WO2002053607A1 - Procede de production d'homo- et de copolymeres ethyleniques - Google Patents

Procede de production d'homo- et de copolymeres ethyleniques Download PDF

Info

Publication number
WO2002053607A1
WO2002053607A1 PCT/KR2001/002241 KR0102241W WO02053607A1 WO 2002053607 A1 WO2002053607 A1 WO 2002053607A1 KR 0102241 W KR0102241 W KR 0102241W WO 02053607 A1 WO02053607 A1 WO 02053607A1
Authority
WO
WIPO (PCT)
Prior art keywords
compound
chloride
group
copolymer
bromide
Prior art date
Application number
PCT/KR2001/002241
Other languages
English (en)
Inventor
Sang-Yull Kim
Chun-Byung Yang
Ji-Yong Park
Weon Lee
Original Assignee
Samsung General Chemicals Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR10-2001-0076519A external-priority patent/KR100476881B1/ko
Application filed by Samsung General Chemicals Co., Ltd. filed Critical Samsung General Chemicals Co., Ltd.
Priority to EP01272946A priority Critical patent/EP1360212A4/fr
Publication of WO2002053607A1 publication Critical patent/WO2002053607A1/fr

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
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • 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
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene

Definitions

  • the present invention relates to a method for preparing homopolymer and copolymer of ethylene, and more particularly, to a method for preparing homopolymer and copolymer of ethylene, by using a preactivated catalyst as a main catalyst and by introducing saturated hydrocarbon compound containing halogen during polymerization, the preactivated catalyst being prepared by reacting a magnesium solution dissolved in alcohol with phosphorus compound, silane compound and mixture of titanium compound and silicone compound in turn, and with titanium compound again, and then by preactivating the reacted solution through the reaction with organomagnesium compound.
  • Magnesium containing catalysts for polymerization and copolymerization of ethylene are known to exhibit very high catalytic activity and are suitable for liquid phase or gas phase polymerization.
  • the catalyst should have high catalytic activity.
  • molecular weight distribution is an important factor which determines the physical properties of ethylene polymers. Especially, narrow molecular weiglit distribution of the polyethylene is a very important and advantageous feature for the injection molding processed products. As the molecular weight of the polymer increases, tensile strength becomes high but processability is reduced so causing the problem of occurring split during processing.
  • One method to solve this problem is to introduce high molecular weight tail to molecular weight distribution while raising molecular weight. Especially, the introduction of high molecular weight tail is ideal since it can increase tensile strength while not affecting the processability.
  • the object of the present invention is to provide a method for preparing polymer and copolymer of ethylene which have narrow molecular weight distribution and show bidentate structure in the molecular weight distribution curve, by using the simple method which includes preactivating prepared catalyst and introducing saturated hydrocarbon containing halogen during polymerization.
  • the method for producing homo- and co-polymers of ethylene comprises carrying out polymerization or copolymerization of ethylene in the presence of (1) a solid titanium complex catalyst prepared by the steps of (a) preparing a magnesium solution by contacting halogenated magnesium compound, which is a support, with alcohol, (b) reacting said magnesium solution with phosphorus compound and silane compound containing alkoxy group as electron donors, (c) preparing a catalyst precursor through recrystallization into solids by contacting the solution prepared in step (b) with solution of mixture of titanium compound and silicone compound, (d) preparing a solid titanium complex catalyst by reacting the catalyst precursor with titanium compound, and (e) preactivating the solid titanium complex catalyst by reacting with organomagnesiurn compound; (2) organometallic compound in Group U or HI of the Periodic Table; and (3) a saturated hydrocarbon containing halogen, which is introduced during polymerization.
  • a solid titanium complex catalyst prepared by the steps of (a) preparing a magnesium solution by contacting halogenated
  • halogenated magnesium compounds used include but are not limited to: dihalogenated magnesiums such as magnesium chloride, magnesium iodide, magnesium fluoride, and magnesium bromide; alkymagnesium halides such as methylmagnesium halide, ethylmagnesium halide, propylmagnesium halide, butylmagnesium halide, isobutylmagnesium halide, hexylmagnesium halide, and amylmagnesium halide; alkoxymagnesium halides such as methoxymagnesium halide, ethoxymagensium halide, isopropoxymagnesium halide, butoxymagnesium halide, octoxymagnesium halide; or aryloxymagnesium halides such as phenoxymagnesium halide and methyl-phenoxymagnesium halide.
  • dihalogenated magnesiums such as magnesium chloride, magnesium iodide, magnesium fluor
  • magnesium compounds can be used in the mixture of two or more of said compounds or in the form of a complex compound with other metals.
  • the magnesium solution used in the present invention can be produced as solution by using the aforementioned halogenated magnesium compounds in the presence a hydrocarbon solvent or in the absence thereof, by using alcohol.
  • the hydrocarbon solvents used in the present invention include but are not limited to aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, and kerosene; alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, and methylcyclohexane; or aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, and cymene.
  • aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, and kerosene
  • alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, and methylcyclohexane
  • aromatic hydrocarbons such as benzene, toluene, x
  • alcohol When a halogenated magnesium compound is converted into a magnesium solution, alcohol is used in the presence of the aforementioned hydrocarbons or in the absence thereof.
  • the types of alcohol include but are not limited to those containing 1 ⁇ 20 carbon atoms, such as methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, decanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, isopropyl benzyl alcohol, and cumyl-alcohol, although alcohol containing 1 - 12 carbon atoms is preferable.
  • the total amount of alcohol is preferably 2.0-10 mol per each mole of magnesium compounds, and the dissolving temperature, while depending on the types of alcohol, is about 0 ⁇ 150°C, and the dissolving time is about 15 minutes ⁇ 5 hours or preferably about 30 minutes ⁇ 4 hours.
  • the phosphoruos compound used in the present invention is expressed by the following general formula:
  • the type of these includes phosphorus trichloride, phosphorus tribromide, diethylchlorophosphite, diphenylchlorophosphite, diethylbromophosphite, diphenylbromophosphite, dimethylchlorophosphite, phenylchlorophosphite, trimethylphosphite, triethylphosphite, tri-n-butylphosphite, trioctylphosphite, tridecylphosphite, triphenylphosphite, triethylphosphate, tri-n-butylphosphate, or triphenylphophate.
  • Other phosphorous compounds satisfying the aforementioned formula may be used.
  • 0.25 mole or less per 1 mole of magnesium compound, and more preferably 0.2 mole or less per 1 mole of magnesium compound is appropriate.
  • the silane compound having an alkoxy group, another electron donor is represented as the general formula: R n Si(OR) 4 _ n .
  • R is a hydrocarbon group having 1 ⁇ 12 carbon atoms, and n natural number between 1 and 3. More specifically, the following compounds can be used: dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, methylphenylmethoxysilane, diphenylethoxysilane, ethyltrimethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, ethylsilicate
  • the titanium compounds used in the present invention is expressed by the following general formula:
  • Ti(OR) a X 4 -a where R stands for an alkyl group with 1—10 carbon atoms, X a halogen atom, and "a" is a natural number between 0 and 4.
  • titanium compounds which satisfy the general formula of Ti(OR) a X 4 - a include 4-halogenated titanium such as TiCl 4 , TiBr 4 , and Tilt; 3-halogenated allcoxy-titanium such as Ti(OCH 3 )Cl 3 , Ti(OC 2 H 5 )Cl 3 , Ti(OC 2 H 5 )Br 3 , and Ti(O(i-C 4 H 9 ))Br ; 2-halogenated alkoxy-titanium such as Ti(OCH 3 ) 2 Cl 2 , Ti(OC 2 H 5 ) 2 Cl 2 , Ti(O(i-C 4 H 9 )) 2 Cl 2 and Ti(OC 2 H 5 ) 2 Br 2 ; and tetra-alkoxy titanium such as Ti
  • a mixture of the above titanium compounds can also be used in the present invention.
  • the preferable titanium compounds are those containing halogen, or more preferably titanium tetrachloride.
  • the silicon compounds used in the present invention is expressed by the following general formula; R n SiCl 4 - n where R stands for hydrogen; or an alkyl, alkoxy, haloalkyl, or aryl group having 1—10 carbons; or a halosilyl or halosilylalkyl group having 1 ⁇ 8 carbons; and n is a natural number between 0 and 3.
  • silicon compounds satisfying the above general formula include silicon tetrachloride; trichlorosilane such as methyltrichlorosilane, ethylti ⁇ chlorosilane, phenyltrichlorosilane; dichlorosilane such as dimethyldichlorosilane, diethyldichlorosilane, diphenyldichlorosilane, and methylphenyldichlorosilane; monochlorosilane such as trimethylchlorosilane; and a mixture of these silicon compounds can also be used in the present invention.
  • the preferable compound is silicon tetrachloride.
  • the appropriate amount of the mixture of a titanium compound and a silicon compound used during recrystallization of the magnesium compound solution is 0.1 ⁇ 200 moles per 1 mole of magnesium compound and preferably 0.1 ⁇ 100 moles, more preferably 0.2 ⁇ 80 moles.
  • the appropriate mole ratio of a titanium compound to a silicon compound in the mixture is 0.05 ⁇ 0.95 and more preferably 0.1 ⁇ 0.8.
  • the reaction of a magnesium compound with the mixture of a titanium compound and a silicon compound should preferably be carried out at a sufficiently low temperature to crystallize particles of the catalyst since the shape and the size of the resultant re- crystallized solid components vary a great deal according to the reaction conditions and affect the bulk density of polymer.
  • reaction should be carried out by contacting at -70 ⁇ 70 ° C , or more preferably at -50 ⁇ 50 ° C . After the contact-reaction, the temperature is slowly raised and reaction is carried out for the duration of 0.5 ⁇ 5 hours at 50 - 150 ° C .
  • the catalyst precursor prepared as above is further reacted with titanium compound represented by general formula Ti(OR) a X 4 . a , where R stands for a hydrocarbon group, X a halogen atom, and "a" is a natural number between 0 and 4.
  • the most preferable compound is titanium tetrachloride and the amount is preferably 1 ⁇ 20 moles per 1 mole of magnesium compounds and more preferably 1-10 moles. Reaction is carried out for 0.5 -5 hours at 40 ° C - 150 ° C
  • the amount of the organomagnesium compound used is preferably 0.02 - 1 mol per 1 mole of halogenated magnesium compound and more preferably 0.1 - 0.5 mol.
  • the catalyst activity can be drastically reduced or the shape of catalyst can be destroyed, fn addition, since the shape of the catalyst changes with reacting temperature, the reaction should by carry out at sufficiently low temperature.
  • the reaction should be carried out at -50 ° C - 50 ° C or more preferably at -20 ° C - 30 ° C. After the contact-reaction, the temperature is slowly raised and the reaction is carried out for 0.5 -5 hours at 40 ° C - 150 ° C
  • the catalyst produced according to the process of the present invention can be utilized for homo- and co-polymerization of ethylene.
  • ⁇ -olefin such as propylene, 1-butene, 1-pentene, 4-methyl-l-pentene, or 1-hexene having three or more carbons can be used.
  • a titanium catalyst prepared as above uses, as a cocatalyst, organometallic compounds of Group H or El of the Periodic Table.
  • the organometallic compound used as a cocatalyst of the present invention can be represented by a general formula of MR n , .
  • M stands for a metal component of Group II or IHA in the Periodic Table such as magnesium, calcium, zinc, boron, aluminum or gallium, and R an alkyl group with 1 -20 carbons such as methyl, ethyl, butyl, hexyl, octyl or decyl group, and n the atomic valence of the metal component.
  • the trialkyl aluminums such as triethylaliiminum and triisobutylalurr ⁇ ium, having an alkyl group of 1 - 6 carbons, or mixture of these are preferable.
  • organoaluminum compound having one or more of halogen or hydride group such as emylaluminum dichloride, (tiemylaluiriinum chloride, ethylaluminum sesquichloride, or dusobutylaluminum hydride, can be used.
  • the polymerization process can be gas phase polymerization or bulk polymerization which is carried without organic solvent, or the process can be liquid slurry polymerization which is carried with organic solvent, h the case of gas phase polymerization, the amount of the catalyst in the reaction system is, in terms of the titanium atom in catalyst, about 0.001 - 5 mmol, and preferably
  • the concentration of the organometallic compound, as calculated by organometallic atom, is preferably 1 - 2,000 moles per 1 mole of titanium atoms in catalyst, and more preferably about 5 -
  • nonpolar organic solvent of alkane compounds such as hexane, n-heptane, octane, nonan or decane, and aromatic compounds such as cycloalkane is used.
  • alkane compounds such as hexane, n-heptane, octane, nonan or decane, and aromatic compounds such as cycloalkane
  • hexane is most preferable and must be purified before use so as not to affect catalyst activity.
  • the concentration of solid titanium complex catalyst in the polymerization reacting system is preferably about 0.001 - 5 mmol, in terms of titanium atoms in catalyst, per one liter of the solvent, and more preferably about 0.001 - 0.5 mmol.
  • saturated hydrocarbon containing halogen it is essential to add saturated hydrocarbon containing halogen during polymerization to obtain polymers having molecular weight distribution in which high molecular weight tail is manifested.
  • Saturated hydrocarbon such as ethylchloride, chloroform, t-butylchloride, tetrachloromethane, ethylbromide, t-butyliodide, n-butylbromide, n-butyliodide and n-butylfluoride, or their mixtures, which contains one or more of halogen of chlorine, bromine, fluorine and iodine, and has 1-10 carbons, can be used. Among these ethylchloride is most preferable.
  • the appropriate temperature of polymerization is generally about 20 - 200 °C, and more preferably about 20 - 95 °C.
  • the appropriate pressure of monomers is between 1 and 100 atm, and more preferably between 2 and 50 atm.
  • the molecular weight of polymers can be controlled by adjusting the amount of hydrogen injected, which is well known in the art.
  • the molecular weight of the polymers is represented as melt index (ASTM D 1238), which is generally known in the art, and the value of the melt index generally becomes larger as the molecular weight decreases.
  • the molecular weight distribution of polymers is measured with gel permeation chromatography (GPC), which is measured by commonly used method in the art.
  • a solid titanium complex catalyst component is produced by following steps.
  • step (c) Treating with solution of mixture of titanium compound and silicone compound
  • a solution of mixture of 90 ml of titanium tetrachloride and 90 ml of silicon tetrachloride is dripped for 2 hours.
  • the temperature of the reactor is raised to 80° C for an hour and maintained at that temperature for an hour.
  • the supernatant of the solution is removed, and to the remaining solid layer, 300 ml of decane and 100 ml of titanium tetrachloride are added continuously. Then, the temperature is raised to 100°C and maintained thereat for two hours.
  • a 2L high-pressure reactor is dried in an oven and assembled while hot. In order to make the inside of the reactor nitrogen atmosphere, nitrogen and vacuum are alternatively manipulated three times in the reactor. Then 1,000 ml of dry n-hexane is injected to the reactor and 0.09 mmol of tn ⁇ sobuthylaluminum and 0.09 mmol of ethylchloride are injected in order and the solid catalysts of 0.03 mmol in terms of titanium atom and 1000 ml of hydrogen are added thereto. The temperature of the reactor is raised to 80 ° C while stirring at 700 ⁇ m with a stirrer and the pressure of ethylene is adjusted to 80psi, and the polymerization is carried out for an hour.
  • the temperature of the reactor was lowered to room temperature, and an excessive amount of ethanol solution is added to tenninate the reaction.
  • the polymer produced is collected segregatedly using filters and is dried in a vacuum oven at 50 ° C for at least six hours.
  • the polymerization activity (kg of polyethylene divided by mmol of Ti) is calculated as the weight (kg) ratio of the polymers produced per catalysts used (mmol of Ti).
  • the results of polymerization are shown in Table 1, together with the melt index (g/10 minutes), molecular weight distribution (Mw/Mn), and the degree of manifestation of high molecular weight tail(Mz/Mw).
  • Example 3 60ml of 1 mole solution of diethylmagnesium is added instead of dibutylmagnesium in the process of preactivating the catalyst in example 1, and the results of polymerization are shown in Table 1.
  • Example 4 60ml of 1 mole solution of butylmagnesium chloride is added instead of dibutylmagnesium in the process of preactivating the catalyst in example 1, and the results of polymerization are shown in Table 1.
  • Example 5 The amount of ethyl chloride added is changed to 0.27mmol in the polymerization in example
  • the catalyst preactivation process in example 1 is omitted.
  • the quantity of the titanium in the catalyst prepared is 5.0%.
  • the polymerization is carried out in the same condition as that of example 1 except that ethyl chloride is not added, and the results are shown in Table 1.
  • the catalyst preactivation process in example 1 is omitted.
  • the content of the titanium in the catalyst prepared is 5.0%.
  • the polymerization is carried out in the same condition as that of example 1, and the results are shown in Table 1.
  • high molecular weight tail is manifested while mamtaining high activity of catalyst and narrow molecular weight distribution, making it possible to obtain polymer having bidentate molecular weight distribution.
  • the polymer having narrow molecular weight distribution, and molecular weight distribution wherein high molecular weight tail is manifested exhibits excellent physical properties and can be usefully applied to injection processed products.

Landscapes

  • 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)

Abstract

La présente invention concerne un procédé de production d'homo- et de copolymères éthyléniques. Ce procédé consiste en particulier à utiliser un catalyseur produit selon un procédé consistant à faire réagir un composé phosphoré, un composé silane et une solution de mélange de composés de titane et de silicone avec une solution de magnésium dissoute dans des alcools, à faire à nouveau réagir la solution obtenue avec un composé de titane puis à préactiver le catalyseur obtenu par mise en réaction avec des composés de magnésium organiques de manière à produire un catalyseur principal. Selon le procédé de cette invention, des homo- et copolymères éthyléniques sont ensuite produits par l'addition d'hydrocarbures saturés halogénés pendant la polymérisation. La présente invention concerne également un procédé pour la production d'homo- et de copolymères éthyléniques à haut rendement ainsi que pour l'obtention d'une structure moléculaire bimodale provenant d'un résidu de poids moléculaire élevé, tout en conservant leur distribution moléculaire étroite.
PCT/KR2001/002241 2000-12-29 2001-12-22 Procede de production d'homo- et de copolymeres ethyleniques WO2002053607A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP01272946A EP1360212A4 (fr) 2000-12-29 2001-12-22 Procede de production d'homo- et de copolymeres ethyleniques

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20000085530 2000-12-29
KR2000-0085530 2000-12-29
KR2001-0076519 2001-12-05
KR10-2001-0076519A KR100476881B1 (ko) 2000-12-29 2001-12-05 에틸렌 중합체 및 공중합체 제조방법

Publications (1)

Publication Number Publication Date
WO2002053607A1 true WO2002053607A1 (fr) 2002-07-11

Family

ID=26638676

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2001/002241 WO2002053607A1 (fr) 2000-12-29 2001-12-22 Procede de production d'homo- et de copolymeres ethyleniques

Country Status (2)

Country Link
EP (1) EP1360212A4 (fr)
WO (1) WO2002053607A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1401883A1 (fr) * 2001-06-21 2004-03-31 Samsung General Chemicals Co., Ltd. Catalyseur de polymerisation et de copolymerisation d'ethylene
WO2004037873A1 (fr) * 2002-10-24 2004-05-06 Eastman Chemical Company Procede de polymerisation de l'ethylene et interpolymeres associes
WO2006009949A2 (fr) * 2004-06-21 2006-01-26 Exxonmobile Chemical Patents Inc. Procede de polymerisation a faible encrassement et haute activite
WO2006025917A2 (fr) * 2004-06-21 2006-03-09 Exxonmobil Chemical Patents Inc. Procede de polymerisation
JP2008531750A (ja) * 2004-03-11 2008-08-14 エスケー エナジー 株式会社 エチレン重合用触媒の製造方法
CN107880168A (zh) * 2016-09-30 2018-04-06 中国石油化工股份有限公司 用于烯烃聚合的催化剂组分及其制备与应用
US11261198B2 (en) 2016-06-20 2022-03-01 Shionogi & Co., Ltd. Process for preparing substituted polycyclic pyridone derivative and crystal thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4042771A (en) * 1973-09-17 1977-08-16 Naphtachimie Polymerization of olefins with pre-activated catalysts
JPS55151009A (en) * 1979-05-16 1980-11-25 Mitsui Petrochem Ind Ltd Preparation of olefin polymer or copolymer
JPS6254706A (ja) * 1985-09-03 1987-03-10 Mitsubishi Petrochem Co Ltd オレフイン重合体の製造法
JPH107716A (ja) * 1996-06-28 1998-01-13 Mitsui Petrochem Ind Ltd 固体状チタン触媒成分、その調製方法、触媒およびオレフィンの重合方法
KR20000009625A (ko) * 1998-07-27 2000-02-15 유현식 개선된 올레핀 중합 및 공중합용 촉매

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4042771A (en) * 1973-09-17 1977-08-16 Naphtachimie Polymerization of olefins with pre-activated catalysts
JPS55151009A (en) * 1979-05-16 1980-11-25 Mitsui Petrochem Ind Ltd Preparation of olefin polymer or copolymer
JPS6254706A (ja) * 1985-09-03 1987-03-10 Mitsubishi Petrochem Co Ltd オレフイン重合体の製造法
JPH107716A (ja) * 1996-06-28 1998-01-13 Mitsui Petrochem Ind Ltd 固体状チタン触媒成分、その調製方法、触媒およびオレフィンの重合方法
KR20000009625A (ko) * 1998-07-27 2000-02-15 유현식 개선된 올레핀 중합 및 공중합용 촉매

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP1360212A4 *

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1401883A1 (fr) * 2001-06-21 2004-03-31 Samsung General Chemicals Co., Ltd. Catalyseur de polymerisation et de copolymerisation d'ethylene
EP1401883A4 (fr) * 2001-06-21 2005-01-12 Samsung General Chemicals Co Catalyseur de polymerisation et de copolymerisation d'ethylene
US6759492B2 (en) 2001-07-24 2004-07-06 Eastman Chemical Company Process for the polymerization of ethylene and interpolymers thereof
WO2004037873A1 (fr) * 2002-10-24 2004-05-06 Eastman Chemical Company Procede de polymerisation de l'ethylene et interpolymeres associes
CN102417554A (zh) * 2002-10-24 2012-04-18 西湖朗维尤公司 乙烯及其共聚物的聚合方法
JP2008531750A (ja) * 2004-03-11 2008-08-14 エスケー エナジー 株式会社 エチレン重合用触媒の製造方法
WO2006025917A3 (fr) * 2004-06-21 2006-10-12 Exxonmobil Chem Patents Inc Procede de polymerisation
WO2006009949A3 (fr) * 2004-06-21 2007-09-07 Exxonmobil Chem Patents Inc Procede de polymerisation a faible encrassement et haute activite
WO2006025917A2 (fr) * 2004-06-21 2006-03-09 Exxonmobil Chemical Patents Inc. Procede de polymerisation
US7423103B2 (en) 2004-06-21 2008-09-09 Exxonmobil Chemical Patents Inc. Low fouling and high activity polymerization process
US7858714B2 (en) 2004-06-21 2010-12-28 Exxonmobil Chemical Patents Inc. Polymerization process
WO2006009949A2 (fr) * 2004-06-21 2006-01-26 Exxonmobile Chemical Patents Inc. Procede de polymerisation a faible encrassement et haute activite
US11261198B2 (en) 2016-06-20 2022-03-01 Shionogi & Co., Ltd. Process for preparing substituted polycyclic pyridone derivative and crystal thereof
US11807648B2 (en) 2016-06-20 2023-11-07 Shionogi & Co., Ltd. Process for preparing substituted polycyclic pyridone derivative and crystal thereof
CN107880168A (zh) * 2016-09-30 2018-04-06 中国石油化工股份有限公司 用于烯烃聚合的催化剂组分及其制备与应用

Also Published As

Publication number Publication date
EP1360212A4 (fr) 2004-09-15
EP1360212A1 (fr) 2003-11-12

Similar Documents

Publication Publication Date Title
EP1349878B1 (fr) Production d'un catalyseur d'homopolymerisation ou de copolymerisation de l' thylene
EP1203034B1 (fr) Catalyseur d'homo ou de co-polymerisation de l'ethylene
EP1242472B1 (fr) Catalyseur ameliore pour homo- et copolymerisation d'olefine
US6762145B2 (en) Method of making a catalyst for polymerization and co-polymerization of ethylene
EP1194455B1 (fr) Catalyseur pour l'homo/copolymerisation de l'ethylene
EP1401883B1 (fr) Catalyseur de polymerisation et de copolymerisation d'ethylene
US6958378B2 (en) Method for producing homo-and co-polymers of ethylene
WO2002053607A1 (fr) Procede de production d'homo- et de copolymeres ethyleniques
EP1401882B1 (fr) Catalyseur de polymerisation et de copolymerisation de l'ethylene
EP1358221B1 (fr) Procédé permettant de produire des homopolymères et des copolymères d'ethylène
JP3676343B2 (ja) エチレン共重合用触媒
KR100476881B1 (ko) 에틸렌 중합체 및 공중합체 제조방법
EP1458773A1 (fr) Procede de polymerisation et de copolymerisation d'ethylene
KR20100100433A (ko) 에틸렌 중합 또는 공중합 촉매의 제조 방법
KR100361225B1 (ko) 에틸렌 중합 및 공중합용 촉매의 제조방법
KR20090092023A (ko) 에틸렌 중합 및 공중합용 촉매의 제조방법
KR101265418B1 (ko) 에틸렌 중합 및 공중합용 촉매의 제조방법
KR101222712B1 (ko) 에틸렌 중합 및 공중합용 촉매의 제조방법
KR20090087632A (ko) 에틸렌 중합 또는 공중합용 촉매 및 그를 이용한 에틸렌중합체 또는 공중합체의 제조방법

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PH PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
WWE Wipo information: entry into national phase

Ref document number: 2001272946

Country of ref document: EP

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

WWP Wipo information: published in national office

Ref document number: 2001272946

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: JP

WWW Wipo information: withdrawn in national office

Country of ref document: JP

WWW Wipo information: withdrawn in national office

Ref document number: 2001272946

Country of ref document: EP