polymerization reactor, and a third polymerization reactor connected in series via pipelines. The first polymerization reactor is connected to a protective bed via a pipeline, the protective bed is connected to a mixing feed line, the first polymerization reactor is connected to a static mixer via a pipeline, the static mixer is connected to a main catalyst feed line and a co-catalyst feed line, and a filter is connected to the bottom of the third polymerization reactor via a pipeline.
[0007] Preferably, the inlet of the mixing feed line is connected to an ethylene feed line and an α-feed line. Olefin feed line and solvent feed line.
[0008] Preferably, the filter is connected to a separatory tank via a pipe, the separatory tank is connected to a flash tank via a pipe, and the flash tank is connected to an extruder via a pipe.
[0009] Preferably, it also includes a solvent recovery tank, which is connected to the separating tank and the flash tank via pipelines, and is used to receive and temporarily store the solvent separated from the separating tank and the flash tank.
[0010] Preferably, it also includes an ethylene return pipeline, one end of which is connected to a separatory tank and the other end of which is connected to the first polymerization reactor.
[0011] Preferably, a compressor is installed on the ethylene return pipeline.
[0012] Preferably, two units are provided for both the protective bed and the filter.
[0013] In a second aspect, the present invention provides a production method using the above-described production system for vinyl polyolefin elastomers, comprising the following steps: (1) Ethylene, α After mixing olefins, solvents and co-catalysts, a mixed feedstock is obtained. After mixing the main catalyst and the co-catalyst, a mixed catalyst is obtained. (2) The mixed raw materials and the mixed catalyst are carried out in sequence in the first stage reaction, the second stage reaction and the third stage reaction to obtain vinyl polyolefin elastomer.
[0014] Preferably, the α-olefin is selected from at least one of 1-butene, 1-hexene, and 1-octene; The solvent is selected from at least one of n-hexane, cyclohexane, n-heptane, and methylcyclohexane; The main catalyst is selected from at least one of dimethylsilylbridged-tetramethylcyclopentadienyl-tert-butylamino-titanium dichloride and diphenylcarbazide-cyclopentadienyl-(2-dimethylamino-stilbene)zirconium dichloride; The co-catalyst is selected from triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, dichloroethylaluminum, methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, perfluorophenylboron, triphenylcarbazo(pentafluorophenyl)borate, N,N Dimethylphenylamine tetra(pentafluorophenyl)borate and N,N At least one of the following: di(hexadecyl)phenylammonium tetra(pentafluorophenyl)borate.
[0015] Preferably, in step (2), the reaction temperature of the first stage reaction is 50-120℃ and the pressure is 2.0-2.4MPa; In step (2), the reaction temperature of the second stage reaction is 60-130℃ and the pressure is 2.3-2.6MPa; In step (2), the reaction temperature of the third stage reaction is 90-140℃ and the pressure is 2.4-3.0MPa.
[0016] Compared with the prior art, the present invention has achieved the following beneficial effects: (1) The present invention achieves catalyst premixing through static mixer to solve the problem of insufficient activation efficiency, purifies raw materials through protective bed to avoid catalyst poisoning, reduces oligomer formation through three-stage reactor gradient polymerization, and avoids system blockage through online filter removal. The entire system works synergistically to build an efficient and stable continuous production system, while meeting the performance uniformity requirements of EPOE products. Attached Figure Description
[0017] The accompanying drawings, which form part of this specification, are used to provide a further understanding of the invention. The illustrative embodiments and descriptions of the invention are used to explain the invention and do not constitute an undue limitation thereof. Obviously, those skilled in the art can obtain other drawings based on these drawings without any inventive effort.
[0018] Figure 1 A simplified process flow diagram of the vinyl polyolefin elastomer provided by the present invention; Figure descriptions: 1. First polymerization reactor; 2. Second polymerization reactor; 3. Third polymerization reactor; 4. Protective bed; 5. Static mixer; 6. Filter; 7. Separator; 8. Flash tank; 9. Extruder; 10. Solvent recovery tank; 11. Compressor. Detailed Implementation
[0019] It should be noted that the following detailed descriptions are exemplary and intended to provide further illustration of the invention. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains.
[0020] There are no particular restrictions on the source of any raw materials used in this invention; they can be purchased from the market or prepared using conventional methods known to those skilled in the art.
[0021] The purity of the raw materials used in this invention is not particularly limited. Preferred raw materials are industrially pure or of the purity commonly used in the preparation of polyolefin elastomers.
[0022] All processes and equipment in this invention are abbreviated as conventional abbreviations in the field. Each abbreviation is clear and unambiguous within its relevant application area, and those skilled in the art can understand its conventional process steps and equipment structure based on the abbreviation.
[0023] The present invention will be further described below with reference to the accompanying drawings and embodiments.
[0024] Example 1 In a typical embodiment of the present invention, a production system for vinyl polyolefin elastomers is provided, see [link to relevant documentation]. Figure 1 The reactor comprises a first polymerization reactor 1, a second polymerization reactor 2, and a third polymerization reactor 3 connected in series by pipelines. The first polymerization reactor 1 is connected to a protective bed 4 by pipelines. The protective bed 4 is connected to a mixing feed pipeline. The first polymerization reactor 1 is connected to a static mixer 5 by pipelines. The static mixer 5 is connected to a main catalyst feed pipeline and a co-catalyst feed pipeline. The bottom of the third polymerization reactor 3 is connected to a filter 6 by pipelines.
[0025] By installing a static mixer 5 before the first polymerization reactor 1, the main catalyst and co-catalyst are pre-mixed before entering the reaction system, avoiding the uneven mixing problem caused by direct mixing in the reactor in traditional processes. This improves catalyst activation efficiency and makes the distribution of catalyst active centers more uniform. The invention also includes a protective bed 4 before the raw materials enter the first polymerization reactor 1. This protective bed 4 can efficiently adsorb or convert trace amounts of water, oxygen, sulfur-containing compounds, and other catalytic poisons that may be carried in the raw material stream (ethylene, α-olefins, solvent), purifying the reaction raw materials at the source. Finally, the invention includes a filter 6 at the bottom of the third polymerization reactor 3, which can directly intercept oligomers and solid impurities in the reaction products, preventing impurities from entering subsequent pipelines and equipment.
[0026] In this embodiment, the inlet of the mixing feed line is connected to an ethylene feed line and an α-feed line. Olefin feed line and solvent feed line. The mixing feed line connects to the ethylene, α-olefin, solvent and co-catalyst feed lines, allowing the various raw materials to be fully mixed before entering the reactor, further ensuring the homogeneity of the reaction raw materials, which is beneficial to improving the efficiency of the polymerization reaction and the quality of the product.
[0027] In this embodiment, the filter 6 is connected to a separating tank 7 via a pipe, the separating tank 7 is connected to a flash tank 8 via a pipe, and the flash tank 8 is connected to an extruder 9 via a pipe. The separating tank 7 achieves gas-liquid separation, the flash tank 8 removes solvent and unreacted monomers, and the extruder 9 completes granulation.
[0028] In this embodiment, a solvent recovery tank 10 is also included. The solvent recovery tank 10 is connected to the separating tank 7 and the flash tank 8 via pipelines, and is used to receive and temporarily store the solvent separated from the separating tank 7 and the flash tank 8.
[0029] In this embodiment, an ethylene return pipeline is also included, one end of which is connected to the separator 7 and the other end is connected to the first polymerization reactor 1.
[0030] In this embodiment, a compressor 11 is installed on the ethylene return pipeline. The ethylene return pipeline, in conjunction with the compressor 11, enables the recycling of unreacted ethylene.
[0031] In this embodiment, two protective beds 4 and two filters 6 are provided. This allows the other device to continue operating while one device is being maintained or replaced, ensuring production continuity.
[0032] The working principle of the vinyl polyolefin elastomer production system provided in this embodiment is as follows: Ethylene, α-olefins, and solvents are initially mixed in the mixing feed line and then enter the protective bed 4. In the protective bed 4, trace amounts of catalytic poisons such as water, oxygen, and sulfides that may be present in the feed are efficiently adsorbed and removed, resulting in a purified mixed feed. This purified feed then enters the first polymerization reactor 1 from the top.
[0033] Meanwhile, the main catalyst and the co-catalyst are fed into the static mixer 5 via independent feed lines, precisely metered according to a preset molar ratio, for thorough premixing and activation, forming a highly active mixed catalyst solution. The activated mixed catalyst is continuously injected into the first polymerization reactor 1, where it comes into contact with the purified mixed raw materials, initiating and completing the first stage of polymerization under mild conditions, mainly generating low molecular weight polymer segments.
[0034] The products from the first stage reaction are continuously fed into the second polymerization reactor 2 by the system pressure difference. Here, by increasing the reaction temperature and pressure, the active chains are further extended, the polymer molecular weight increases, and the elastomer structure is initially formed.
[0035] Subsequently, the material enters the third polymerization reactor 3, where the third stage of the reaction is completed under a higher reaction intensity. This stage aims to achieve the final chain extension of the molecular chains and the perfection of the microstructure, ensuring that the product achieves the target molecular weight distribution and performance indicators. After the reaction is completed, the EPOE-rich polymer slurry is discharged from the bottom of the third polymerization reactor 3, first passing through filter 6 to remove any trace amounts of oligomers or mechanical impurities that may be generated, preventing blockage of downstream pipelines and equipment.
[0036] The filtered slurry enters the separator 7 for gas-liquid separation. The gaseous ethylene is compressed by the compressor 11 and returned to the first polymerization reactor 1. The solvent enters the solvent recovery tank 10, and the liquid enters the flash tank 8 for further separation of solvent and product. The flashed solvent enters the solvent recovery tank 10, and the reaction product enters the extruder 9 for deashing and drying to obtain dried vinyl polyolefin elastomer.
[0037] Example 2 In a typical embodiment of this invention, a method for producing a vinyl polyolefin elastomer is provided, comprising the following steps: (1) Ethylene, α After mixing olefins, solvents and co-catalysts, a mixed feedstock is obtained. After mixing the main catalyst and the co-catalyst, a mixed catalyst is obtained. (2) The mixed raw materials and the mixed catalyst are carried out in sequence in the first stage reaction, the second stage reaction and the third stage reaction to obtain vinyl polyolefin elastomer.
[0038] In this embodiment, the α-olefin is selected from at least one of 1-butene, 1-hexene, and 1-octene; The solvent is selected from at least one of n-hexane, cyclohexane, n-heptane, and methylcyclohexane; The main catalyst is selected from at least one of dimethylsilylbridged-tetramethylcyclopentadienyl-tert-butylamino-titanium dichloride and diphenylcarbazide-cyclopentadienyl-(2-dimethylamino-stilbene)zirconium dichloride; The co-catalyst is selected from triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, dichloroethylaluminum, methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, perfluorophenylboron, triphenylcarbazo(pentafluorophenyl)borate, N,N Dimethylphenylamine tetra(pentafluorophenyl)borate and N,N At least one of the following: di(hexadecyl)phenylammonium tetra(pentafluorophenyl)borate.
[0039] In this embodiment, in step (2), the reaction temperature of the first stage reaction is 50-120℃ and the pressure is 2.0-2.4MPa; In step (2), the reaction temperature of the second stage reaction is 60-130℃ and the pressure is 2.3-2.6MPa; In step (2), the reaction temperature of the third stage reaction is 90-140℃ and the pressure is 2.4-3.0MPa.
[0040] The specific steps are as follows: Step 1: Raw material preparation and purification Fresh ethylene, α-olefins, and solvents from the storage tank are mixed in a mixing feed line. The mixed feed stream continuously passes through a protective bed 4 filled with molecular sieves and deoxidizer to remove trace amounts of water, oxygen, and other impurities, resulting in purified feed.
[0041] Step 2, Catalyst Pre-activation: The main catalyst and the co-catalyst are fed into the static mixer 5 via separate feed lines at a molar ratio of 500-1500:1 to form a homogeneous mixed catalyst solution.
[0042] Step 3, Three-segment gradient aggregation: The purified raw material obtained in step 1 and the mixed catalyst solution obtained in step 2 are continuously fed into the first polymerization reactor 1, and the first stage of polymerization reaction is carried out under the conditions of temperature of 50-120℃ and pressure of 2.0-2.4MPa.
[0043] The products from the first stage reaction are driven by system pressure and enter the second polymerization reactor 2, where the second stage polymerization reaction takes place under the conditions of 60-130℃ and 2.3-2.6MPa.
[0044] The product from the second stage reaction continues to enter the third polymerization reactor 3, where the third stage polymerization reaction is carried out under the conditions of 90-140℃ and 2.4-3.0MPa to obtain a vinyl polyolefin elastomer polymer slurry.
[0045] Step 4: Product separation and purification: The polymer slurry flowing from the bottom of the third polymerization reactor 3 first undergoes online filtration through filter 6 to trap and remove any solid impurities that may be present.
[0046] The filtered slurry then enters the separator 7 for gas-liquid separation. The separated ethylene gas is pressurized by compressor 11 and returned to the inlet of the first polymerization reactor 1 for recycling. The separated solvent enters the solvent recovery tank 10. The separated liquid enters the flash evaporator 8 for further separation of solvent and product. The distilled solvent is recovered to the solvent recovery tank 10.
[0047] Step 5, Post-processing: The reaction product obtained from the bottom of flash tank 8 enters extruder 9 for deashing and drying to obtain dried vinyl polyolefin elastomer.
[0048] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.
Claims
1. A production system for vinyl polyolefin elastomers, characterized in that, The reactor comprises a first polymerization reactor, a second polymerization reactor, and a third polymerization reactor connected in series via pipelines. The first polymerization reactor is connected to a protective bed via a pipeline, and the protective bed is connected to a mixing feed pipeline. The first polymerization reactor is also connected to a static mixer via a pipeline, and the static mixer is connected to a main catalyst feed pipeline and a co-catalyst feed pipeline. The bottom of the third polymerization reactor is connected to a filter via a pipeline.
2. The production system for vinyl polyolefin elastomers according to claim 1, characterized in that, The mixing feed line inlet is connected to an ethylene feed line, α Olefin feed line and solvent feed line.
3. The production system for vinyl polyolefin elastomers according to claim 1, characterized in that, The filter is connected to a separatory tank via a pipe, the separatory tank is connected to a flash tank via a pipe, and the flash tank is connected to an extruder via a pipe.
4. The production system for vinyl polyolefin elastomers according to claim 3, characterized in that, It also includes a solvent recovery tank, which is connected to the separator and flash tank via pipelines to receive and temporarily store the solvent separated from the separator and flash tank.
5. The production system for vinyl polyolefin elastomers according to claim 3, characterized in that, It also includes an ethylene return pipeline, one end of which is connected to a separatory tank and the other end of which is connected to the first polymerization reactor.
6. The production system for vinyl polyolefin elastomers according to claim 5, characterized in that, A compressor is installed on the ethylene return pipeline.
7. The production system for vinyl polyolefin elastomers according to claim 1, characterized in that, Two units of each are provided for the protective bed and the filter.
8. A method for producing vinyl polyolefin elastomers using a production system according to any one of claims 1-6, characterized in that, Includes the following steps: (1) Ethylene, α After mixing olefins and solvents, a mixed feedstock is obtained. After mixing the main catalyst and the co-catalyst, a mixed catalyst is obtained. (2) The mixed raw materials and the mixed catalyst are carried out in sequence in the first stage reaction, the second stage reaction and the third stage reaction to obtain vinyl polyolefin elastomer.
9. The production method according to claim 8, characterized in that, The α-olefin is selected from at least one of 1-butene, 1-hexene, and 1-octene; The solvent is selected from at least one of n-hexane, cyclohexane, n-heptane, and methylcyclohexane; The main catalyst is selected from at least one of dimethylsilylbridged-tetramethylcyclopentadienyl-tert-butylamino-titanium dichloride and diphenylcarbazide-cyclopentadienyl-(2-dimethylamino-stilbene)zirconium dichloride; The co-catalyst is selected from triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, dichloroethylaluminum, methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, perfluorophenylboron, triphenylcarbazo(pentafluorophenyl)borate, N,N Dimethylphenylamine tetra(pentafluorophenyl)borate and N,N At least one of the following: di(hexadecyl)phenylammonium tetra(pentafluorophenyl)borate.
10. The production method according to claim 8, characterized in that, In step (2), the reaction temperature of the first stage reaction is 50-120℃ and the pressure is 2.0-2.4MPa; In step (2), the reaction temperature of the second stage reaction is 60-130℃ and the pressure is 2.3-2.6MPa; In step (2), the reaction temperature of the third stage reaction is 90-140℃ and the pressure is 2.4-3.0MPa.