CN1213667A - Olefin copolymer multi-stage polymeric process - Google Patents
Olefin copolymer multi-stage polymeric process Download PDFInfo
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- CN1213667A CN1213667A CN 98117938 CN98117938A CN1213667A CN 1213667 A CN1213667 A CN 1213667A CN 98117938 CN98117938 CN 98117938 CN 98117938 A CN98117938 A CN 98117938A CN 1213667 A CN1213667 A CN 1213667A
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Abstract
A multi-segment polymerization process for olefin copolymer features easy copolymerization, low content of oligomer, wide range of densities and high quality of product.
Description
The invention belongs to petrochemical industry.
Along with succeeding in developing of high-performance new catalyst, very big development is being arranged aspect the poly preparation, be characterized in cancelling the postprocessing working procedures that removes catalyst residue, reduced consumption, reduced investment, under the condition of vapour phase polymerization, can in the scope of broad, regulate the content of comonomer, thereby in the scope of broad, regulate the density of product.But traditional is that the slurry method polymerization technique of solvent still occupies a tiny space with hexane, Trimethylmethane etc.
The polymerization technique of slurry method, vapor phase process is broadly divided into following several types: the clear 45-30832 of (1) Japanese Patent, clear 45-24786, clear 41-19914, clear 41-14589, clear 42-22441 are that solvent is produced poly slurry method polymerization technique with the hexane.Slurries leave after the polymeric kettle, tell solvent hexane through whizzer, and the oligopolymer that meanwhile is dissolved in the solvent is also simultaneously separated, so product is cleaner, and mass ratio is better.But its shortcoming is to produce relatively difficulty of multipolymer, and multipolymer can be dissolved in the hexane solvent.Therefore, the multipolymer content of product is generally lower, is difficult to the lower product of production density.(2) U.S. combinating carbide company (Union Carbide Corp.) patent 4003712, fluidized bed gas-phase polymerization.Under the condition of vapour phase polymerization, produce multipolymer time ratio and be easier to, but oligopolymer stay in the product and can't take away, homopolymer second-rate must be by improving the quality of products with the high alpha-olefin copolymerization.(3) USS oil company (Standard Oil Company) patent 3965083, stir at horizontal band center, quench liquid refrigerative vapor phase polymerizer.Heat of polymerization is removed by the vaporization heat that sprays into quench liquid in still.The energy expenditure of this method is less, and the material flow pattern in the equipment is near piston flow, and the efficient of catalyzer is higher, and when producing multipolymer, the content of multipolymer is more even in the polymkeric substance, good product quality.Oligopolymer was stayed in the product and can't be taken away equally when but the horizontal retort vapour phase polymerization was produced polyethylene, and homopolymer second-rate must be by improving the quality of products with the high alpha-olefin copolymerization.(4) U.S. Fei Lipu company (Phillips Petroleum Co.) patent, the annular tube type polymeric kettle, propeller pump circulation is a solvent with the Trimethylmethane when producing polyethylene, the slurry method polymerization technique.Slurries leave after the polymeric kettle, by the flash separation solvent.This polymerization technique and Mitsui oiled are that the slurry method technology of solvent is compared with the hexane, because Trimethylmethane is more much smaller than hexane to the solubleness of oligopolymer, multipolymer, therefore, produces the multipolymer ratio and are easier to, and the co-monomer content in the product can be higher.But after the flash distillation, oligopolymer is all stayed in the product, and homopolymer second-rate must be by improving the quality of product with the high alpha-olefin copolymerization, and this point is about the same with vapour phase polymerization.(5) the Chinese Shanghai medicine patent CN87100218 of designing institute, slurry method and the combined technology of horizontal retort vapour phase polymerization.This technology is applicable to the mass polymerization of alkene, and is also proper to producing multipolymer.But when being solvent production polyethylene with the hexane, slurries enter horizontal retort, and after the heat of polymerization evaporating solvent, oligopolymer is all stayed in the product, has influenced the quality of product.
The objective of the invention is to propose a new olefin copolymer multi-stage polymeric process, in the hope of overcoming with the hexane on the one hand is that the slurry method of solvent is produced the relatively shortcoming of difficulty of multipolymer when preparing polyethylene, keep simultaneously its by the centrifugation solvent after lower, the quality product of oligomer in product advantage preferably; Overcoming on the other hand with the Trimethylmethane is higher, the shortcoming that influences quality product of oligomer in the slurry method of solvent and the vapor phase process product, keep simultaneously its produce multipolymer content density higher, product can very wide advantage.
Olefin copolymer multi-stage polymeric process of the present invention can be divided into three phases, and the fs, its material form was the slurry of the about 400 grams per liter solvents of solid concentration in order to be the slurry method polymerization of solvent with alkane such as hexane, heptane.The form of its polymeric kettle can be the horizontal retort of vertical stirring tank or annular-pipe reactor or horizontal mounting strap central stirring shaft, and their quantity can be connected for one or more, also can be in parallel.Fs requires also can add an amount of comonomer according to product performance based on homopolymerization.
Subordinate phase is the solvent removal stage, removes the oligopolymer that is dissolved in the solvent simultaneously.Solvent removal equipment can remove solvent by centrifugation as far as possible with the pressurization whizzer.Filter cake enters phase III continuation polymerization.
Phase III is a gas phase copolymerization.The polymeric kettle form is the horizontal retort of band central stirring shaft, and horizontal retort can be one or more series connection.Agitating vane can be T type, II type, ribbon or rectangle, and rotating speed is 6-30 rev/min, and the polymerization in the phase III horizontal retort is made up of polymerization evaporation drying district and vapour phase polymerization district, can be made of the vapour phase polymerization district separately when producing some trade mark.
In the evaporation drying district, owing to feed monomeric polyreaction, residual solvent is steamed.
The vapour phase polymerization district is except that feeding the polymerization main monomer, and when producing multipolymer, visual product performance require to feed comonomer simultaneously by different proportionings.Bed temperature is higher than the dew point of gas phase, is lower than the softening temperature of polymkeric substance.The method of removing heat of polymerization has two, one, squeezes into quench liquid, is generally solvent itself, comprises the polymerization single polymerization monomer in being dissolved in, and the 2nd, utilize the heat of removing of horizontal jacket of polymerization.
Available plate washer separates between polymerization evaporation drying district and the vapour phase polymerization district.Polymkeric substance can move to discharge port by the breach of plate washer.
Accompanying drawing is that example has shown that this flow process is used for the summary situation of solvent polymeric with ethene, propylene copolymer.
With raw material ethene, catalyst, alkyl aluminum, hydrogen (molecular weight regulator), solvent (take hexane as example) Join in the liquid phase polymerizer, this still is vertical stirred tank, with turbine stirrer. Polymerization pressure is 0.2-1.0MPa polymerization temperature is 80-85 ℃, concentration of slurry is 400g solid phase/rise solvent. Polymeric kettle can be one Individual, also can be several serial or parallel connections, the pressured difference of material flows, and also can carry with pump. After the polymerization Slurries are by polymeric kettle bottom or sidewall discharging, pressured difference or deliver into the pressurization centrifuge with pump after flash distillation. From Heart equipment removes solvent by centrifugation as far as possible for the pressurization centrifuge, and the moisture content of filter cake is about 30 % (parts by weight). The polymer beads of desolvation is sent into horizontal retort one endfeed mouth. Horizontal retort can Be divided into two districts, one is polymerization evaporation drying district, and it two is the gas-phase polymerization district, also can only be a gas phase Polymeric area. Add polymerization single polymerization monomer ethene in polymerization evaporation drying district, do not add the backflow lime set, owing to pass into polymerization The polymerization of monomer is constantly evaporated solvent, the very fast exsiccation of polymer. In the gas-phase polymerization district, add polymerization single polymerization monomer Ethene and comonomer propylene, owing to continue polymerization, polymer temperature constantly rises, and can replenish the backflow lime set (suddenly Cold liquid), make bed temperature be higher than dew point, be lower than the softening point of copolymer, and it is all the time high to keep the discharging opening temperature In dew point. Suitably regulate the amount of phegma or by directly adding the equal discharge adjustable of phegma district to discharge zone Temperature. Gas-phase polymerization pressure is 0.1-1.0MPa, and polymerization temperature is 80-105 ℃. Leave the polymerization evaporation drying The gas phase in district is after condensation is reclaimed, and incoagulable gas is returned polymerization evaporation drying district with circulating fan, leaves gas phase The gas phase of polymeric area is after condensation is reclaimed, and incoagulable gas is returned the gas-phase polymerization district with circulating fan.
Under above-mentioned similar condition, also can in liquid phase polymerizer, carry out the slurry polymerization of propylene, then through from In horizontal retort, carry out the gas-phase copolymerization of propylene and ethene behind the heart.
The present invention is particularly useful for making ethene and propylene, butene-1,4-methylpentene-1, hexene etc. The copolymer of high alpha-olefin. The present invention can prepare binary and the above copolymer of binary.
Olefin copolymer multi-stage polymeric process of the present invention is compared with present existing technology to have significantly actively Effect. Taken away oligomer when it has kept the solvent method polymerization by the centrifugation solvent, product quality Good advantage has overcome it and has produced the relatively shortcoming of difficulty of copolymer; It has kept again gas-phase polymerization production copolymerization Thing is relatively easy to advantage, and overcome it and can't take oligomer away, affect the shortcoming of product quality, thus can Produce the product of the special trade mark that oligomer is low, co-monomer content is high; Owing to selected the horizontal retort work Be vapor phase polymerizer, the present invention can produce that oligomer is low, copolymer content height, and co-monomer content The copolymer of very uniform excellent quality. In addition, horizontal retort is to the strong adaptability of catalyst, even urge from now on Horizontal retort still can adapt to the device efficiency height of horizontal retort, catalyst when the change agent developed into production bulky grain powder The series of advantages such as utilization ratio height have all obtained sufficient embodiment in the present invention.
The present invention compares with Chinese patent CN87100218, owing to increased the pressurization centrifuge, effectively separates Solvent, avoided the oligomer in the solvent to enter horizontal retort and finally enter product, end product quality is got To further improving.
Further specify the present invention below in conjunction with embodiment, but and the scope of unrestricted claim protection of the present invention.Embodiment 1
Solvent method liquid polymerization is the vertical stainless steel stirring tanks of 90 liters, and agitator is the hinged joint turbine, and rotating speed is 375-500RPM.Horizontal retort 600 liters, L/D are 4.5, and inside is provided with stirring along central shaft, π shape agitator, mixing speed is 6-30RPM, and the opening for feed of horizontal retort places an end, and discharge port places the other end, inside is provided with plate washer, leaves the space on the dividing plate, can allow polymkeric substance to pass through.The ratio in polymerization evaporation drying district and vapour phase polymerization district can be regulated by the quantity, position and the operation that change dividing plate.
Ti-base catalyst (PZ catalyzer) and triethyl aluminum (AT catalyzer) that employing loads on the carrier are contained in the special container respectively, and in catalyst dilution jar separately, be diluted to the concentration of regulation with hexane, the PZ catalyzer is 5mmol Ti/L PZ slurries, the AT catalyst concn is a 100mmol Al/L AT solution, add the pump metering by catalyzer respectively then, join in the liquid phase polymerizer.High-purity ethylene and hydrogen are sent into liquid phase polymerizer after mixing, about 85 ℃ and under the condition of about 0.5MPa, in hexane solvent (be called for short HX, below identical), carry out slurry polymerization under the catalyzer existence.Material proportion is: the ethene add-on is that 4.7kg/h, hexane add-on are that 8.8kg/h, PZ concentration are that 0.09mmol Ti/L HX, AT concentration are 1.0mmol Al/LHX.Slurries after the liquid phase reaction remove solvent through the pressurization whizzer, the moisture content of filter cake is about 30% (parts by weight), the polyethylene particle that removes solvent is sent into the polymerization evaporating area of horizontal retort, feed ethene in the polymerization evaporating area, vapour phase polymerization district at horizontal retort, the comonomer propylene with join simultaneously in the horizontal retort after ethene mixes by 1: 1 (weight ratio), the polymerization pressure of horizontal retort is 0.4MPa, polymerization temperature is 95 ℃.
The density of product is 0.9446g/cm
3, tensile strength is 27.70MPa, propylene actual measurement content is 1.30% (parts by weight) in the product, activity of such catalysts is 1.5 * 10
6G product/mol Tih.Embodiment 2
Polymerization process and processing condition are with embodiment 1, just the comonomer propylene with join simultaneously in the vapour phase polymerization district of horizontal retort after ethene mixes by 1: 3 (weight ratio), the density of product is 0.9140g/cm
3, tensile strength is 29.30MPa, propylene actual measurement content is 3.70% (parts by weight) in the product, activity of such catalysts is 1.2 * 10
6G product/mol Tih.Embodiment 3
Polymerization process and processing condition are with embodiment 1, and just comonomer is a butene-1, and the density of product is 0.9410g/cm
3, tensile strength is 26.60MPa, butene-1 actual measurement content is 0.35% (parts by weight) in the product, activity of such catalysts is 2.4 * 10
6G product/mol Tih.Embodiment 4
Polymerization process, processing condition and comonomer still are not provided with polymerization evaporation drying district separately with embodiment 1.Product density is 0.9440g/cm
3, tensile strength is 27.6MPa, and propylene actual measurement content is 1.60% (parts by weight) in the product, and activity of such catalysts is 1.6 * 10
6G product/mol Tih.Embodiment 5
Poly-unit, polymerization process and polymerization temperature, pressure condition are with embodiment 1, what just drop in liquid phase polymerizer is propylene monomer, the propylene add-on is 3.4kg/hr, the hexane add-on is 6kg/hr, the add-on of Ti-base catalyst is 2g/hr, and triethyl aluminum (AT) add-on is 4.8g/hr, and the add-on of dimethoxydiphenylsilane is 1.5g/hr, add an amount of molecular weight regulator hydrogen, the slurries filter cake after centrifugal branch desolvates that leaves liquid phase polymerizer enters horizontal retort.The polymerization evaporating area is not set separately in the horizontal retort, and comonomer ethene joins with appropriate amount of hydrogen in the ratio of 4: 1 (molecular ratio) with propylene and carries out vapour phase polymerization in the horizontal retort.Product density is 0.90g/cm
3, tensile strength is 20MPa, ethylene content is 25% in the product.
Claims (8)
1 one kinds of polymerization processs that prepare olefin copolymer, it is characterized in that: first section is the equal polymerization of alkene solvent slurry method workshop section, second section is slurries solvent removal workshop section, the 3rd section is gas phase copolymerization workshop section, the 3rd section is carried out in horizontal retort, and horizontal retort is formed or is made up of the vapour phase polymerization district by polymerization evaporation drying district and vapour phase polymerization district.By the 3rd section polymerization, directly do not contained the polymkeric substance of liquid phase.
2 methods according to claim 1, it is characterized in that: first section equal polymerization of solvent method liquid phase is reflected in vertical stirring tank or annular-pipe reactor or the horizontal retort to be carried out, the quantity of first section reactor can be one, or several are combined by serial or parallel connection.
3 methods according to claim 1, it is characterized in that: second section solvent removal finished by the pressurization whizzer, with the solvent removal in first section homopolymer slurries that obtain, the material form of horizontal retort opening for feed is the homopolymer pellets of solid concentration about 70% (parts by weight).
4 methods according to claim 1, it is characterized in that: the 3rd section copolymerization has in the horizontal retort that central shaft stirs one and carries out, plate washer can be set in the still horizontal retort is divided into polymerization evaporation drying district and vapour phase polymerization district, polymkeric substance does not contain or contains hardly liquid phase when leaving polymerization evaporation drying district, the temperature in vapour phase polymerization district is higher than dew point, but is lower than the fusing point of polymkeric substance.The quantity of horizontal retort can be one or several.
5 methods according to claim 1 is characterized in that: first section equal polymerization reaction of only carrying out alkene, and the copolymerization of alkene carries out at the 3rd section, and comonomer only adds in the 3rd section horizontal retort.
6 methods according to claim 1 are applicable to that solvent method prepares the multipolymer of ethene or propylene and alpha-olefin, are specially adapted to the copolymer of ethene, propylene, butene-1,4-methylpentene-1, hexene.Its multipolymer is not limited to binary, also can be terpolymer.
7 methods according to claim 1 is characterized in that: the requirement according to product performance can be at first section copolymerization that carries out alkene.
8 according to claim 1,2 described methods, and it is characterized in that: horizontal retort is in series by two, and wherein first is polymerization evaporation drying district, and second is the vapour phase polymerization district.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98117938A CN1076357C (en) | 1998-09-07 | 1998-09-07 | Olefin copolymer multi-stage polymeric process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98117938A CN1076357C (en) | 1998-09-07 | 1998-09-07 | Olefin copolymer multi-stage polymeric process |
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| CN1213667A true CN1213667A (en) | 1999-04-14 |
| CN1076357C CN1076357C (en) | 2001-12-19 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN98117938A Expired - Fee Related CN1076357C (en) | 1998-09-07 | 1998-09-07 | Olefin copolymer multi-stage polymeric process |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107602739A (en) * | 2017-10-18 | 2018-01-19 | 浙江卫星能源有限公司 | The multi-stage polymeric process and device of a kind of propylene |
| CN114907505A (en) * | 2021-02-08 | 2022-08-16 | 中国科学院上海有机化学研究所 | Production process of ultrahigh molecular weight polyethylene |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56139520A (en) * | 1980-04-02 | 1981-10-31 | Mitsui Petrochem Ind Ltd | Preparation of block copolymer |
| CN1014523B (en) * | 1987-01-24 | 1991-10-30 | 国家医药管理局上海医药设计院 | Multi-stage polymerzation for alkenes |
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1998
- 1998-09-07 CN CN98117938A patent/CN1076357C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107602739A (en) * | 2017-10-18 | 2018-01-19 | 浙江卫星能源有限公司 | The multi-stage polymeric process and device of a kind of propylene |
| CN114907505A (en) * | 2021-02-08 | 2022-08-16 | 中国科学院上海有机化学研究所 | Production process of ultrahigh molecular weight polyethylene |
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| CN1076357C (en) | 2001-12-19 |
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