WO2000056776A1 - Verfahren zur herstellung von ethylen-copolymer - Google Patents
Verfahren zur herstellung von ethylen-copolymer Download PDFInfo
- Publication number
- WO2000056776A1 WO2000056776A1 PCT/EP2000/002234 EP0002234W WO0056776A1 WO 2000056776 A1 WO2000056776 A1 WO 2000056776A1 EP 0002234 W EP0002234 W EP 0002234W WO 0056776 A1 WO0056776 A1 WO 0056776A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- reactor
- stage
- copolymer
- ethylene
- mixture
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
Definitions
- the invention relates to a method for producing a copolymer based on ethylene.
- Polyethylenes are produced by polymerizing ethylene using two fundamentally different methods, the high pressure and the low pressure Z medium pressure process.
- the low pressure Z medium pressure process can be carried out as solution polymerization, as suspension ZE emulsion polymerization or as gas phase polymerization.
- the high pressure process is carried out at pressures higher than 1500 bar and takes place according to a radical mechanism.
- the low-pressure Z medium-pressure process is carried out at pressures below 100 bar and is usually catalyzed.
- products from the high pressure process which have a high branching, a lower crystallinity and a low density
- products from the low pressure Z medium pressure process are mostly of linear, little branched structure, have a high crystallinity (mostly 60 - 90%), a high melting range (typically 120 - 135 ° C) and a high density (usually 0.93 - 0.97 g / cm 3 ).
- a high density of the polyethylenes is usually combined with a high glass transition temperature, high hardness, a high melting range, high brittleness and low stickiness. The above properties generally characterize low-pressure Z medium-pressure polyethylene.
- Low-pressure, medium-pressure polymerization of ethylene in which olefins are used as comonomers, will be considered below. It is a copolymerization in which the crystallinity of the product obtained can be controlled by varying the amount of olefin in the monomer mixture.
- Such a copolymerization of ethylene with comonomer is described in EP-B-0 555 747. In the corresponding process, ethylene is polymerized catalytically with ⁇ -olefins at pressures below 100 bar.
- the present invention has for its object to provide a method in which the production plant for the polyethylene no longer has to be shut down to remove deposits.
- the disruptive deposits should be removed during production.
- the process according to the invention is then a process for the production of copolymer based on ethylene by continuously copolymerizing ethylene and comonomer in a reactor in the presence of a catalyst, a mixture of such composition containing an ethylene and comonomer being introduced into the reactor in a first stage of the copolymerization metered in andZ or generated in the reactor such that a coating comprising copolymer is deposited in the reactor and in a second stage the concentration of the comonomer in the metered-in mixture andZor in the mixture produced in the reactor is reduced so much andZor the concentration of ethylene in the metered-in mixture andZor im Reactor generated mixture is increased so much that the coating is either partially or completely removed from the reactor.
- the term reactor means, inter alia, the entire area of the production device in which the copolymer can separate. In particular, this can also be the discharge area of a reactor, in which the actual polymerization no longer takes place, but polymer is separated - in particular, pipelines are affected (the reactor usually contains a production area and a discharge area).
- One or more species can be used simultaneously as a comonomer in the copolymerization.
- Particularly suitable comonomers are ⁇ -olefins such as butene and / or hexene and Z or octene. In principle, however, all alkenes (except ethylene) can be used - including cyclo-olefins and higher alkenes.
- the second stage is not started until the free inner cross-sectional area of the reactor has been reduced by at least 5% at any point due to the deposition of a polyethylene copolymer coating. In such a case, the space-time yield of the method is already noticeably reduced and blockages or signs are announced. In order to avoid such damage, the second stage is then initiated.
- the polymer produced in the first stage is softer, has a lower density and is stickier than the product of the second stage which already has a high degree of crystallization.
- the copolymer produced in stage 1 generally has ball pressure hardnesses of 30 to 50 MPa, preferably 32 to 42 MPa.
- the underlying standardized method of determining the ball indentation is: (H 132/90): ISOZIEC 2039/1.
- copolymers are often produced that have ball pressure hardnesses of greater than 50 MPa.
- stage 1 and stage 2 or stage 2 varies. The smaller the diameter of the discharge lines or the product valves, the more frequently phase 2 has to be initiated. For production units, a stage can last from several days to several weeks. In principle, however, considerably longer and shorter or shorter times are also possible in this regard.
- level 2 immediately follows level 1. When the two stages are carried out alternately, stage 2 usually follows stage 1 and / or stage 1 immediately follows stage 2. Intermediate stages, e.g. purging with inert gas or purging with pure dispersant are, in principle, also possible. Then at least one further stage is carried out between stage 1 and stage 2 and Z or between stage 2 and stage 1.
- the copolymer coating formed during the copolymerization usually contains at least 95% by weight of copolymer.
- catalyst may be present in the covering as an impurity.
- the catalysts in question are preferably catalysts for
- Phillips catalysts are generally used with a support.
- Phillips catalysts are usually chromium catalysts, which in addition to chromium can also contain other elements such as molybdenum, tungsten, magnesium or zinc.
- Suitable carrier materials for Phillips catalysts are, in particular, inorganic compounds, in particular porous oxides such as Si0 2 , Al 2 SiO 3 , MgO, ZrO 2 , B 2 O 3 , CaO, ZnO or mixtures of these oxides.
- the carrier materials preferably have a particle diameter between 1 and 300 ⁇ m, in particular from 30 to 70 ⁇ m.
- Particularly preferred carriers are silica gels and aluminosilica gels.
- metallocene catalysts can also be used.
- supported systems are used, with finely divided solids based on silica gels preferably being suitable as support materials.
- Examples of particularly suitable complex compounds of the metallocenes include dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (2-methylindenyl) zirconium dichloride, [2,6-diacetylpyridinbis (2,6-diisopropylphenylimine)] iron (II) chloride, [2,6-diacetyl-4-trifluoromethylpyridine- bis ((2,6-diisopropyl) phenylimine)] cobalt (II) chloride, [1,4-die (2,6-diisopropylphenyl) 2 , 3-dimethyldiazylbutadiene] paladium (II) dichloride or [1, 4-di (2,6-di-isopropylphenyl) 2,3-dimethyldiazylbutadiene] nickel (II) dichloride.
- the copolymerization can in particular be carried out as suspension, gas phase or solution polymerization. Accordingly, a dispersant, a fluidizing gas or a solvent must then be used for the copolymerization process.
- Cascade, loop or tube reactors are particularly suitable as reactors for the continuous copolymerization process.
- the copolymerization is carried out at pressures below 100 bar. Usually the temperature in the reactor is lower than the melting point or melting range of all the copolymer contained in the reactor.
- soft and hard copolymers are thus alternately produced, softer copolymers being produced in the first stage than in the second stage. The deposits are removed by producing harder polymer.
- the copolymerization takes place in a 180 l loop reactor and is carried out as a suspension polymerization, with isobutane being used as the dispersant.
- the pressure during the copolymerization is 40 bar in each case.
- the diameter of the discharge line of the loop reactor is tapered and is 25 mm in each case. Further reaction parameters and the concentrations of the feed materials present in the reactor are listed in the following table:
- Catalyst 1 wt% Cr on silica gel; remaining gas volume _ ⁇ 2 ;
- HLMI high load reporting index - measured according to ISO 1 133
- Density (measured according to ISO 183);
- stage 1 a polyethylene copolymer of the type MD 1 (see table above) is produced. After a polymerization time of 70 hours, stage 1 is terminated and stage 2 is initiated by reducing the hexane concentration. The witch concentration is reduced from 3.6 to 0.3% by volume. The polymer HD 2 is thus produced in stage 2 (see table above).
- stage 2 that is to say the metering in of an ethene / hexene mixture with a lower hexene content, a deposit which had formed in stage 1 and had formed in the discharge line is removed from the reactor. The removal of the coating takes about 24 hours, so that stage 1 can then be initiated again by increasing the hexane content in the starting mixture again. A cleaning of the discharge lines is not necessary with this procedure.
- the method on which the comparative example is based is carried out in accordance with the above experiment - only stage 2 is omitted. Only the type MD1 polymer is produced. After a runtime of 76 hours, the system had to be shut down because no product could be discharged through the 25 mm discharge line of the loop reactor. The system was blocked and had to be cleaned.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000606636A JP2002540226A (ja) | 1999-03-22 | 2000-03-14 | エチレン共重合体の製造方法 |
EP00918794A EP1171474A1 (de) | 1999-03-22 | 2000-03-14 | Verfahren zur herstellung von ethylen-copolymer |
AU39620/00A AU3962000A (en) | 1999-03-22 | 2000-03-14 | Method for producing an ethylene copolymer |
US09/889,607 US6586540B1 (en) | 1999-03-22 | 2000-03-14 | Method for producing an ethylene copolymer |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19912855.3 | 1999-03-22 | ||
DE19912855A DE19912855A1 (de) | 1999-03-22 | 1999-03-22 | Verfahren zur Herstellung von Ethylen-Copolymer |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2000056776A1 true WO2000056776A1 (de) | 2000-09-28 |
Family
ID=7901939
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2000/002234 WO2000056776A1 (de) | 1999-03-22 | 2000-03-14 | Verfahren zur herstellung von ethylen-copolymer |
Country Status (7)
Country | Link |
---|---|
US (1) | US6586540B1 (de) |
EP (1) | EP1171474A1 (de) |
JP (1) | JP2002540226A (de) |
CN (1) | CN1159345C (de) |
AU (1) | AU3962000A (de) |
DE (1) | DE19912855A1 (de) |
WO (1) | WO2000056776A1 (de) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10030306A1 (de) | 2000-06-27 | 2002-01-10 | Basf Ag | Prozeßoptimierung der Peroxid-Einspritzung während der Polyethylenherstellung |
US6729906B1 (en) * | 2003-01-13 | 2004-05-04 | Tyco Electronics Corporation | Signal conditioned modular jack assembly with improved shielding |
US7406960B2 (en) * | 2004-12-10 | 2008-08-05 | Fleetguard, Inc. | Oil mist removal device with oil fill |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0095848A2 (de) * | 1982-06-01 | 1983-12-07 | Imperial Chemical Industries Plc | Verfahren zum Mischpolymerisieren von Äthylen |
US5071927A (en) * | 1990-10-09 | 1991-12-10 | Phillips Petroleum Company | High-temperature slurry polymerization of ethylene |
US5627242A (en) * | 1996-03-28 | 1997-05-06 | Union Carbide Chemicals & Plastics Technology Corporation | Process for controlling gas phase fluidized bed polymerization reactor |
EP0848021A2 (de) * | 1996-12-13 | 1998-06-17 | Phillips Petroleum Company | Ethylenpolymerisationsverfahren und daraus erhaltene Produkte |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4204259A1 (de) | 1992-02-13 | 1993-08-19 | Basf Ag | Phillips-katalysator und seine verwendung zur herstellung von ethylenhomopolymerisaten und -copolymerisaten |
-
1999
- 1999-03-22 DE DE19912855A patent/DE19912855A1/de not_active Withdrawn
-
2000
- 2000-03-14 JP JP2000606636A patent/JP2002540226A/ja active Pending
- 2000-03-14 AU AU39620/00A patent/AU3962000A/en not_active Abandoned
- 2000-03-14 US US09/889,607 patent/US6586540B1/en not_active Expired - Fee Related
- 2000-03-14 WO PCT/EP2000/002234 patent/WO2000056776A1/de not_active Application Discontinuation
- 2000-03-14 EP EP00918794A patent/EP1171474A1/de not_active Withdrawn
- 2000-03-14 CN CNB008041385A patent/CN1159345C/zh not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0095848A2 (de) * | 1982-06-01 | 1983-12-07 | Imperial Chemical Industries Plc | Verfahren zum Mischpolymerisieren von Äthylen |
US5071927A (en) * | 1990-10-09 | 1991-12-10 | Phillips Petroleum Company | High-temperature slurry polymerization of ethylene |
US5627242A (en) * | 1996-03-28 | 1997-05-06 | Union Carbide Chemicals & Plastics Technology Corporation | Process for controlling gas phase fluidized bed polymerization reactor |
EP0848021A2 (de) * | 1996-12-13 | 1998-06-17 | Phillips Petroleum Company | Ethylenpolymerisationsverfahren und daraus erhaltene Produkte |
Also Published As
Publication number | Publication date |
---|---|
CN1159345C (zh) | 2004-07-28 |
EP1171474A1 (de) | 2002-01-16 |
JP2002540226A (ja) | 2002-11-26 |
US6586540B1 (en) | 2003-07-01 |
DE19912855A1 (de) | 2000-09-28 |
CN1341127A (zh) | 2002-03-20 |
AU3962000A (en) | 2000-10-09 |
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