WO2018050127A2 - 一种通用的α-烯烃聚合工业催化剂及其应用 - Google Patents

一种通用的α-烯烃聚合工业催化剂及其应用 Download PDF

Info

Publication number
WO2018050127A2
WO2018050127A2 PCT/CN2017/107601 CN2017107601W WO2018050127A2 WO 2018050127 A2 WO2018050127 A2 WO 2018050127A2 CN 2017107601 W CN2017107601 W CN 2017107601W WO 2018050127 A2 WO2018050127 A2 WO 2018050127A2
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
electron donor
polymerization
alpha
olefin
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/CN2017/107601
Other languages
English (en)
French (fr)
Other versions
WO2018050127A3 (zh
Inventor
王立才
高占先
于丽梅
王焕
李伟
郑国彤
董庆新
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
YINGKOU XIANGYANG CATALYST CO Ltd
Dalian University of Technology
Original Assignee
YINGKOU XIANGYANG CATALYST CO Ltd
Dalian University of Technology
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 YINGKOU XIANGYANG CATALYST CO Ltd, Dalian University of Technology filed Critical YINGKOU XIANGYANG CATALYST CO Ltd
Priority to US16/335,929 priority Critical patent/US11220560B2/en
Publication of WO2018050127A2 publication Critical patent/WO2018050127A2/zh
Publication of WO2018050127A3 publication Critical patent/WO2018050127A3/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/06—Propene
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/642—Component covered by group C08F4/64 with an organo-aluminium compound
    • C08F4/6423—Component of C08F4/64 containing at least two different metals
    • C08F4/6425—Component of C08F4/64 containing at least two different metals containing magnesium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B01J19/1868—Stationary reactors having moving elements inside resulting in a loop-type movement
    • 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
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/34—Polymerisation in gaseous state
    • 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
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/646—Catalysts comprising at least two different metals, in metallic form or as compounds thereof, in addition to the component covered by group C08F4/64
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/647—Catalysts containing a specific non-metal or metal-free compound
    • C08F4/649—Catalysts containing a specific non-metal or metal-free compound organic
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/647—Catalysts containing a specific non-metal or metal-free compound
    • C08F4/649—Catalysts containing a specific non-metal or metal-free compound organic
    • C08F4/6494—Catalysts containing a specific non-metal or metal-free compound organic containing oxygen
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used

Definitions

  • the invention belongs to the field of research and application of ⁇ -olefin polymerization and copolymerization catalyst industry, and particularly relates to a large-scale industrial production catalyst and its application which are commonly used in various processes of ⁇ -olefin polymerization and copolymerization.
  • the Ziegler-Natta (ZN) catalyst is still the main catalyst for industrial olefin polymerization, and the olefin, especially the ⁇ -olefin polymerized, copolymerized ZN catalyst comprises (A) a titanium-containing magnesium chloride supported catalyst component, (B) a cocatalyst organoaluminum compound and (C) an external electron donor that modulates the structure and properties of the polyalphaolefin.
  • the titanium-containing magnesium chloride support catalyst component includes an internal electron donor, and the internal electron donor is the core of the Z-N catalyst.
  • the titanium-containing magnesium chloride supported catalyst component is abbreviated as a catalyst component, and there are mainly three methods for preparing the same, one is a magnesium chloride alcoholate, an internal electron donor, a titanium compound, and a coprecipitated catalyst component;
  • the second method is a spherical magnesium chloride alcoholate carrier-supporting titanium compound, an internal carrier electron donor to obtain a catalyst component, and a third method for preparing a catalyst by reacting magnesium chloride formed by diethoxymagnesium with a titanium chloride compound and an internal electron donor.
  • Component Component.
  • the internal electron donor is the core of the Z-N catalyst because the internal electron donor plays a key role in regulating the activity of the catalyst and the structure of the poly- ⁇ -olefin and is the core component of the catalyst component.
  • the number of internal electron donors that are widely used in the industry is limited, and the performance is limited, which makes it difficult to meet the growing polyolefin.
  • Industrial needs. In recent years, it has been found that two or more electron donors are combined as internal electron donors, which can produce a coordination effect, obtain different performance from a single internal electron donor, and have the advantages of both internal electron donors, and even coordinate to produce new ones. The nature.
  • the performance of the catalyst component prepared by compounding the two electron donors into the internal electron donor can be adjusted, thereby obtaining a catalyst component which satisfies the industrial demand in meeting the increasingly developed multi-brand, special-performance poly- ⁇ -olefin.
  • the preparation of catalyst components for the internal electron donors of two kinds of electron donors is a new idea and a new method for developing new catalyst components with excellent comprehensive performance or excellent performance.
  • the internal electron donor of the composite internal electron donor as an industrial polymerization catalyst must meet the basic requirements of industrial production, such as stable source, low price, stable performance, special performance, adjustable performance and the like.
  • Di-n-butyl phthalate and diisobutyl phthalate are internal electron donors commonly used in industrial ZN catalysts, and their overall performance is higher. Good, moderate price, but exposed some safety issues, low activity at lower polymerization temperatures, lack of special properties of polymers, etc.; and 9,9-bis(methoxymethyl)anthracene
  • the special properties are outstanding, such as high catalyst activity, low polymerization temperature, high molecular weight of polyolefin, high degree of polyolefin and other narrow molecular weight distribution, and can be used as both internal electron donor and external electron donor. .
  • the Applicant developed the industrial production method of 9,9-bis(methoxymethyl)anthracene (CN 1166608C) and established a production facility for the supply of 9,9-bis(methoxymethyl)anthracene to the international market. .
  • the invention selects an internal electron donor of a magnesium chloride carrier catalyst component which is a composite of zirconium phthalate and 9,9-bis(methoxymethyl)phosphonium as an industrial ZN catalyst, and prepares an internal electron donor.
  • a general-purpose industrial polyolefin catalyst component suitable for use in various industrial polymerization reactor polymerization processes.
  • the industrial large-scale preparation of a poly- ⁇ -olefin catalyst product suitable for various polymerization processes comprises a catalyst component A, a cocatalyst alkyl aluminum B and an external electron donor C; wherein:
  • Catalyst component A is a mixture of magnesium chloride supported titanium ions, a composite internal electron donor dialkyl aryl diester and 1,3-diether;
  • the cocatalyst alkyl aluminum B is triethyl aluminum, triisobutyl aluminum or a mixture thereof; the most frequently used is triethyl aluminum;
  • the external electron donor C is an alkyl alkoxysilane or an organic acid ester or an alkyl alkoxysilane and an organic acid ester complex.
  • the catalyst described in the above-disclosed technical means is characterized in that in the catalyst component A, the dialkyl aryl dicarboxylate is di(n-)isobutyl phthalate.
  • the catalyst described in the above-disclosed technical scheme is characterized in that, in the catalyst component A, the 1,3-diether is 9,9-bis(methoxymethyl)anthracene.
  • the catalyst described in the above technical solution is characterized in that: in the catalyst component A, the mass fraction of titanium is 2.0-3.8%, and the mass fraction of magnesium is 15.0-20.0%, and the phthalic acid is The mass fraction of (n-) isobutyl ester is 1.0-7.0%, and the mass fraction of 9,9-bis(methoxymethyl) oxime is 1.0-9.0%.
  • di(n-)isobutyl phthalate and 9,9-di(methoxy) The molar ratio of methyl) oxime determines the properties of the catalyst component. Specifically, the molar ratio of di(n-)isobutyl phthalate to 9,9-bis(methoxymethyl)anthracene is 1-9.9:10.
  • a series of polymerization catalysts are obtained, thereby obtaining various grades of polyolefins that meet market needs.
  • a ZN catalyst component A composite internal electron donor diisobutyl phthalate content of 2.5% and 9,9-bis(methoxymethyl) hydrazine content of 5% can produce a general polypropylene film material;
  • ZN catalyst component A of 7% diisobutyl phthalate and 8% of 9,9-bis(methoxymethyl) hydrazine polypropylene drawing material can be produced by adjusting the process, and polypropylene injection molding can also be produced.
  • propylene homopolymerization products can be produced, and ethylene can also be produced.
  • Propylene copolymer product if the content of diisobutyl phthalate is 4%-5% and the content of 9,9-bis(methoxymethyl) ruthenium is 3%-5%, propylene homopolymerization products can be produced, and ethylene can also be produced. Propylene copolymer product.
  • the preparation method of the catalyst component A includes the following methods: 1 magnesium chloride alcoholate, composite internal electron donor and titanium tetrachloride coprecipitation method Preparation; 2 spherical magnesium chloride alcoholate carrier supported by titanium tetrachloride and composite internal electron donor method; 3 diethoxy magnesium, titanium tetrachloride reaction formed magnesium chloride supported composite internal electron donor.
  • the methods described in 1-3 of the present invention are all prior art and are a common method for preparing catalyst component A by those skilled in the art.
  • As the Applicant used Method 1 a technique for the preparation and application of some new catalyst components A was developed (CN 100,491,415 C, US 8,344,080 B 2 , US 7,964,678 B 2 ).
  • the external electron donor C is a hydrocarbyl alkoxysilane, or an organic acid ester, or a hydrocarbyl alkoxysilane and an organic acid ester complex
  • the hydrocarbyl alkoxysilane is selected from the group of external electron donors commonly used in the industry, including C 1-10 alkyltrimethoxysilane, C 1-8 dialkyldimethoxysilane, alkylcycloalkyl dimethyl Silicon oxysilane, dicycloalkyldimethoxysilane or diphenyldimethoxysilane, typical hydrocarbyl alkoxysilane is propyltrimethoxysilane, diisopropyldimethoxysilane, diiso Butyl dimethoxy silicon, methyl cyclohexyl dimethoxy silicon, dicyclopentyl dimethoxy silicon, diphenyl dimethoxy silicon, etc.; the organic acid este
  • the molar ratio of the hydrocarbyl alkoxysilane to the organic acid ester is from 1 to 9.9:10.
  • the molar ratio of the base silicon to the organic acid ester depends on the ratio of the complex internal electron donor di(n-)isobutyl phthalate to 9,9-bis(methoxymethyl)anthracene, ie, depending on the production of poly- ⁇ - The grade of the olefin.
  • the ⁇ -olefin is polymerized into propylene polymerization, 1-butene polymerization, ethylene and propylene copolymerization, ethylene and 1-butene copolymerization or propylene. Copolymerization with 1-butene.
  • the catalyst according to any one of the above-disclosed embodiments which can be applied to large-scale industrial production of ⁇ -olefin polymers of various polymerization processes, specifically, the application includes: (1) gas phase Reaction: ⁇ -olefin polymerization in UNIPOL gas phase fluidized bed reactor process, ⁇ -olefin polymerization in NOVOLEN stereo stirred tank gas phase reactor process, ⁇ -olefin polymerization in INNOVENE horizontal stirred tank gas phase reactor process, JPP Japan ⁇ -olefin polymerization in a tank gas phase reactor process; (2) batch bulk reaction: ⁇ -olefin polymerization in a tank reactor polymerization process; (3) continuous bulk reaction: ⁇ -olefin polymerization in a SPHERIPOL loop reactor process, A horizontal bulk reactor of the ZHG process is coupled to an alpha-olefin polymerization in a horizontal gas phase reactor process.
  • the most and most important application of ⁇ -olefin polymerization is propy
  • the applications include the production of a plurality of grades of polyolefins having a large difference in properties in the same apparatus in the same process.
  • the composite external electron donor C of the present invention has different choices in a specific process, such as a propylene polymerization in a polymerization process of a NIPOL gas phase fluidized bed reactor, and the external electron donor used is an alkyl alkoxysilane and an organic acid.
  • Binary complexes of ester composition such as propyltrimethoxysilane and isopropyl myristate, produce versatile polypropylene.
  • the long-chain fatty acid ester is selected as the component of the external electron donor C, and it can be used as a plasticizer in the polymer.
  • the isotactic index of the polypropylene produced by the catalyst of the present invention is greater than the isotactic index of the polypropylene produced by the catalyst of the apparatus belt, the bulk density is higher than the polypropylene bulk density of the catalyst of the apparatus belt, and the average particle size of the polypropylene and the apparatus
  • the catalyst is comparable in that the fine powder content of the polypropylene is lower than the finely divided content of the polypropylene produced by the catalyst of the apparatus, and the activity of the catalyst of the present invention is significantly higher than that of the catalyst carried by the apparatus.
  • the polypropylene product produced by the catalyst of the present invention has a lower ash content than the polypropylene product of the catalyst of the apparatus belt; the yellow index is lower than the yellow index of the polypropylene produced by the catalyst of the apparatus belt.
  • the single consumption of the catalyst of the invention has an average unit consumption of 19.6% lower than that of the device, and the catalyst consumption per unit of the triethyl aluminum unit consumption ratio is 30.6% lower than that of the unit, and the unit consumption of the external electron donor is lower than that of the imported electron donor. 32.6%.
  • the polypropylene produced in the fluidized bed reactor is a versatile polypropylene.
  • the efficiency of the catalyst was 24 kg pp / g catl.
  • the catalyst A component of the present invention contains 2.7% titanium, 18.5% magnesium, and 9,9-two (a). Oxymethyl group ⁇ 8% and bis isobutyl phthalate 7%, cocatalyst triethyl aluminum, external electron donor methyl cyclohexyl dimethoxy silicon ZN modified catalyst. According to the process parameters of the device itself, it produces 1638.5 tons of qualified drawing material number 1080K, plastic injection card No. 1100N of 10984.4 tons and grades of HPPSS products of 794.9 tons. The catalyst activity was 28.85 kg pp / g catalyst.
  • the isotacticity of the brushed material 1080K is adjusted to the isotacticity of the BOPP film material, and the plastic grade 1100N polyolefin is converted into a product with a high melt index by hydrogen adjustment.
  • the catalyst efficiency is equal to greater than 46 kg pp/g. catalyst.
  • the content of 9,9-bis(methoxymethyl)anthracene containing 3% of the invention is used. -5%, 4%-5% of diisobutyl phthalate, 2.5%-3% of titanium, 18.0%-20% of magnesium, catalyst A component, cocatalyst triethylaluminum, external electron donation
  • the body is methylcyclohexyldimethoxysilane.
  • the present invention contains 2,9-bis(methoxymethyl)anthracene content of 2%, phthalic acid
  • the catalyst A component having an isobutyl ester content of 6%, a titanium content of 2.5%, a magnesium content of 18.9%, a cocatalyst of triethylaluminum, and an external electron donor is a usual diisopropyldimethoxysilane.
  • the use evaluation results are obtained: (1) The operation of the device is normal. (2) The activity is up to 52kgPP/gcat, the hydrogen sensitivity is good, the polypropylene is highly regular, and the polypropylene powder is low. (3) It can meet the control requirements of product quality. (4) Can meet the requirements of use.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Emergency Medicine (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

本发明公开一种通用的α-烯烃聚合工业催化剂及其应用，具体涉及一类由(A)固体催化剂组分、(B)助催化剂有机铝化合物和(C)外给电子体化合物组成的、用于α-烯烃聚合或共聚合的各种工艺的工业生产催化剂，提供了一种由邻苯二甲酸二正丁酯或邻苯二甲酸二异丁酯与9,9-二(甲氧基甲基)芴复合内给电子体制备的(A)固体催化剂组分。由烃基烷氧基硅、有机酸酯或烃基烷氧基硅与有机酸酯复合物做外给电子体C组分。(A)固体催化剂组分，(B)助催化剂有机铝化合物和(C)外给电子体化合物的组合使用，用于各种α-烯烃聚合或共聚合工艺的大规模的工业装置，生产出多种新牌号聚α-烯烃。

Description

一种通用的α-烯烃聚合工业催化剂及其应用 技术领域
本发明属于α-烯烃聚合、共聚合催化剂工业研究应用领域，具体涉及一种通用于α-烯烃聚合、共聚合各种工艺的大规模工业生产催化剂及其应用。
背景技术
目前，齐格勒-纳塔(简称Z-N)催化剂仍是工业烯烃聚合的主体催化剂，烯烃尤其是α-烯烃聚合、共聚合的Z-N催化剂包括(A)含钛的氯化镁载体催化剂组分，(B)助催化剂有机铝化合物和(C)调节聚α-烯烃结构、性质的外给电子体。其中含钛的氯化镁载体催化剂组分中包括内给电子体，内给电子体是Z-N催化剂的核心。在本发明中，将含钛的氯化镁载体催化剂组分简称催化剂组分，其制备主要有三种方法，一种是氯化镁醇合物、内给电子体、钛化合物反应,共沉淀的催化剂组分；第二种方法是球形氯化镁醇合物载体载钛化合物、载内给电子体得到催化剂组分；第三种是二乙氧基镁与氯化钛化合物生成的氯化镁与内给电子体反应制备催化剂组分。
内给电子体是Z-N催化剂的核心，因为内给电子体起到调节催化剂活性和聚α-烯烃结构的关键作用，是催化剂组分的核心组分。但是开发出一种实用于各种工艺的工业生产用内给电子体并非是件容易的事，工业上真正广泛应用的内给电子体的数量不多，性能有限，难以满足日益发展的聚烯烃工业的需求。近年发现两种或多种给电子体复合做内给电子体，能产生协调作用，得到不同于单一的内给电子体的性能，兼备两种内给电子体的优点，甚至发生协调作用产生新的性质。由两种给电子体复配做内给电子体制备的催化剂组分的性能可调节，进而得到满足日益发展的多牌号、特殊性能的聚α-烯烃，满足工业需求的催化剂组分。两种给电子体复合做内给电子体制备催化剂组分是开发综合性能优良或某种性能优秀的新催化剂组分的一种新思路、新方法。尽管两种给电子体复合做内给电子体的研究很多，但适应于各种工艺的通用的工业生产的催化剂组分没有报道。
作为工业聚合催化剂的复合内给电子体的内给电子体必须满足工业生产的基本要求，如来源稳定、价格便宜、性能稳定、有特殊性能、性能可调节等等。
邻苯二甲酸二正丁酯和邻苯二甲酸二异丁酯(以下统称为邻苯二甲酸二(正)异丁酯)是目前工业用Z-N催化剂普遍使用的内给电子体，综合性能较好，价格适中，但暴露出一些安全问题、较低聚合温度下活性不高、聚合物缺乏特殊性能等；而9,9-二(甲氧基甲基)芴 的特殊性能突出，如高催化剂活性、聚合温度低、聚烯烃分子量高、聚烯烃等规度高、分子量分布窄、既可作内给电子体又可作外给电子体，是重要给电子体。
本申请人开发了9,9-二(甲氧基甲基)芴的工业生产方法(CN 1166608C)，并建立了生产装置，产品9,9-二(甲氧基甲基)芴供应国际市场。
目前两种给电子体复合做内给电子体制备催化剂组分都停留在靠实验经验组合内给电子体的层面，缺乏理性方法指导内给电子体复合催化剂组分的研究，不仅有可能得不到最期望的复合催化剂组分制备配方，还可能造成内给电子体的极大浪费，筛选出好的内给电子体复合需要做大量的实验，消耗大量的时间、人力、物力。
发明内容
本发明选择了邻苯二甲酸二(正)异丁酯与9,9-二(甲氧甲基)芴复合做工业用Z-N催化剂的氯化镁载体催化剂组分的内给电子体，制备出一种通用的工业用聚烯烃催化剂组分，适用于各种工业聚合反应器聚合工艺的催化剂。
具体本发明所述的适于各种聚合工艺的工业大规模制备聚α-烯烃的催化剂产品，其包括催化剂组分A、助催化剂烷基铝B和外给电子体C；其中:
(1)催化剂组分A是氯化镁负载钛离子、复合内给电子体芳香二酸二烷基酯和1,3-二醚的混合物；
(2)助催化剂烷基铝B是三乙基铝、三异丁基铝或它们的混合物；最经常用的是三乙基铝；
(3)外给电子体C是烷基烷氧基硅或有机酸酯或烷基烷氧基硅与有机酸酯复合物。
对于上文公开的技术方案中所述的催化剂，其特征在于：所述催化剂组分A中，芳香二酸二烷基酯是邻苯二甲酸二(正)异丁酯。
对于上文公开的技术方案中所述的催化剂，其特征在于：所述催化剂组分A中，1,3-二醚是9,9-二(甲氧甲基)芴。
对于上文公开的技术方案中所述的催化剂，其特征在于：所述催化剂组分A中，钛的质量分数为2.0-3.8％，镁的质量分数为15.0-20.0％，邻苯二甲酸二(正)异丁酯的质量分数为1.0-7.0％，9,9-二(甲氧甲基)芴的质量分数为1.0-9.0％。
对于上文公开的技术方案中所述的催化剂，邻苯二甲酸二(正)异丁酯与9,9-二(甲氧 甲基)芴的摩尔比决定催化剂组分的性能。具体而言，所述邻苯二甲酸二(正)异丁酯与9,9-二(甲氧甲基)芴的摩尔比为1-9.9:10。
通过调节邻苯二甲酸二(正)异丁酯与9,9-二(甲氧甲基)芴的用量，得到一系列的聚合催化剂，进而得到满足市场需要的多种牌号的聚烯烃。例如，使用了Z-N催化剂组分A复合内给电子体邻苯二甲酸二异丁酯含量2.5％和9,9-二(甲氧甲基)芴含量5％可以生产通用的聚丙烯膜料；使用邻苯二甲酸二异丁酯7％和9,9-二(甲氧甲基)芴8％的Z-N催化剂组分A，通过调节工艺可以生产聚丙烯拉丝料，也可以生产聚丙烯注塑料；再如使用邻苯二甲酸二异丁酯含量4％-5％和9,9-二(甲氧甲基)芴含量3％-5％、可以生产丙烯均聚产品，也可以生产乙烯/丙烯共聚产品。
对于上文公开的技术方案中所述的催化剂，具体而言，所述催化剂组分A的制备方法包括下述方法：①氯化镁醇合物、复合内给电子体和四氯化钛共沉淀方法制备；②球形氯化镁醇合物载体负载四氯化钛和复合内给电子体的方法制备；③二乙氧基镁、四氯化钛反应生成的氯化镁负载复合内给电子体。本发明所列举的①～③所述方法，均为现有技术，是本领域技术人员制备催化剂组分A的常用方法。如申请人利用方法①开发了一些新催化剂组分A的制备及应用的技术(CN100,491,415C,US 8,344,080B2，US 7,964,678B2)。
对于上文公开的技术方案中所述的催化剂，外给电子体C是烃基烷氧基硅，或有机酸酯，或烃基烷氧基硅与有机酸酯复合物，具体而言，所述的烃基烷氧基硅选自工业上常用的外给电子体，包括C1-10的烷基三甲氧基硅、C1-8的二烷基二甲氧基硅、烷基环烷基二甲氧基硅、二环烷基二甲氧基硅或二苯基二甲氧基硅，典型的烃基烷氧基硅是丙基三甲氧基硅、二异丙基二甲氧基硅、二异丁基二甲氧基硅、甲基环己基二甲氧基硅、二环戊基二甲氧基硅、二苯基二甲氧基硅等；所述的有机酸酯是C10-20的直链天然脂肪酸C3-5的支链烷基酯，典型的是十二酸异丙酯、十二酸异戊酯、十四酸异丙酯、十四酸异戊酯、十六酸异丙酯等；所述的烷基烷氧基硅和有机酸酯组成的复合物，典型的复合物选自丙基三甲氧基硅与十四酸异丙酯、二环戊基二甲氧基硅与十四酸异丙酯、二苯基二甲氧基硅与十四酸异丙酯进行复合。
对于上文公开的技术方案中所述的催化剂，具体而言，所述烃基烷氧基硅和有机酸酯的摩尔比为1-9.9:10。选取烃基烷氧基硅、有机酸酯还是烃基烷氧基硅与有机酸酯复合物做外给电子体，以及复合外给电子体的烃基烷氧基硅和有机酸酯的种类、烃基烷氧基硅和有机酸酯的摩尔比，取决于复合内给电子体邻苯二甲酸二(正)异丁酯与9,9-二(甲氧甲基)芴的比例，即取决于生产聚α-烯烃的牌号。
对于上文公开的技术方案中所述的催化剂，具体而言，所述的α-烯烃聚合为丙烯聚合、1-丁烯聚合、乙烯与丙烯共聚合、乙烯与1-丁烯共聚合或丙烯与1-丁烯共聚合。
对于上文公开的技术方案中任一项所述的催化剂，其可以应用于各种聚合工艺的大规模工业生产α-烯烃聚合物中，具体而言，所述应用包括到：(1)气相反应：UNIPOL气相流化床反应器工艺的α-烯烃聚合，NOVOLEN立体式搅拌釜气相反应器工艺的α-烯烃聚合，INNOVENE卧搅拌釜式气相反应器工艺的α-烯烃聚合，JPP日本窒素卧釜式气相反应器工艺的α-烯烃聚合；(2)间歇本体反应：釜式反应器聚合工艺的α-烯烃聚合；(3)连续本体反应：SPHERIPOL环管反应器工艺的α-烯烃聚合，ZHG工艺的一个卧式本体反应器串联一个卧式气相反应釜工艺的α-烯烃聚合。在这些工艺中，α-烯烃聚合应用最多、最重要的是丙烯聚合和丙烯与乙烯的共聚合工艺。
对于上文公开的技术方案中所述的催化剂的应用，具体而言，所述的应用包括在同一种工艺同一装置中生产性质差异大的多种牌号聚烯烃。本发明的复合外给电子体C，在特定的工艺中的选择有所不同，如NIPOL气相流化床反应器聚合工艺丙烯聚合，使用的外给电子体是烷基烷氧基硅和有机酸酯组成的二元复合物，如丙基三甲氧基硅与十四酸异丙酯可生产通用性聚丙烯。
本发明的工业用催化剂的优势：
1.适用面广，几乎包括了工业上使用的α-烯烃聚合工艺；
2.复合内给电子体邻苯二甲酸二(正)异丁酯与9,9-二(甲氧甲基)芴，以不同摩尔比复合制备的催化剂组分具有优良的可调节性能，甚至产生特殊性能的聚丙烯，满足聚丙烯牌号的需求。
3.众所周知目前通用的内给电子体邻苯二甲酸二丁酯对人畜有安全问题，而9,9-二(甲氧甲基)芴可以看成是绿色内给电子体，二者复合使用会大幅度减少邻苯二甲酸二丁酯的用量。
4.不同的聚合工艺，选取烃基烷氧基硅、有机酸酯还是烃基烷氧基硅与有机酸酯复合物做外给电子体，以及复合外给电子体的烷基烷氧基硅和有机酸酯的种类、烃基烷氧基硅和有机酸酯的摩尔比，可方便的调节催化剂的性能。
5.选用长链的脂肪酸酯做外给电子体C的组分,留在聚合物中可以做增塑剂用。
具体实施方式
下述非限定性实施例可以使本领域的普通技术人员更全面地理解本发明，但不以任何方式限制本发明。
实施例1
引进的某UNIPOL气相流化床反应器工艺的60万吨丙烯聚合装置，使用了Z-N催化剂组分A复合内给电子体9,9-二(甲氧甲基)芴含量5％、邻苯二甲酸二异丁酯含量2.5％、三乙基铝助催化剂、丙基三甲氧基硅与十四酸异丙酯复合外给电子体，反应器温度为68.5-71.5℃、丙烯分压2.7-2.8MPag、TEAL/Ti为60-75、H2/C3比为0.0028、催化剂停留时间为1.29h的运行参数下，分别采用本发明的催化剂与装置本身带的催化剂生产聚丙烯粉料取样分析结果如下表：
Figure PCTCN2017107601-appb-000001
通过对比，本发明催化剂生产的聚丙烯的等规指数大于装置带的催化剂生产聚丙烯的等规指数，堆积密度高于装置带的催化剂的生产聚丙烯堆积密度，聚丙烯的平均颗粒尺寸与装置带的催化剂的相当，聚丙烯的细粉含量低于装置带的催化剂生产的聚丙烯的细分含量，本发明催化剂活性明显高于装置带的催化剂的活性。
本发明催化剂生产的聚丙烯产品的灰分比装置带的催化剂的聚丙烯产品的灰分低；黄色指数低于装置带的催化剂生产的聚丙烯的黄色指数。
本发明催化剂的单耗比装置带的催化剂单耗平均低19.6％，三乙基铝单耗比装置带的催化剂单耗平均低30.6％，外给电子体单耗比进口给电子体单耗低32.6％。
本流化床反应器生产的聚丙烯是通用性聚丙烯。催化剂的效率为24kgpp/gcatl。
实施例2
在某引进年产55万吨的NOVOLEN立体式搅拌釜气相反应器工艺的丙烯烃聚合工艺装置上，使用本发明的催化剂A组分含钛2.7％、镁18.5％、9,9-二(甲氧甲基)芴8％和邻苯二甲酸二异丁酯7％，助催化剂三乙基铝，外给电子体甲基环己基二甲氧基硅的Z-N改进的催化剂。按装置本身的工艺参数操作，生产出合格的拉丝料牌号1080K的1638.5吨,注塑料牌 号1100N的10984.4吨和牌号HPPSS产品794.9吨。催化剂活性为28.85kgpp/g催化剂。通过调节工艺参数，将符合拉丝料1080K的等规度调节到生产BOPP薄膜料的等规度，通过氢调，把注塑料牌号1100N聚烯烃，转变成生产高熔融指数的产品。催化剂效率等于大于46kgpp/g.催化剂。
实施例3
在某年产20万吨气相INNOVENE单反应器工艺上以及某引进30万吨/年INNOVENE工艺串联双反应器工艺上，使用本发明含9,9-二(甲氧甲基)芴含量3％-5％、邻苯二甲酸二异丁酯含量4％-5％、钛含量2.5％-3％、镁含量18.0％-20％的催化剂A组分，助催化剂三乙基铝，外给电子体是甲基环己基二甲氧基硅烷。可以生产丙烯均聚及乙烯/丙烯共聚产品，其中INNOVENE单反应器上应用催化剂催化效率达到27Kg.PP/g.cat,在串联双反应器上应用催化剂催化效率达到32Kg.PP/g.cat。
实施例4
在连续本体法，在SPHERIPOL年产30万吨聚丙烯环管反应器工艺的丙烯聚合装置上，使用本发明含9,9-二(甲氧甲基)芴含量2％、邻苯二甲酸二异丁酯含量6％、钛含量2.5％、镁含量18.9％的催化剂A组分，助催化剂三乙基铝，外给电子体是通常的二异丙基二甲氧基硅。按装置的生产工艺参数(包括预聚合)操作，得到使用评价结论：(1)装置运行情况正常。(2)活性最高达到52kgPP/gcat、氢调敏感性好、聚丙烯等规度较高、聚丙烯细粉量较低。(3)能满足产品质量的控制要求。(4)能满足使用要求。

Claims (10)

  1. 一种用于多种聚合工艺的工业大规模制备聚α-烯烃的催化剂，其特征在于：包括催化剂组分A、助催化剂烷基铝B和外给电子体C；其中:
    (1)催化剂组分A是由氯化镁负载钛离子、复合内给电子体芳香二酸二烷基酯和1,3-二醚组成；
    (2)助催化剂烷基铝B是三乙基铝、三异丁基铝或它们的混合物；
    (3)外给电子体C是烃基烷氧基硅、有机酸酯或烃基烷氧基硅与有机酸酯复合物。
  2. 根据权利要求1所述的催化剂，其特征在于：所述催化剂组分A中，芳香二酸二烷基酯是邻苯二甲酸二(正)异丁酯。
  3. 根据权利要求1所述的催化剂，其特征在于：所述催化剂组分A中，1,3-二醚是9,9-二(甲氧甲基)芴。
  4. 根据权利要求1所述的催化剂，其特征在于：所述催化剂组分A中，钛的质量分数为2.0-3.8％，镁的质量分数为15.0-20.0％，邻苯二甲酸二(正)异丁酯的质量分数为1.0-7.0％，9,9-二(甲氧甲基)芴的质量分数为1.0-9.0％。
  5. 根据权利要求1或4所述的催化剂，其特征在于：所述邻苯二甲酸二(正)异丁酯与9,9-二(甲氧甲基)芴的摩尔比为1-9.9:10。
  6. 根据权利要求1所述的催化剂，其特征在于：所述催化剂组分A的制备方法包括下述方法：①氯化镁醇合物、复合内给电子体和四氯化钛共沉淀方法制备；②球形氯化镁醇合物载体负载四氯化钛和复合内给电子体的方法制备；③二乙氧基镁、四氯化钛反应生成的氯化镁负载复合内给电子体。
  7. 根据权利要求1所述的催化剂，其特征在于：所述的烃基烷氧基硅选自C1-10的烷基三甲氧基硅、C1-8的二烷基二甲氧基硅、烷基环烷基二甲氧基硅、二环烷基二甲氧基硅或二苯基二甲氧基硅；
    所述的有机酸酯是C10-20的直链天然脂肪酸C3-5的支链烷基酯；
    所述的烃基烷氧基硅和有机酸酯组成的复合物选自丙基三甲氧基硅与十四酸异丙酯、二环戊基二甲氧基硅与十四酸异丙酯、二苯基二甲氧基硅与十四酸异丙酯的复合物。
  8. 根据权利要求1或7所述的催化剂，其特征在于：所述烃基烷氧基硅和有机酸酯的摩 尔比为1-9.9:10。
  9. 根据权利要求1所述的催化剂，其特征在于：所述的α-烯烃聚合为丙烯聚合、1-丁烯聚合、乙烯与丙烯共聚合、乙烯与1-丁烯共聚合或丙烯与1-丁烯共聚合。
  10. 根据权利要求1～9中任一项所述的催化剂在各种聚合工艺的大规模工业生产α-烯烃聚合物中的应用，其特征在于：所述应用包括(1)气相反应：UNIPOL气相流化床反应器工艺的α-烯烃聚合，NOVOLEN立体式搅拌釜气相反应器工艺的α-烯烃聚合，INNOVENE卧搅拌釜式气相反应器工艺的α-烯烃聚合，JPP日本窒素卧釜式气相反应器工艺的α-烯烃聚合；(2)间歇本体反应：釜式反应器聚合工艺的α-烯烃聚合；(3)连续本体反应：SPHERIPOL环管反应器工艺的α-烯烃聚合，ZHG工艺的一个卧式本体反应器串联一个卧式气相反应釜工艺的α-烯烃聚合；
    所述应用还包括在同一种工艺同一装置中生产性质差异大的多种牌号聚烯烃。
PCT/CN2017/107601 2017-09-29 2017-10-25 一种通用的α-烯烃聚合工业催化剂及其应用 Ceased WO2018050127A2 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US16/335,929 US11220560B2 (en) 2017-09-29 2017-10-25 Universal alpha-olefin polymerization catalyst, and application thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201710908838.4 2017-09-29
CN201710908838.4A CN107602736B (zh) 2017-09-29 2017-09-29 一种通用的α-烯烃聚合工业催化剂及其应用

Publications (2)

Publication Number Publication Date
WO2018050127A2 true WO2018050127A2 (zh) 2018-03-22
WO2018050127A3 WO2018050127A3 (zh) 2018-05-03

Family

ID=61067177

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2017/107601 Ceased WO2018050127A2 (zh) 2017-09-29 2017-10-25 一种通用的α-烯烃聚合工业催化剂及其应用

Country Status (3)

Country Link
US (1) US11220560B2 (zh)
CN (1) CN107602736B (zh)
WO (1) WO2018050127A2 (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11214666B2 (en) 2020-04-15 2022-01-04 Prc-Desoto International, Inc. Controlling cure rate with wetted filler
US11220560B2 (en) 2017-09-29 2022-01-11 Yingkou Xiangyang Catalyst Co., Ltd. Universal alpha-olefin polymerization catalyst, and application thereof

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110003367B (zh) * 2019-04-26 2020-07-17 营口市向阳催化剂有限责任公司 一种具有双功能的外给电子体的齐格勒-纳塔催化剂及其应用
EP4638527A1 (en) * 2022-12-22 2025-10-29 SABIC Global Technologies B.V. Process for making polypropylene using a selectivity control agent and an activity limiting agent
CN115873155B (zh) * 2023-01-03 2024-04-02 湖北华邦化学有限公司 外给电子体组合物、丙烯聚合催化组合物及丙烯聚合方法

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999057160A1 (en) * 1998-05-06 1999-11-11 Montell Technology Company B.V. Catalyst components for the polymerization of olefins
WO2005035594A1 (en) * 2003-09-23 2005-04-21 Union Carbide Chemicals & Plastics Technology Corporation Self-extiguishing catalyst compostion with monocarboxylic acid ester internal donor and propylene polymerization process
CN102040693A (zh) * 2009-10-23 2011-05-04 中国石油化工股份有限公司 一种聚丁烯-1的气相聚合方法及其聚合物
CN102603941B (zh) * 2011-01-20 2014-06-25 中国科学院化学研究所 β晶型聚丙烯树脂的制备方法
CN103214602B (zh) * 2013-05-13 2016-01-06 任丘市利和科技发展有限公司 一种二烷氧基镁载体型固体催化剂及其制备方法和应用
CN103554312B (zh) * 2013-10-18 2016-08-17 营口市向阳催化剂有限责任公司 一种用于制备α-烯烃聚合催化剂组分的内给电子体复配物
CN105849141B (zh) * 2013-10-29 2020-10-16 格雷斯公司 适用于管道的丙烯乙烯无规共聚物
EP2966099B1 (en) * 2014-07-08 2020-03-11 Indian Oil Corporation Limited Particle size distribution control through internal donor in ziegler-natta catalyst
CN105566742B (zh) * 2014-10-10 2017-09-15 中国石化扬子石油化工有限公司 一种聚烯烃合金的制备方法
EP3018150B1 (en) * 2014-11-07 2020-03-11 Indian Oil Corporation Limited Process for the preparation of spherical catalyst particles
CN106699932B (zh) * 2015-11-12 2019-03-22 营口市向阳催化剂有限责任公司 含有磷酸酯类外给电子体的聚丙烯聚合用催化体系及其应用
CN107602736B (zh) 2017-09-29 2020-02-07 营口市向阳催化剂有限责任公司 一种通用的α-烯烃聚合工业催化剂及其应用

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11220560B2 (en) 2017-09-29 2022-01-11 Yingkou Xiangyang Catalyst Co., Ltd. Universal alpha-olefin polymerization catalyst, and application thereof
US11214666B2 (en) 2020-04-15 2022-01-04 Prc-Desoto International, Inc. Controlling cure rate with wetted filler

Also Published As

Publication number Publication date
US11220560B2 (en) 2022-01-11
WO2018050127A3 (zh) 2018-05-03
CN107602736A (zh) 2018-01-19
US20190309099A1 (en) 2019-10-10
CN107602736B (zh) 2020-02-07

Similar Documents

Publication Publication Date Title
CN105934449B (zh) 用于烯烃聚合的催化剂组合物
EP3083723B1 (en) Catalyst system for polymerisation of an olefin
EP3157966B1 (en) Process for the polymerization of propylene
WO2018050127A2 (zh) 一种通用的α-烯烃聚合工业催化剂及其应用
CN105339393B (zh) 生产聚乙烯组合物的多级方法
KR102288227B1 (ko) 올레핀 중합용 촉매 시스템
KR20160102018A (ko) 올레핀 중합용 전구 촉매
KR102365377B1 (ko) 올레핀 중합용 촉매 시스템
DE102011018780A1 (de) Verfahren zur Herstellung einer festen Katalysatorkomponente zur Olefinpolymerisation
KR20110083478A (ko) 프로필렌 중합용 고체촉매 및 그 제조 방법
EP3033348B1 (en) Catalyst system for polymerisation of an olefin
KR20110080616A (ko) 프로필렌 중합용 고체촉매의 제조 방법
CN108349873B (zh) 取代的酰胺基苯甲酸酯化合物的合成及其作为不含邻苯二甲酸酯的内给电子体的用途
CN109096416B (zh) 烯烃聚合催化剂组分及其制备方法和烯烃聚合催化剂以及烯烃聚合物的制备方法
EP3126403B1 (en) Catalyst composition
CN113004451A (zh) 具有改善性能的护套
DE102012019961A1 (de) Verfahren zur Herstellung einer festen Katalysatorkomponente für die Olefinpolymerisation
JP5564337B2 (ja) 結晶性プロピレン重合体、その製造方法及びそれを含む樹脂組成物
JP2017115142A (ja) α−オレフィン重合用固体触媒成分の製造方法、及びそれを用いたα−オレフィン重合体の製造方法
JP2008115321A (ja) ポリプロピレン系ランダム共重合体、それを含む組成物および射出成形体の製造方法
CN106459247A (zh) 用于烯烃的聚合的原催化剂
CN110903418B (zh) 用于烯烃聚合的固体催化剂组分、催化剂及其应用
CN110903419B (zh) 用于烯烃聚合的固体催化剂组分、催化剂及其应用
KR20120002790A (ko) 프로필렌 중합용 고체촉매의 제조방법
JP2010095601A (ja) プロピレン系重合体の製造方法

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: 17850328

Country of ref document: EP

Kind code of ref document: A2

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17850328

Country of ref document: EP

Kind code of ref document: A2