WO2018026331A1 - Catalyseur de polymérisation d'oléfines et procédé pour sa préparation - Google Patents

Catalyseur de polymérisation d'oléfines et procédé pour sa préparation Download PDF

Info

Publication number
WO2018026331A1
WO2018026331A1 PCT/TH2016/000067 TH2016000067W WO2018026331A1 WO 2018026331 A1 WO2018026331 A1 WO 2018026331A1 TH 2016000067 W TH2016000067 W TH 2016000067W WO 2018026331 A1 WO2018026331 A1 WO 2018026331A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
preparing
olefin polymerization
range
electron donor
Prior art date
Application number
PCT/TH2016/000067
Other languages
English (en)
Inventor
Likhasit Sinthusai
Siriporn THUMSURUK
Awiruth ITSARIYYA-ANAN
Original Assignee
Irpc Public Company Limited
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
Application filed by Irpc Public Company Limited filed Critical Irpc Public Company Limited
Priority to PCT/TH2016/000067 priority Critical patent/WO2018026331A1/fr
Publication of WO2018026331A1 publication Critical patent/WO2018026331A1/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
    • 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
    • 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
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/06—Catalyst characterized by its size

Definitions

  • the present invention relates to a process for preparing olefin polymerization catalyst, and an olefin polymerization catalyst.
  • this olefin polymerization catalyst is used for the production of high density polyethylene (HDPE) with an improvement of comonomer response and comonomer distribution.
  • HDPE high density polyethylene
  • Ziegler-Natta catalysts have been used for olefin polymerization such as polyethylene, polypropylene, etc. due to their benefits of providing a high molecular weight, high melting point, and controllable morphology of polymers. It's been known that the synthesis method and the catalyst compositions are important for the nature of active species and the performances of the catalyst.
  • the chemical route for preparation process of Ziegler- Natta catalyst comprises the step of: (i) preparation of magnesium compound suspension, (ii) titanation with ⁇ 3 ⁇ 4, and (iii) pre-activation with aluminum alkyl at the elevated temperature.
  • the high density polyolefin film produced by extrusion blow process requires polyolefin raw material with low gel content.
  • factors affecting gel content are, for example, polymer's molecular weight, amount of unmelted particles (i.e. agglomeration of additives), degree of crosslinking, and so on.
  • the titanium (Ti) oxidation state of the catalysts, especially Ti(II) and Ti(III) normally affects molecular weight of polyolefin fractions, i.e. greater percentage of Ti(II) and Ti(III) content providing higher molecular weight polyolefin fractions.
  • US Patent No. 5,292,837 discloses the process of Ziegler-Natta catalyst preparation and the process of (co)polymerization of ethylene to obtain a large particle size polyethylene with a narrow particle size distribution and high bulk density.
  • the catalysts are prepared by reducing the fraction of Ti(III)-containing catalyst obtained from the reaction of magnesium alkoxide, tetravalent transition-metal compound, and organoalurninum compound with metal halides, in particular T1CI .
  • EP Patent No. 0 319 913 Bl discloses the process of olefin polymerization in the presence of a catalyst obtained from the specific components.
  • the catalyst is obtained from a reaction of dialkoxymagnesium, organic acid ester, and silicon compound; then reacting the reaction product with titanium tetrahalide.
  • the catalyst product consumes shorter time to reach a high polymerization activity and can produce the polyolefin with a high stereoregularity polypropylene.
  • EP 0 123 245 discloses the polymerization of olefins and catalyst.
  • the catalyst can be prepared from the reaction of the first catalyst component, organoalurninum halide and halogenating agent comprised a titanium halide.
  • the first catalyst component is obtained from the first mixing between a magnesium dihalide - alkanol adduct, and an alkoxytitanium compound (such as Ti(OR) 4 ) under stirring at 90-100°C and then reacting the resulting product with benzoic acid ester or the combination of benzoic acid ester and phenol.
  • this invention relates to a process for preparing a catalyst for olefin polymerization comprising
  • step (d) heating the reaction mixture obtained in step (c) to 100-120°C and mixing for 1-4 hours, then cooling said reaction mixture to 50-65°C;
  • step (e) adding aluminum alkyl or aluminum alkyl halide into said reaction mixture obtained in step (d), then heating said mixture to 80-100°C for 1-4 hours.
  • transition metal compound is selected from titanium tetrachloride (TiC ), vanadium tetrachloride (VC ), zirconium tetrachloride (ZrC ) or hafnium tetrachloride (HfC ).
  • said hydrocarbon medium is selected from hexane, heptane, octane, nonane, n-decane or white spirit.
  • said aluminum alkyl or aluminum alkyl halide is selected from a group consisting of ethyl aluminum chloride (EADC), diethylaluminum chloride (DEAC), ethyl aluminum sesquichloride (EASC), and triethyl aluminum chloride (TEA).
  • said electron donor is selected from a group consisting of ethyl benzoate, propyl benzoate, butyl benzoate, pentyl benzoate, hexyl benzoate, and a combination thereof.
  • this invention relates to an olefin polymerization catalyst, which is prepared from the above-mentioned process, wherein the catalyst comprises titanium (Ti), magnesium (Mg), aluminum (Al), and electron donor.
  • the olefin polymerization catalyst contains Ti content is in a range of 5-8%wt based on the total weight of catalyst.
  • the olefin polymerization catalyst have the percentage of preactivation less than 80%, preferably in a range of 60-80%, more preferably in a range of 65-75%.
  • the olefin polymerization catalyst contains electron donor content is in a range of 8-12%wt based on the total weight of catalyst.
  • the olefin polymerization catalyst has a particle size in a range of 7-13 ⁇ .
  • the object of this present invention is to provide the catalyst for the production of olefin polymerization with an improvement of comonomer and hydrogen response, high catalytic activity, and comonomer distribution.
  • Another object of this present invention is to provide an efficient catalyst for producing olefin polymer, especially high density polyethylene (HDPE) with low gel content, and good chemical composition distribution.
  • the high density polyethylene produced by this inventive catalyst is suitable for injection, extrusion, and blow moulding process.
  • the object of the present invention is to provide a catalyst for olefin polymerization by using the specifically sequential step of preparation in order to control the titanium content with oxidation state of Ti(III) and reduce the dimeric form of transition metal compound such as TiC -
  • This process is recognized as an environmental friendly process of catalyst production for producing olefin polymer.
  • the present invention relates to a process for preparing a catalyst for olefin polymerization comprising
  • step (d) heating the reaction mixture obtained in step (c) to 100-120°C and mixing for 1-4 hours, then cooling said reaction mixture to 50-65°C;
  • step (e) adding aluminum alkyl or aluminum alkyl halide into said reaction mixture obtained in step (d), then heating said mixture to 80-100°C for 1-4 hours.
  • the magnesium ethoxide suspension was mixed with electron donor for hydrogen response as well as stereocontrol for higher alpha olefin polymerization at ambient temperature for utmost 24 hrs.
  • the preferred time period is 10-24 hrs.
  • the transition metal compound used in this invention is selected from titanium tetrachloride (TiCL t ), vanadium tetrachloride (VC ), zirconium tetrachloride (ZrCLt) or hafnium tetrachloride (HfCk).
  • the preferred transition metal compound is titanium tetrachloride (TiC ).
  • the hydrocarbon medium used in this invention is selected from hexane, heptane, octane, nonane, n-decane, or white spirit.
  • the preferred hydrocarbon medium is n-decane or white spirit (Exsol D80X).
  • the electron donor used in this invention is selected from a group consisting of ethyl benzoate, propyl benzoate, butyl benzoate, pentyl benzoate, hexyl benzoate, and a combination thereof.
  • the electron donor is propyl benzoate.
  • the advantage of propyl benzoate as electron donor is useful for the hydrogen response optimization of the catalyst. This parameter is very crucial for polymerization operating control and polymer properties consistency.
  • the aluminum alkyl or aluminum alkyl halide is selected from a group consisting of ethyl aluminum chloride (EADC), diethylaluminum chloride (DEAC), ethyl aluminum sesquichloride (EASC), triethyl aluminum chloride (TEA), and a combination thereof.
  • the mi um alkyl or aluminum alkyl halide is ethyl alurninum sesquichloride.
  • the mixing time in step (b) is in a range of 10-12 hours.
  • the heating temperature in step (c) is at 80-90°C.
  • the heating temperature and mixing time in step (d) is at 100-110°C, and 2-3 hours, respectively.
  • a molar ratio of Ti/Mg and electron donor/Mg is in a range of 0.22 - 0.27, and 0.10 - 0.30, respectively.
  • a molar ratio of EASC/Ti is in a range of 1.50 - 2.50, preferably in a range of 1.80 - 2.00.
  • a molar ratio of electron donor/Ti is in a range of 0.5-1.0.
  • a particle size of said Mg(OEt) 2 is in a range of 4 - 6 ⁇ ⁇ .
  • the present invention also relates to an olefin polymerization catalyst prepared from the above mentioned process comprising titanium (Ti), magnesium (Mg), aluminum (Al), and electron donor.
  • the olefin polymerization catalyst contains Ti content is in a range of 5-8%wt based on the total weight of catalyst.
  • the olefin polymerization catalyst have the % of preactivation is less than 80%, preferably in a range of 60-80%, more preferably in a range of 65-75%).
  • the percentage of catalyst preactivation relates to a ratio of Ti(III) to total Ti content in catalyst.
  • the electron donor used in this invention is selected from a group consisting of ethyl benzoate, propyl benzoate, butyl benzoate, pentyl benzoate, hexyl benzoate, and a combination thereof.
  • the electron donor is propyl benzoate.
  • the preferred electron donor content in the olefin polymerization catalyst is in a range of 8-12%wt based on the total weight of catalyst.
  • the olefin polymerization catalyst has a particle size in a range of 7 - 13 ⁇
  • catalyst is basically important for both olefin polymerization operation and polymer properties. Poor morphology of catalyst particles usually causes poor morphology of polymer powder and problems of polymerization processing control such as high fine powder content, drying process efficiency, powder transportation, etc. In addition, some catalyst may cause high wax content in mother liquor. Beside this invention, it is true that the synergy of specific electron donor and active species control of this catalytic system does not only minimize the gel formation of polyethylene by reducing high molecular weight fraction but also enhances the comonomer incorporation of copolymerization as well.
  • reaction mixture of T1CI4 and gel-liked magnesium ethoxide was heated up to 110°C and stirred for further 2 hours before cooling down the reaction to 60-65°C.
  • solution of 0.175 mole of ethyl aluminum sesquichloride diluted in hexane (10 wt%) was slowly added to the reaction mixture.
  • the reaction mixture was then heated up to 100°C and stirred at 250 rpm for 2 hours.
  • 5.4 ml (0.03 mole) of ethyl benzoate was added into to the reaction mixture, and heated to 60°C with stirring for 2 hours.
  • the reaction mixture was cooled down to room temperature and the catalyst product was drained to a conical flask under nitrogen atmosphere blanketing.
  • the catalysts A3 was prepared by mean of the preparation of catalyst A2, with the exception that, 10 ml (0.07 mole) of ethyl benzoate and 6.97 ml (0.063 mole) of TiCU was used to create the molar ratio of electron donor/Ti of 1.1.
  • Example 5 Preparation of the catalyst A4
  • the catalysts A4 was prepared by mean of the preparation of catalyst A2, with the exception that, 8 ml (0.056 mole) of ethyl benzoate and 6.97 ml (0.063 mole) of TiCU was used to create the molar ratio of electron donor/Ti of 0.89.
  • the catalysts A5 was prepared by mean of the preparation of catalyst A4, with the exception that, the preactivation with EASC was performed at 80°C.
  • the catalysts A6 was prepared by mean of the preparation of catalyst A5, with the exception that, 6.02 ml (0.075 mole) of n-propyl benzoate and 7.25 ml (0.075 mole) of TiCU was used to create the molar ratio of electron donor/Ti of 1.0.
  • the catalysts B2 was prepared by mean of the preparation of catalyst Bl, with the exception that, 6.1 ml (0.038 mole) of n-propyl benzoate and 0.15 mole of EASC was used.
  • the catalysts B3 was prepared by mean of the preparation of catalyst Bl, with the exception that, 6.1 ml (0.038 mole) of n-propyl benzoate was used to create the molar ratio of electron donor/Ti of 0.5.
  • the mixture of propyl benzoate and Mg(OEt) 2 was stirred overnight at ambient temperature before the titanation step.
  • the pre-activation with EASC (0.15 mole) was performed at 80 °C.
  • the molar ratio of EASC/Ti is 2.0.
  • the obtained catalysts were characterized by redox titration with Ce(IV) sulfate for determining Ti contents; by Atomic Absorption Spectroscopy (AAS) for deterrnining Mg, Ti and Al content; by Fourier transform Infrared Spectroscopy (FTIR) for deterrnining the amount of an electron donor; and by laser scattering technique for determining particle size of each of the catalysts.
  • AAS Atomic Absorption Spectroscopy
  • FTIR Fourier transform Infrared Spectroscopy
  • Table 1 shows the analytical results of the obtained catalysts.
  • the catalyst prepared using ethyl benzoate, particularly catalysts A2 to A6 shows the lower percentage of preactivated degree due to the higher Ti(IV) species than the catalyst prepared without using the electron donor (catalyst C).
  • the comonomer incorporation of catalysts A2 to A6 was better because the Ti(IV) species was active for a- olefin polymerization, while Ti(III) and Ti(II) exhibited the lower performance.
  • the polymerization of ethylene was performed in the presence of each of prepared catalysts in the 20 liters stainless steel reactor under two-stages of condition polymerization.
  • the polymerization was carried out by using 1-butene as comonomer, triethylalurninum (TEA) as cocatalyst, H 2 gas as the molecular weight controller.
  • the polymerization was performed in 14 liters of hexane medium under the condition of using 0.8 mmol of prepared catalyst; 50:50 of ethylene ratio of low molecular weight and high molecular weight fraction (EE ratio); 100 of TEA/Ti molar ratio; 5 bars of H 2 pressure at 84°C for 40 min.
  • the total pressure of this reaction stage is 8 bars.
  • the H 2 content in the reactor was removed by flashing off the mixed gas after termination of the polymerization at 60°C. The ventilation was done by diluting the off- gas with 5 bars of N 2 gas for 10 times.
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • Mv viscosity average molecular weight
  • Mz Z-average molecular weight
  • Mw molecular weight distribution
  • the gel content determination was performed by mixing the polymer powder with additives (0.2 phr of calcium stearate, 0.1 phr of Irganox 1010) and then melt mixing it in twin screw extruder (feed zone: 160°C, heating zone: 180-200°C, mixing zone: 200°C, screw conveying zone: 200°C, die zone 200°C).
  • additives 0.2 phr of calcium stearate, 0.1 phr of Irganox 1010
  • the polymer noodle was passed into the cooled water and pelletized.
  • the gel content was evaluated after blow film extrusion at below 30 ⁇ film thickness.
  • Table 2 showed the activities of catalyst and analytical results of the prepared high density polyethylene (HDPE).
  • Catalyst activity (g 10,000 12,000 10,000 10,000 10,000 12,000 10,000 PE/mmol Ti)
  • MFI5 (g/10min) 2 0.30 0.3.2 0.23 0.22 0.28 0.30 0.11 MFR 16.0 19.5 15.0 15.0 16.0 17.0 18.00
  • the melt flow index (MFI 5 ) of the polymer product obtained from all catalyst prepared by pre-treating with an electron donor before the titanation step is well- controlled in the range of polymer film grade.
  • the gel content in HDPE film was determined according to in-house standard method.
  • the results showed that the catalyst prepared by pre-treating with an electron donor before the titanation step can generate polymer product with low gel content (FN 0-1) after conducting film application test.
  • the high Mz value of the synthesized polymer represents a very high molecular weight fraction capable of forming unmelted polymer (gel formation). From the results, the HDPE obtained from the polymerization in the presence of catalysts A4 and A5 showed a significantly low Mz due to longer polymer chain length than others obtained from the catalysts C and Al . The effect of the molecular structure of electron donor on the chemical composition of catalyst and the properties of polymer product was observed as showed in Table 3. Table 3

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 préparation d'un catalyseur de polymérisation d'oléfines et un catalyseur de polymérisation d'oléfines. De préférence, ce catalyseur de polymérisation d'oléfines est utilisé pour la production de polymère oléfinique, en particulier de polyéthylène haute densité (HDPE) présentant une faible teneur en gel et une bonne distribution de composition chimique. Le polyéthylène haute densité produit par le catalyseur de l'invention est approprié pour un procédé d'injection, d'extrusion et de moulage par soufflage. Le catalyseur pour la polymérisation d'oléfines a été préparé à l'aide de l'étape de préparation spécifiquement séquentielle de préparation, afin de réguler la teneur en titane présentant l'étage d'oxydation Ti(III) et de réduire la forme dimère d'un composé de métal de transition tel que le TiCU.
PCT/TH2016/000067 2016-08-04 2016-08-04 Catalyseur de polymérisation d'oléfines et procédé pour sa préparation WO2018026331A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/TH2016/000067 WO2018026331A1 (fr) 2016-08-04 2016-08-04 Catalyseur de polymérisation d'oléfines et procédé pour sa préparation

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/TH2016/000067 WO2018026331A1 (fr) 2016-08-04 2016-08-04 Catalyseur de polymérisation d'oléfines et procédé pour sa préparation

Publications (1)

Publication Number Publication Date
WO2018026331A1 true WO2018026331A1 (fr) 2018-02-08

Family

ID=61072999

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/TH2016/000067 WO2018026331A1 (fr) 2016-08-04 2016-08-04 Catalyseur de polymérisation d'oléfines et procédé pour sa préparation

Country Status (1)

Country Link
WO (1) WO2018026331A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112745406A (zh) * 2019-10-30 2021-05-04 中国石油化工股份有限公司 细粉含量少聚乙烯催化剂的制备方法

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59142206A (ja) * 1983-02-02 1984-08-15 Toho Titanium Co Ltd α−オレフィン類重合用触媒成分の製造方法
EP0294767A1 (fr) * 1987-06-10 1988-12-14 Idemitsu Petrochemical Co. Ltd. Procédé de production de polybutène-1
JPS6411111A (en) * 1987-07-03 1989-01-13 Idemitsu Petrochemical Co Ethylene copolymer for molding
JPH02123108A (ja) * 1988-11-02 1990-05-10 Showa Denko Kk エチレン系重合体の製造方法
JPH0455406A (ja) * 1990-06-22 1992-02-24 Mitsui Petrochem Ind Ltd 固体状チタン触媒成分、これを用いるオレフィン重合用触媒およびオレフィンの重合方法
US20010051586A1 (en) * 1999-06-30 2001-12-13 Job Robert Charles Methods of making magnesium/transition metal alkoxide complexes and polymerization catalysts made therefrom
US6545106B1 (en) * 1994-09-22 2003-04-08 Solvay (Societe Anonyme) Process for the polymerization of olefines
US20030153454A1 (en) * 2001-03-30 2003-08-14 Motoki Hosoka Solid catalyst ingredient and catalyst each for olefin polymerization and propylene block copolymer
WO2011133313A1 (fr) * 2010-04-22 2011-10-27 Fina Technology, Inc. Formation de catalyseur de ziegler-natta par utilisation de composants non mélangés

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59142206A (ja) * 1983-02-02 1984-08-15 Toho Titanium Co Ltd α−オレフィン類重合用触媒成分の製造方法
EP0294767A1 (fr) * 1987-06-10 1988-12-14 Idemitsu Petrochemical Co. Ltd. Procédé de production de polybutène-1
JPS6411111A (en) * 1987-07-03 1989-01-13 Idemitsu Petrochemical Co Ethylene copolymer for molding
JPH02123108A (ja) * 1988-11-02 1990-05-10 Showa Denko Kk エチレン系重合体の製造方法
JPH0455406A (ja) * 1990-06-22 1992-02-24 Mitsui Petrochem Ind Ltd 固体状チタン触媒成分、これを用いるオレフィン重合用触媒およびオレフィンの重合方法
US6545106B1 (en) * 1994-09-22 2003-04-08 Solvay (Societe Anonyme) Process for the polymerization of olefines
US20010051586A1 (en) * 1999-06-30 2001-12-13 Job Robert Charles Methods of making magnesium/transition metal alkoxide complexes and polymerization catalysts made therefrom
US20030153454A1 (en) * 2001-03-30 2003-08-14 Motoki Hosoka Solid catalyst ingredient and catalyst each for olefin polymerization and propylene block copolymer
WO2011133313A1 (fr) * 2010-04-22 2011-10-27 Fina Technology, Inc. Formation de catalyseur de ziegler-natta par utilisation de composants non mélangés

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112745406A (zh) * 2019-10-30 2021-05-04 中国石油化工股份有限公司 细粉含量少聚乙烯催化剂的制备方法
CN112745406B (zh) * 2019-10-30 2023-04-14 中国石油化工股份有限公司 细粉含量少聚乙烯催化剂的制备方法

Similar Documents

Publication Publication Date Title
US8557931B2 (en) Multistage process for the polymerization of ethylene
KR101453636B1 (ko) 폴리올레핀 제조 방법
CN105518062B (zh) 分子量分布加宽的聚乙烯
KR102001440B1 (ko) 촉매 시스템의 존재 하에 2형식 폴리에틸렌을 생산하는 방법
JP5011106B2 (ja) エチレンポリマー組成物を製造するためのマルチステージ方法
CN110036044B (zh) 用于bopp应用的聚丙烯
TWI519346B (zh) 使用非經摻合之組分來形成齊格勒－納塔（ｚｉｅｇｌｅｒ－ｎａｔｔａ）觸媒之方法
EP1717269A1 (fr) Compositions à base de alpha-oléfin homo-or copolymères
CN113646338B (zh) 用于乙烯聚合的氧化铬催化剂
EP2800766A2 (fr) Procédés de production de compositions de catalyseur et produits polymères produits à partir de celles-ci
WO2014096297A1 (fr) Procédé de production d'un procatalyseur de ziegler-natta pour la polymérisation de l'éthylène
KR101990665B1 (ko) 비균질계 지글러-나타 촉매 시스템 및 이를 이용한 올레핀 중합 공정
US9631077B2 (en) Process for preparing ziegler-natta produced polyethylene blends
WO2018026331A1 (fr) Catalyseur de polymérisation d'oléfines et procédé pour sa préparation
JP4976129B2 (ja) ポリオレフィン用チーグラー・ナッタ触媒
US9701770B2 (en) Catalyst for the polymerisation of olefins, process for its production and use
WO2012119954A1 (fr) Procédé de préparation de mélange de polyéthylène comprenant des résines produites avec un métallocène et des résines produites avec un catalyseur ziegler-natta
CN102015783A (zh) 制备聚合催化剂的方法
JP2010533775A (ja) チーグラー・ナッタ触媒の形態を調節する方法
US20110245070A1 (en) Catalyst Components for the Polymerization of Olefins and Catalysts Therefrom Obtained
Thongdonjui et al. Effect of electron donor on PE polymerization
CN113024697B (zh) 用于乙烯聚合的催化剂的制备方法
KR101948387B1 (ko) 실리카 담지형 초고분자량 폴리에틸렌 중합 촉매의 제조 방법 및 이를 이용한 초고분자량 폴리에틸렌 중합체
EA038377B1 (ru) Прокатализатор для полимеризации олефинов
KR20230059020A (ko) 고밀도 폴리에틸렌 및 이를 포함하는 필름

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16911751

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16911751

Country of ref document: EP

Kind code of ref document: A1