CN1289543C - Process for preparing olefin copolymer with low content oligomer - Google Patents
Process for preparing olefin copolymer with low content oligomer Download PDFInfo
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- CN1289543C CN1289543C CN 200410062498 CN200410062498A CN1289543C CN 1289543 C CN1289543 C CN 1289543C CN 200410062498 CN200410062498 CN 200410062498 CN 200410062498 A CN200410062498 A CN 200410062498A CN 1289543 C CN1289543 C CN 1289543C
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- 229920000089 Cyclic olefin copolymer Polymers 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title abstract description 3
- 239000002904 solvent Substances 0.000 claims abstract description 79
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 59
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000001704 evaporation Methods 0.000 claims abstract description 23
- 230000008020 evaporation Effects 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 22
- 239000002002 slurry Substances 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 15
- 239000012071 phase Substances 0.000 claims abstract description 15
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 14
- 239000007791 liquid phase Substances 0.000 claims abstract description 13
- 150000001336 alkenes Chemical class 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims description 27
- 239000007921 spray Substances 0.000 claims description 19
- 238000012725 vapour phase polymerization Methods 0.000 claims description 19
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 14
- 239000012065 filter cake Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 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
- 229920001897 terpolymer Polymers 0.000 claims description 4
- -1 butene-1 Chemical compound 0.000 claims description 3
- 238000007613 slurry method Methods 0.000 claims description 3
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004711 α-olefin Substances 0.000 claims description 2
- 238000010574 gas phase reaction Methods 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 6
- 238000012685 gas phase polymerization Methods 0.000 abstract description 5
- 230000008030 elimination Effects 0.000 abstract 2
- 238000003379 elimination reaction Methods 0.000 abstract 2
- 238000005507 spraying Methods 0.000 abstract 2
- 230000002708 enhancing effect Effects 0.000 abstract 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 17
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 16
- 239000007789 gas Substances 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 9
- 239000000178 monomer Substances 0.000 description 6
- 238000007599 discharging Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000007701 flash-distillation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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Abstract
The present invention relates to a process for preparing an olefin copolymer. The process comprises a homopolymerization or copolymerization working section by an olefin solvent slurry process, a slurry solvent elimination working section and a gas-phase copolymerization working section which comprises a polymerization evaporation drying region and a gas-phase polymerization region. A polymer without a liquid-phase is directly obtained by the polymerization at the third section, wherein a centrifugal machine or a filtering machine with spraying wash is used for the solvent elimination working section; after a solvent is eliminated by the centrifugal machine or the filtering machine, and the polymer is washed by a freshsolvent or a recovered solvent, the polymer is separated. The process has the advantages that the oligomer dissolved in the solvent can be eliminated at maximum by a separating device with the spraying wash, and the present invention is good for enhancing the thermal stability and the mechanical property of a product.
Description
Technical field
The present invention relates to the preparation method of a kind of preparation method's of olefin copolymer, particularly a kind of low content oligomer olefin copolymer.
Background technology
When producing olefin copolymer with two sections slurry processs, second section copolyreaction is to carry out in solvent, because low-molecular-weight multipolymer is dissolved in the solvent easily, on the one hand cause the aftertreatment technology process that plugging easily takes place, be difficult on the other hand the production co-monomer content higher in, new LDPE (film grade).For addressing the above problem, Chinese patent CN1076357C discloses a kind of olefin copolymer multi-stage polymeric process, wherein first section is equal polymerization of alkene solvent slurry method or copolymerization workshop section, second section for making the workshop section of slurries solvent removal by the pressurization whizzer, the 3rd section is gas phase copolymerization workshop section, and 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.Its shortcoming is through behind second section solvent removal, still contain certain amount of solvent in the filter cake, part oligopolymer still is dissolved in this part solvent, when the heat of polymerization in polymerization evaporation drying district by the 3rd section steamed this part solvent, the oligopolymer that is dissolved in wherein still can be stayed in the polymkeric substance of final generation.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of olefin copolymer, this method can make the content of oligopolymer in the olefin copolymer of gained further reduce.
For achieving the above object, the invention provides a kind of preparation method of olefin copolymer, comprise: first section is equal polymerization of alkene solvent slurry method or copolymerization workshop section, second section is the workshop section of slurries solvent removal, the 3rd section is gas phase copolymerization workshop section, it is made up of polymerization evaporation drying district and vapour phase polymerization district, by the polymerization in the 3rd section vapour phase polymerization district, is not directly contained the polymkeric substance of liquid phase.Wherein adopt whizzer or the filter have spray washing in solvent removal workshop section, through centrifugal or filtering and removing solvent, again with fresh solvent or recovered solvent spray washing after centrifugation again.
First section solvent method liquid-phase polymerization of the present invention can carry out in vertical stirring tank or annular-pipe reactor or horizontal stirring tank, the horizontal retort of preferred levels mounting strap central stirring shaft when adopting horizontal retort.The quantity of first section reactor is that one or several combine by serial or parallel connection.First section based on homopolymerization, requires also can add an amount of comonomer according to product performance.Described solvent can be alkane solvent, as alkane solvents such as hexane, heptane.Polymer concentration can require to select according to products characteristics and output in the slurry, and the concentration of industrial operation is about 30～500g/l, preferred 70～400g/l.
Second section described solvent workshop section that removes of the present invention can adopt continuous mode to carry out, and also can carry out by intermittent mode.When carrying out in a continuous manner, carry out centrifugal, washing and centrifugal again in the different zones of whizzer or filter respectively from the slurry of last workshop section.When carrying out with intermittent mode, from first section slurry after whizzer or filter remove solvent again with fresh solvent or reclaim the solvent wash one or many, come out with the solvent exchange that will stay in the polymkeric substance, certainly, the oligopolymer that is dissolved in the solvent also is displaced with solvent, thereby removes the oligopolymer that is dissolved in the solvent.What be dissolved in oligopolymer in the solvent thoroughly removes thermostability and the mechanical property that helps improving product.The filter of the whizzer of band spray washing or band spray washing all is applicable to the present invention.The whizzer of described band spray washing is preferably filtering centrifuge, as being horizontal spiral filtering centrifuge, vertical helical filtering centrifuge, horizontal scraper discharging centrifuge, piston push centrifuge etc., preferred horizontal spiral filtering centrifuge.The filter of described band spray washing can be a filtration washing all-in-one etc.Whizzer or filter can be selected according to washing amount.
When filter cake was washed, the volume of the solvent that spray washing is used was at least for the first time centrifugal or filtering separation and removes 0.3 times of filter cake volume behind the solvent.The amount of the solvent that spray washing is used is big more, the solvent exchange that contains oligopolymer that helps more remaining in the polymkeric substance comes out, but solvent load is too big, need the recovered solvent amount also big more, consider that from economic angle doubly, more preferably 0.5-2 is doubly for the 0.4-3 that the volume of the solvent that preferred spray washing is used removes filter cake volume behind the solvent for centrifugal or filtering separation for the first time.
Whizzer of the present invention is operated under pressurization or is operated under normal pressure.When under pressurization, operating, after the slurries flash distillation that first workshop section can be obtained, carry out solvent removal with being pumped into the pressurization whizzer, perhaps first workshop section is obtained polymerization product with pressure and directly send into whizzer and carry out solvent removal, remove and wet polymer with pressure is directly sent into the 3rd section again after solvent and washing separate; When under normal pressure, operating, send into whizzer after the slurries flash distillation that first workshop section can be obtained and carry out solvent removal, remove to be admitted to from the material of whizzer again after solvent and washing separate and send into the 3rd section after surge tank pressurizes.
The 3rd section described polymerization evaporation drying of the present invention district is to finish in same reactor or finish in two different reactors with the vapour phase polymerization district; When finishing, baffle plate is set in the still in same still, reactor is divided into polymerization evaporation drying district and vapour phase polymerization district, polymkeric substance can move to the discharging direction by the breach of baffle plate.The reactor that satisfies above-mentioned requirements all can adopt, preferred horizontal stirring tank, when adopting horizontal retort preferably with the horizontal retort of central stirring shaft, the more preferably horizontal retort of horizontal mounting strap central stirring shaft.When finishing in two differential responses stills, wherein first is polymerization evaporation drying district, and second is the 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 the gas phase dew point, but is lower than the softening temperature of polymkeric substance.The used reactor in polymerization evaporation drying district and vapour phase polymerization district can be vertical stirring tank, horizontal stirring tank or fluidized-bed reaction still, when adopting horizontal retort preferably with the horizontal retort of central stirring shaft, the more preferably horizontal retort of horizontal mounting strap central stirring shaft.Reactor can be one or more series connection.Agitating vane can be T type, door type, ribbon or rectangle.
In polymerization 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 gas phase dew point, 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.
The preferred first section equal polymerization reaction of only carrying out alkene of method of the present invention, the copolymerization of alkene carries out at the 3rd section, and comonomer only adds in the 3rd section gas phase copolymerization still.
Olefin copolymer of the present invention is the binary or the terpolymer of ethene or propylene and alpha-olefin, is preferably the binary or the terpolymer of ethene, propylene, butene-1,4-methylpentene-1, hexene-1.
Description of drawings
Accompanying drawing is the schema of preparation olefin copolymer
Describe the present invention in detail as an example of ethene, 1-Butylene copolymer example below in conjunction with accompanying drawing:
With raw material ethene, catalyst, alkyl aluminum, hydrogen (molecular weight regulator), solvent (with oneself Alkane is example) join in the liquid phase polymerizer, this still is vertical stirred tank, with turbine stirrer, Polymerization pressure is 0.2-1.0Mpa, and polymerization temperature is 80-85 ℃, concentration of slurry is 30～500g/l, preferred 70～400g/l. Polymeric kettle can be one, also can be several series connection or Parallel connection, the pressured difference of material flows, and also can carry with pump. Slurries after the polymerization are by polymeric kettle Bottom or sidewall discharging, pressured difference or after flash distillation, be transported to centrifuge with spray washing with pump Or filter, by separating solvent is removed as far as possible, obtain containing the filter cake of certain moisture content, Again with fresh solvent or reclaim the solvent wash filter cake, and then separate. To remove most of solvent The polymer filter cake send into the charging aperture of the 3rd section reactor, can adopt horizontal retort. The 3rd section branch Be two districts, one is polymerization evaporation drying district, and it two is the gas-phase polymerization district, can be anti-at one Answer in the still and finish, also can in two reactors, finish. Add polymerization in polymerization evaporation drying district Monomer ethylene can add the backflow lime set, owing to pass into the polymerization of polymerization single polymerization monomer, makes solvent continuous Evaporation, the very fast exsiccation of polymer. In the gas-phase polymerization district, add polymerization single polymerization monomer ethene and copolymerization list The body butene-1, owing to continue polymerization, the polymerization system temperature constantly rises, and can replenish the backflow lime set (quench liquid) makes bed temperature be higher than the gas phase dew point, is lower than the softening point of copolymer, and tie up Hold the discharging opening temperature and be higher than all the time the gas phase dew point, suitably regulate phegma amount or by directly to Discharge zone adds the temperature in the equal discharge adjustable of phegma district. Gas-phase polymerization pressure is 0.1-1.0Mpa polymerization temperature is 75-105 ℃. Leave the gas phase in polymerization evaporation drying district through cold After solidifying the recovery, incoagulable gas is returned polymerization evaporation drying district with circulating fan, and it is poly-to leave gas phase Close the gas phase in district after condensation is reclaimed, incoagulable gas is returned the gas-phase polymerization district with circulating fan.
The slurry that also can carry out butene-1 under above-mentioned similar condition in liquid phase polymerizer is poly-Close, after centrifugal and washing, in horizontal retort, carry out then the gas-phase copolymerization of butene-1 and ethene.
With compare near prior art (CN1076357C), adopt method of the present invention, logical The separator of crossing with washing can remove the oligomer that is dissolved in the solvent to greatest extent, Be conducive to improve heat endurance and the mechanical property of product.
Embodiment
The following examples will help to illustrate the present invention, but be not limited to its scope.
With following analysis instrument and method the product of embodiment and Comparative Examples gained is analyzed:
The content of Mw in the finished product＜10,000 parts adopts the Britain PL GPC of PL company 220 type gel permeation chromatographies (GPC) to analyze, and 140 ℃ of high temperature, solvent are 1,2, the 4-trichlorobenzene, and moving phase speed is 1.0ml/min.
Initial decomposition temperature adopts the hot weightless instrument TGA-2050 of du pont company to analyze, nitrogen protection, 10 ℃/min of temperature rise rate, intensification scope: room temperature-540 ℃.
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 is 4.5, inside is provided with stirring along central shaft, and π shape agitator, mixing speed are 6～30RPM, the opening for feed of horizontal retort places an end, discharge port places the other end, and inside is provided with baffle plate, 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 and triethyl aluminum 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 concentration of Primary Catalysts is 4mmolTi/L, the concentration of promotor is 100mmol/L, add the pump metering by catalyzer respectively then, join in the liquid phase polymerizer, send into liquid phase polymerizer after high-purity ethylene and hydrogen are mixed, about 85 ℃ and under the condition of about 0.6MPa, in hexane solvent, catalyzer carries out slurry polymerization under existing, the concentration of Primary Catalysts is 0.08mmolTi/LHX, the concentration of promotor is 5mmol/LHX, slurries after the liquid phase reaction remove solvent through the centrifugation of horizontal spiral filtering centrifuge, spray washing, separate again, the spray washing solvent is a fresh hexane, and its consumption removes 1.5 times of filter cake volume behind the solvent for centrifugation for the first time.Remove that the moisture content of filter cake is about 30% (parts by weight) behind the solvent, the polyethylene particle that removes solvent is sent into vapour phase polymerization workshop section, feed ethene in the polymerization evaporation drying district of horizontal retort earlier, after enter the copolymerization of vapour phase polymerization district, comonomer butene-1 and ethene are by 3: 200 (weight ratio) reaction, the polymerization pressure of horizontal retort is 0.4MPa, and polymerization temperature is 90 ℃.
Product density is 0.9470g/cm
3, tensile strength is 30.7MPa, and butene-1 actual measurement content is 0.35wt% in the product, and activity of such catalysts is 2.7*10
6GPE/molTihr.The part of Mw in the finished product＜10,000 is 8.0%, and initial decomposition temperature is 432.9 ℃.
Comparative Examples 1
Polymerization process and processing condition are with embodiment 1, and just the whizzer that adopts does not possess washing function, and butene-1 actual measurement content is 0.35wt% in the product, and product density is 0.9410g/cm
3, tensile strength is 26.60MPa, activity of such catalysts is 2.4*10
6GPE/molTihr.The part of Mw in the finished product＜10,000 is 10.8%, and initial decomposition temperature is 429.5 ℃.
Embodiment 2
Polymerization process and processing condition are with embodiment 1, just the comonomer butene-1 is with ethene reacts in horizontal retort by 7: 100 (weight ratio), the spray washing solvent load is 1 times that the centrifugation first time removes filter cake volume behind the solvent, and product density is 0.9239g/cm
3, tensile strength is 24.5MPa, and butene-1 actual measurement content is 4.0wt% in the product, and activity of such catalysts is 1.9*10
6GPE/molTihr.
Embodiment 3
Polymerization process and processing condition are with embodiment 1, and just comonomer is that hexene-1, spray washing solvent load are 1.2 times that the centrifugation first time removes filter cake volume behind the solvent, and product density is 0.9398g/cm
3, tensile strength is 28.5MPa, and hexene in the product-1 actual measurement content is 1.8wt%, and activity of such catalysts is 1.35*10
6GPE/molTihr.
Claims (11)
1. the preparation method of an olefin copolymer, comprise: first section is equal polymerization of alkene solvent slurry method or copolymerization workshop section, second section is the workshop section of slurries solvent removal, the 3rd section is gas phase copolymerization workshop section, it is made up of polymerization evaporation drying district and vapour phase polymerization district, polymerization by the 3rd section, the polymkeric substance that is not directly contained liquid phase, it is characterized in that adopting whizzer or the filter that has spray washing in solvent removal workshop section, through centrifugal or filtering and removing solvent, again with centrifugation again behind fresh solvent or the recovered solvent spray washing, wherein the volume of the used solvent of spray washing is at least centrifugal or filtering separation for the first time and removes 0.3 times of filter cake volume behind the solvent.
2. method according to claim 1, the volume that it is characterized in that the solvent that spray washing is used are at least 0.4-3 that centrifugal or filtering separation for the first time removes filter cake volume behind the solvent doubly.
3. the 0.5-2 that method according to claim 2, the volume that it is characterized in that the solvent that spray washing is used remove filter cake volume behind the solvent for centrifugal or filtering separation for the first time doubly.
4. method according to claim 1 is characterized in that described whizzer is to operate or operate under normal pressure under pressurization.
5. according to each described method of claim 1-4, it is characterized in that first section solvent method liquid-phase polymerization carries out in vertical stirring tank or annular-pipe reactor or horizontal stirring tank, the quantity of first section reactor is that one or several combine by serial or parallel connection.
6. according to each described method of claim 1-4, it is characterized in that described polymerization evaporation drying district and vapour phase polymerization district finish or finish in same reactor in two different reactors; When in same still, finishing, baffle plate is set in the still, reactor is divided into polymerization evaporation drying district and vapour phase polymerization district.
7. according to each described method of claim 1-4, it is characterized in that polymkeric substance does not contain or contain hardly liquid phase when leaving polymerization evaporation drying district, the temperature in vapour phase polymerization district is higher than the gas phase dew point, but is lower than the softening temperature of polymkeric substance.
8. according to each described method of claim 1-4, first section equal polymerization of only carrying out alkene reacted, and the copolymerization of alkene carries out at the 3rd section, and comonomer only adds in the 3rd section gas phase reaction kettle.
9. according to each described method of claim 1-4, it is characterized in that described olefin copolymer is the binary or the terpolymer of ethene or propylene and alpha-olefin.
10. method according to claim 9 is characterized in that described olefin copolymer is the binary or the terpolymer of ethene, propylene, butene-1,4-methylpentene-1, hexene-1.
11. according to each described method of claim 1-4, it is characterized in that described polymerization evaporation drying district and vapour phase polymerization district finish in two different reactors, wherein first is polymerization evaporation drying district, second is the vapour phase polymerization district.
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| CN 200410062498 CN1289543C (en) | 2004-07-13 | 2004-07-13 | Process for preparing olefin copolymer with low content oligomer |
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| CN 200410062498 CN1289543C (en) | 2004-07-13 | 2004-07-13 | Process for preparing olefin copolymer with low content oligomer |
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| CN102558448B (en) * | 2010-12-30 | 2014-03-19 | 中国石油化工股份有限公司 | Method for preparing olefin copolymer |
| CN103254342B (en) * | 2012-02-17 | 2015-10-21 | 中国石油化工股份有限公司 | For the manufacture of the preparation method of the bimodal Linear low-density polyethylene composition of film |
| CN103254341B (en) * | 2012-02-17 | 2016-03-30 | 中国石油化工股份有限公司 | A kind of Bi-modal polyethylene composition and method of making the same for tubing |
| CN103319639B (en) * | 2013-01-07 | 2016-06-29 | 中国石油化工股份有限公司 | A kind of manufacture method of injection grade high density polyethylene (HDPE) |
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