WO1995010548A1 - Procede de production de polyethylene a large repartition de poids moleculaire - Google Patents
Procede de production de polyethylene a large repartition de poids moleculaire Download PDFInfo
- Publication number
- WO1995010548A1 WO1995010548A1 PCT/BE1993/000065 BE9300065W WO9510548A1 WO 1995010548 A1 WO1995010548 A1 WO 1995010548A1 BE 9300065 W BE9300065 W BE 9300065W WO 9510548 A1 WO9510548 A1 WO 9510548A1
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- WO
- WIPO (PCT)
- Prior art keywords
- reactor
- molecular weight
- vol
- compound
- component
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 24
- 229920000573 polyethylene Polymers 0.000 title claims description 17
- -1 polyethylene Polymers 0.000 title description 16
- 239000004698 Polyethylene Substances 0.000 title description 9
- 238000009826 distribution Methods 0.000 title description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000005977 Ethylene Substances 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 3
- 230000001105 regulatory effect Effects 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 8
- 150000003609 titanium compounds Chemical class 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 150000002901 organomagnesium compounds Chemical class 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 150000002899 organoaluminium compounds Chemical class 0.000 claims 1
- 238000007334 copolymerization reaction Methods 0.000 abstract 1
- 239000011777 magnesium Substances 0.000 description 14
- 239000010936 titanium Substances 0.000 description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 229910052749 magnesium Inorganic materials 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000002902 bimodal effect Effects 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 239000003701 inert diluent Substances 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 150000003623 transition metal compounds Chemical class 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 101100378709 Arabidopsis thaliana AIR3 gene Proteins 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004705 High-molecular-weight polyethylene Substances 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/02—Ethene
-
- 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 present invention concerns a process for producing polyethylene having a broad molecular weight distribution. More particularly, the present invention relates to the production of high density polyethylene having a broad or bimodal molecular weight distribution.
- the molecular weight distribution is one of the basic properties that determines the properties of the polymer, and thus its end-uses.
- the molecular weight mostly determines the mechanical properties while the molecular weight dispersion mostly determines the rheological properties .
- the lower molecular weight portion aids in processing while the higher molecular weight portion contributes to the good impact resistance of the film, such polyethylene can be processed at higher throughput rate with lower energy requirements .
- the MWD may be described completely by the curve obtained by gel permeation chromatography.
- a good evaluation also called the polydispersity index, is represented by the ratio of the weight average to the number average molecular weight.
- the required MWD will range from 10 to 30.
- a process is furthermore known for the preparation of olefin polymers by a two-stage polymerization, a highmolecular polymer being prepared in the first stage at a low H2/C2H4 ratio and a low-molecular polymer being prepared in the second stage at high H2/C2H4 ratio (EP-A 57,352).
- the catalyst used is, inter alia, a halogen-containing organoaluminum compound together with the reaction product of an oxygen-containing organomagnesium compound and an oxygen-containing organotitanium compound, both of which are in solution, and an aluminum halide.
- polyalkenes with a wide molecular weight distribution and a very good homogeneity can be obtained by the process of polymerizing ethylene, optionally with at most 20 mole % of one or more other alpha-alkene of 3 to 10 carbon atoms, in two liquid full loop reactors in series at a temperature of 50 to 120°C, preferably 60 to 110°C under an absolute pressure of 1 to 100 bar in the presence of a catalyst consisting of a transition metal component (component A) which is the reaction product of an organomagnesium compound with a titanium compound and an organoaluminum compound (compound B) , the average molecular mass being regulated with hydrogen, which process comprises carrying out the polymerization such that the introduction of a co-monomer if any is carried out essentially in the first reactor and that the hydrogen concentration is at a very low concentration in the first reactor to form ethylene polymers having HLMI between 0.01 and 5g/10', while maintaining a very high hydrogen pressure in the second reactor to
- transition metal compounds suitable for the preparation of component A there are used tetravalent halogenated titanium compounds, preferably titanium compounds of the general formula TiX n (0R)4_ n in which n is 1 to 4, X stands for chlorine or bromine, and R for identical or different hydrocarbon radicals, especially straight-chain or branched alkyl groups having 1 to 18, preferably 1 to 10, carbon atoms .
- TiCl4 Ti(OC2H5)2Cl2,Ti(OC2H5)3Cl,Ti(OC3H7)2Cl2,Ti(OC3H7)3Cl, Ti(OiC3H7)2Cl2, Ti(OiC3H7)3Cl , Ti(OiC Ho)2Cl2 , Ti(OiC H ⁇ 3)3Cl
- halogeno-ortho-titanic acid esters of the above formula in situ by reacting the respective ortho-titanic acid ester with HCI in a corresponding proportion.
- This reaction is advantageously carried out at temperatures of from 0 to 200° C, the upper temperature limit being determined by the decomposition temperature of the tetravalent halogenated titanium compound used; it is advantageously carried out at temperatures of from 60 to 120° C.
- the reaction may be effected in inert diluents, for example aliphatic or cycloaliphatic hydrocarbons as are currently used for the low pressure process such as butane, pentane, hexane, heptane, cyclohexane, methyl-cyclohexane as well as aromatic hydrocarbons, such as benzene or toluene; hydrogenated Diesel oil fractions which have been carefully freed from oxygen, sulfur compounds and moisture are also useful.
- inert diluents for example aliphatic or cycloaliphatic hydrocarbons as are currently used for the low pressure process such as butane, pentane, hexane, heptane, cyclohex
- reaction product of magnesium alcoholate and tetravalent halogenated titanium compound which is insoluble in hydrocarbons is freed from unreacted titanium compound by washing it several times with one of the above inert diluents in which the titanium- (IV) -compound used is readily soluble.
- magnesium alcoholates preferably those of the general formula Mg(OR)2 are used, in which R stands for identical or different hydrocarbon radicals, preferably straight-chain or branched alkyl groups having 1 to 10 carbon atoms; magnesium alcoholates having alkyl groups of from 1 to 4 carbon atoms are preferred. Examples thereof are Mg(OCH3)2, M (OC2H5)2, Mg(OC3H7)2, Mg(OiC 3 H 7 )2, Mg(OC4H 9 ) 2 . Mg(OiC4H 9 ) 2 , Mg(OCH 2 -CH2-C 6 H 5 )2.
- R stands for identical or different hydrocarbon radicals, preferably straight-chain or branched alkyl groups having 1 to 10 carbon atoms; magnesium alcoholates having alkyl groups of from 1 to 4 carbon atoms are preferred. Examples thereof are Mg(OCH3)2, M (OC2H5)2, Mg(OC3H7)2, Mg(OiC 3 H 7 )2, Mg(OC4H 9
- the magnesium alcoholates can be prepared by known methods, for example by reacting magnesium with alcohols, especially monohydric aliphatic alcohols.
- Magnesium alcoholates of the general formula X-Mg-OR in which X stands for halogen, (S ⁇ 4) 2 carboxylate, especially acetate or OH, and R has the above meaning, may also be used.
- These compounds are, for example, obtained by reacting alcoholic solutions of the corresponding anhydrous acids with magnesium.
- the titanium content of component A may be within the range of from 0.05 to lOmg.-atom, per gram of component A. It can be controlled by the reaction time, the reaction temperature and the concentration of the tetravalent halogenated titanium compound used.
- the concentration of the titanium component fixed on the magnesium compound is advantageously in the range of from 0.005 to 1.5 mmol, preferably from 0.03 to 0.8mmol, per litre of dispersing agent or reactor volume. Generally, even higher concentrations are possible.
- the organo-aluminum compounds used may be reaction products of aluminum-trialkyl or aluminum-dialkyl hydrides with hydrocarbon radicals having 1 to 16 carbon atoms, preferably Al(iBu)3 or Al(iBu)2H and diolefins containing 4 to 20 carbon atoms, preferably isoprene; for example aluminum isoprenyl.
- chlorinated organo-aluminum compounds for example dialkyl-aluminum monochlorides of the formula R2A1C1 or alkyl-aluminum sesquichlorides of the formula R3AI2CI3 , in which formulae R stands for identical or different hydrocarbon radicals , preferably alkyl groups having 1 to 16 carbon atoms , preferably 2 to 12 carbon atoms, for example (C2H5)2A1C1, (iC4H 9 )2AlCl, (C 2 H 5 )3Al2Cl3.
- R stands for identical or different hydrocarbon radicals , preferably alkyl groups having 1 to 16 carbon atoms , preferably 2 to 12 carbon atoms, for example (C2H5)2A1C1, (iC4H 9 )2AlCl, (C 2 H 5 )3Al2Cl3.
- component B aluminum-trialkyls of the formula AIR3 or aluminum-dialkyl hydrides of the formula AIR2H, in which formulae R stands for identical or different hydrocarbons , preferably alkyl groups having 1 to 16, preferably 2 to 6, carbon atoms, for example Al(C2H5)3, Al(C2H5)2H, Al(C3H7)3, Al(C3H7)2H, Al(iC4H 9 )3, or Al(iC4H 9 )2H.
- formulae R stands for identical or different hydrocarbons , preferably alkyl groups having 1 to 16, preferably 2 to 6, carbon atoms, for example Al(C2H5)3, Al(C2H5)2H, Al(C3H7)3, Al(C3H7)2H, Al(iC4H 9 )3, or Al(iC4H 9 )2H.
- the organoaluminum may be used in a concentration of from 0,5 to 10 mmol per litre of reactor volume.
- the polymerization of ethylene is carried out slurry in two liquid full loop reactors connected in series.
- alpha-olefin having from 3 to 10 carbon may be cited, and preferably 1-hexene is used.
- Ethylene is injected with the comonomer in the first loop reactor together the precontacted catalyst.
- the catalyst may comprise an usual electron-donor such as isoalkylphthalate .
- the polymerisation is carried out at a temperature of from 50 to
- 120°C preferably from 60 to 110°C at a pressure of 1 to 100 bar, and preferably 30 to 50 bar.
- the residence time in the first reactor may be shorter or larger than in the second reactor, depending on the HMW/LMW ratio desired for the end polymer.
- the hydrogen is maintained at a low concentration comprised between 0.005-0.07 vol% in the first reactor and between
- the ethylene polymer stream obtained in the first reactor is transferred in the second loop reactor.
- the polymerization is pursued at a pressure comprised between 30 and 50 bar; at a temperature between 50 and 100°C and preferably between 80 and 110°C.
- the residence time is generally comprised between 0.5 and 1 hour.
- this part represents from 10 to 90% and preferable 30 to 70wt% of the bimodal polymer.
- One of the feature of the present invention resides in the fact that the ethylene, catalyst and comonomer are injected in the first reactor leads to better mechanical properties.
- the following examples are given to illustrate the process of the invention without limiting its scope.
- Isobutane 35 gk/h is used as diluant. Tibal concentration is given with regard to iC4 amount.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Procédé d'homo- ou de co-polymérisation d'éthylène dans deux réaceurs à boucle contenant un liquide et raccordés en série, le poids moléculaire moyen étant régulé au moyen de l'hydrogène, ce procédé se caractérisant par l'introduction du comonomère (si celui-ci est présent) dans le premier réacteur, et par une concentration d'hydrogène respectivement très faible et très forte dans les premier et second réacteurs.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/BE1993/000065 WO1995010548A1 (fr) | 1993-10-15 | 1993-10-15 | Procede de production de polyethylene a large repartition de poids moleculaire |
| JP7511106A JPH08504883A (ja) | 1993-10-15 | 1993-10-15 | 幅広い分子量分布を示すポリエチレンの製造方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/BE1993/000065 WO1995010548A1 (fr) | 1993-10-15 | 1993-10-15 | Procede de production de polyethylene a large repartition de poids moleculaire |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1995010548A1 true WO1995010548A1 (fr) | 1995-04-20 |
Family
ID=3886802
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/BE1993/000065 WO1995010548A1 (fr) | 1993-10-15 | 1993-10-15 | Procede de production de polyethylene a large repartition de poids moleculaire |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPH08504883A (fr) |
| WO (1) | WO1995010548A1 (fr) |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997003124A1 (fr) * | 1995-07-10 | 1997-01-30 | Borealis Polymers Oy | Composition de gainage de cable |
| WO1997036942A1 (fr) * | 1996-04-01 | 1997-10-09 | The Dow Chemical Company | Polymerisation en solution d'olefines |
| US5977251A (en) * | 1996-04-01 | 1999-11-02 | The Dow Chemical Company | Non-adiabatic olefin solution polymerization |
| US6165387A (en) * | 1997-02-04 | 2000-12-26 | Borealis A/S | Composition for electric cables |
| US6180721B1 (en) | 1998-06-12 | 2001-01-30 | Borealis Polymers Oy | Insulating composition for communication cables |
| US6185349B1 (en) | 1998-12-18 | 2001-02-06 | Borealis Polymers Oy | Multimodal polymer composition |
| US6268442B1 (en) | 1997-11-18 | 2001-07-31 | Borealis A/S | Process for the reduction of reactor fouling |
| US6416860B1 (en) | 1997-10-20 | 2002-07-09 | Borealis A/S | Electric cable and a method and composition for the production thereof |
| WO2002018461A3 (fr) * | 2000-08-25 | 2002-08-29 | Equistar Chem Lp | Polyethylene de densite moyenne et de poids moleculaire eleve |
| US6586509B1 (en) | 1998-07-03 | 2003-07-01 | Borealis Technology Oy | Composition for electric cables comprising thiodiol fatty acid diesters |
| US6645588B1 (en) | 1995-07-10 | 2003-11-11 | Borealis Technology Oy | Coating composition |
| US6734131B2 (en) | 2001-04-30 | 2004-05-11 | W. R. Grace & Co.-Conn. | Heterogeneous chromium catalysts and processes of polymerization of olefins using same |
| EP1359167A4 (fr) * | 2000-12-21 | 2004-08-25 | Japan Polychem Corp | Polymeres d'ethylene |
| US6921804B2 (en) | 2003-03-25 | 2005-07-26 | Equistar Chemicals L.P. | Cascaded polyolefin slurry polymerization employing disengagement vessel between reactors |
| US6924340B2 (en) | 2002-04-04 | 2005-08-02 | Equistar Chemicals L.P. | Process for removal of intermediate hydrogen from cascaded polyolefin slurry reactors |
| US7714072B2 (en) | 2003-05-12 | 2010-05-11 | Dow Global Technologies Inc | Polymer composition and process to manufacture high molecular weight-high density polyethylene and film therefrom |
| WO2011095629A1 (fr) * | 2010-02-05 | 2011-08-11 | Total Petrochemicals Research Feluy | Polyéthylène bimodal pour des applications de moulage par soufflage |
| CN116041592A (zh) * | 2018-09-17 | 2023-05-02 | 切弗朗菲利浦化学公司 | 改性负载型铬催化剂和由其生产的基于乙烯的聚合物 |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0989141A1 (fr) * | 1998-09-25 | 2000-03-29 | Fina Research S.A. | Elaboration de polyéthylène multimodal |
| EP1842861A1 (fr) * | 2006-04-03 | 2007-10-10 | Total Petrochemicals Research Feluy | Procédé pour améliorer la polymerisation d'éthylène et d'un ou de plusieurs comonomère(s) optionnel(s) dans un réacteur à boucles |
| JP6519414B2 (ja) * | 2014-09-05 | 2019-05-29 | 日本ポリエチレン株式会社 | エチレン系重合体組成物及びそれよりなる成形体 |
| JP6519415B2 (ja) * | 2014-09-05 | 2019-05-29 | 日本ポリエチレン株式会社 | エチレン系重合体組成物及びそれよりなる成形体 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0057420A2 (fr) * | 1981-01-30 | 1982-08-11 | Sumitomo Chemical Company, Limited | Procédé de préparation de polymères d'éthylène |
| EP0274536A1 (fr) * | 1986-07-04 | 1988-07-20 | Mitsui Petrochemical Industries, Ltd. | Composition a base de polyolefine pour le moulage par injection |
| WO1992012181A1 (fr) * | 1990-12-28 | 1992-07-23 | Neste Oy | Procede d'homopolymerisation et de copolymerisation d'ethene |
-
1993
- 1993-10-15 WO PCT/BE1993/000065 patent/WO1995010548A1/fr unknown
- 1993-10-15 JP JP7511106A patent/JPH08504883A/ja active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0057420A2 (fr) * | 1981-01-30 | 1982-08-11 | Sumitomo Chemical Company, Limited | Procédé de préparation de polymères d'éthylène |
| EP0274536A1 (fr) * | 1986-07-04 | 1988-07-20 | Mitsui Petrochemical Industries, Ltd. | Composition a base de polyolefine pour le moulage par injection |
| WO1992012181A1 (fr) * | 1990-12-28 | 1992-07-23 | Neste Oy | Procede d'homopolymerisation et de copolymerisation d'ethene |
Cited By (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997003124A1 (fr) * | 1995-07-10 | 1997-01-30 | Borealis Polymers Oy | Composition de gainage de cable |
| US6645588B1 (en) | 1995-07-10 | 2003-11-11 | Borealis Technology Oy | Coating composition |
| US6329054B1 (en) | 1995-07-10 | 2001-12-11 | Borealis Polymers Oy | Cable and method for using a cable-sheathing composition including an ethylene polymer mixture |
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| US7396892B2 (en) | 2002-04-04 | 2008-07-08 | Equistar Chemicals L.P. | Process for removal of intermediate hydrogen from cascaded polyolefin slurry reactors |
| US6921804B2 (en) | 2003-03-25 | 2005-07-26 | Equistar Chemicals L.P. | Cascaded polyolefin slurry polymerization employing disengagement vessel between reactors |
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| US8609792B2 (en) | 2010-02-05 | 2013-12-17 | Total Research & Technology Feluy | Bimodal polyethylene for blow-moulding applications |
| KR101430847B1 (ko) * | 2010-02-05 | 2014-08-18 | 토탈 리서치 앤드 테크놀로지 펠루이 | 취입-성형 적용물용 바이모달 폴리에틸렌 |
| EA022576B1 (ru) * | 2010-02-05 | 2016-01-29 | Тотал Ресерч Энд Текнолоджи Фелюи | Способ получения бимодальной полиэтиленовой смолы для выдувного формования |
| CN116041592A (zh) * | 2018-09-17 | 2023-05-02 | 切弗朗菲利浦化学公司 | 改性负载型铬催化剂和由其生产的基于乙烯的聚合物 |
| CN116041592B (zh) * | 2018-09-17 | 2024-04-02 | 切弗朗菲利浦化学公司 | 改性负载型铬催化剂和由其生产的基于乙烯的聚合物 |
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