KR-20260063706-A - METHOD FOR PREPARING OLEFIN BASED POLYMER

KR20260063706AKR 20260063706 AKR20260063706 AKR 20260063706AKR-20260063706-A

Abstract

A method for manufacturing an olefin-based polymer according to one embodiment of the present invention may include the step (S1) of manufacturing a catalyst composition comprising a transition metal compound represented by the following chemical formula 1 and a co-catalyst in a molar ratio of 1:1.2 to 1:2.5; and the step (S2) of manufacturing an olefin-based polymer by introducing hydrogen gas in the presence of the catalyst composition to polymerize an olefin-based monomer. [Chemical Formula 1] In the above chemical formula 1, M is Hf or Zr, and L is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, or a halogen, and Y is an alkylene group having 2 to 40 carbon atoms or an arylene group having 6 to 20 carbon atoms, and Cy 1 and Cy 2 are each independently substituted or unsubstituted cycloalkyl groups having 5 to 10 carbon atoms, and the substituents of Cy 1 and Cy 2 are selected from the group consisting of alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, and alkoxy groups having 1 to 10 carbon atoms. R1 to R24 are each independently hydrogen, halogen, cyano group, amino group, alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, alkylsilyl group having 1 to 20 carbon atoms, or alkoxy group having 1 to 20 carbon atoms.

Inventors

신경수
정정연
신창훈
공진삼
박상은
박근태
박근호

Assignees

주식회사 엘지화학

Dates

Publication Date: 20260507
Application Date: 20241031

Claims (11)

Step (S1) of preparing a catalyst composition comprising a transition metal compound represented by the following chemical formula 1 and a co-catalyst in a molar ratio of 1:1.2 to 1:2.5; and A method for producing an olefin polymer comprising the step (S2) of polymerizing an olefin monomer by introducing hydrogen gas in the presence of the catalyst composition to produce an olefin polymer: [Chemical Formula 1] In the above chemical formula 1, M is Hf or Zr, and L is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, or a halogen, and Y is an alkylene group having 2 to 40 carbon atoms or an arylene group having 6 to 20 carbon atoms, and Cy 1 and Cy 2 are each independently substituted or unsubstituted cycloalkyl groups having 5 to 10 carbon atoms, and the substituents of Cy 1 and Cy 2 are selected from the group consisting of alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, and alkoxy groups having 1 to 10 carbon atoms. R1 to R24 are each independently hydrogen, halogen, cyano group, amino group, alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, alkylsilyl group having 1 to 20 carbon atoms, or alkoxy group having 1 to 20 carbon atoms.
In paragraph 1, A method for manufacturing an olefin-based polymer, wherein the amount of hydrogen gas introduced in step (S2) above is 60 Sccm or more and 120 Sccm or less.
In paragraph 1, A method for preparing an olefin-based polymer in which the molar ratio of the transition metal and the co-catalyst in the above (S1) step is 1:1.4 to 1:2.5.
In paragraph 1, A method for producing an olefin polymer in which the olefin monomer comprises ethylene and an alpha-olefin monomer.
In paragraph 4, A method for producing an olefin polymer, wherein the above alpha-olefin monomer comprises one or more selected from the group consisting of propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-eicocene.
In paragraph 1, A method for preparing an olefin-based polymer, wherein the above co-catalyst comprises a compound represented by the following chemical formulas 3 to 6: [Chemical Formula 3] -[Al(R 32 )-O] a - In the above chemical formula 3, R 32 is each independently a halogen group, a hydrocarbyl group having 1 to 20 carbon atoms, or a hydrocarbyl group having 1 to 20 carbon atoms substituted with a halogen group, and a is an integer greater than or equal to 2, and [Chemical Formula 4] E(R 33 ) 3 In the above chemical formula 4, E is aluminum or boron, and R 33 is each independently hydrogen, a halogen group, a hydrocarbyl group having 1 to 20 carbon atoms, or a hydrocarbyl group having 1 to 20 carbon atoms substituted with a halogen group, and [Chemical Formula 5] [Le-H] + [G(A) 4 ] - [Chemical Formula 6] [Le] + [G(A) 4 ] - In the above chemical formulas 5 and 6, Le is a neutral or cationic Lewis acid, and [Le-H] + is a Brønsted acid, and G is a Group 13 element, and A is each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein, when the alkyl group or aryl group is substituted, the substituent is a halogen group, a hydrocarbyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms.
In paragraph 1, A method for preparing an olefinic polymer in which Cy 1 and Cy 2 of the above chemical formula 1 are each independently represented by the following chemical formula 2: [Chemical Formula 2] In the above chemical formula 2, R 25 to R 29 are each independently hydrogen or an alkyl group having 1 to 20 carbon atoms.
In paragraph 1, M is Hf or Zr, and L is an alkyl group having 1 to 20 carbon atoms, and Y is an alkylene group having 2 to 40 carbon atoms, and A method for preparing an olefinic polymer in which R1 to R24 are each independently hydrogen, a halogen, or an alkyl group having 1 to 20 carbon atoms.
In paragraph 1, A method for preparing an olefinic polymer in which the transition metal compound represented by the above chemical formula 1 is represented by the following chemical formula 1A: [Chemical Formula 1A] In the above chemical formula 1A, M is Hf or Zr, and L is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, or a halogen, and Y is an alkylene group having 2 to 40 carbon atoms or an arylene group having 6 to 20 carbon atoms, and R1 to R24 are each independently hydrogen, halogen, cyano group, amino group, alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, alkylsilyl group having 1 to 20 carbon atoms, or alkoxy group having 1 to 20 carbon atoms, and R 30 and R 31 are each independently hydrogen or an alkyl group having 1 to 20 carbon atoms.
In paragraph 1, A method for preparing an olefin-based polymer in which the transition metal compound represented by the above chemical formula 1 is one selected from the group consisting of the following chemical formulas 1-1 to 1-6: [Chemical Formula 1-1] [Chemical Formula 1-2] [Chemical Formula 1-3] [Chemical Formula 1-4] [Chemical Formula 1-5] [Chemical Formula 1-6]
Step of preparing polypropylene (S1-1); Step (S2-1) of preparing a catalyst composition comprising a transition metal compound represented by the following chemical formula 1 and a co-catalyst in a molar ratio of 1:1.2 to 1:2.5; A step (S3-1) of polymerizing an olefin monomer by introducing hydrogen gas in the presence of the catalyst composition to produce an olefin polymer; and A method for manufacturing a polypropylene-based composite material comprising the step (S4-1) of melt-kneading the polypropylene and olefin-based polymers: [Chemical Formula 1] In the above chemical formula 1, M is Hf or Zr, and L is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, or a halogen, and Y is an alkylene group having 2 to 40 carbon atoms or an arylene group having 6 to 20 carbon atoms, and Cy 1 and Cy 2 are each independently substituted or unsubstituted cycloalkyl groups having 5 to 10 carbon atoms, and the substituents of Cy 1 and Cy 2 are selected from the group consisting of alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, and alkoxy groups having 1 to 10 carbon atoms. R1 to R24 are each independently hydrogen, halogen, cyano group, amino group, alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, alkylsilyl group having 1 to 20 carbon atoms, or alkoxy group having 1 to 20 carbon atoms.

Description

Method for Preparing Olefin-Based Polymer The present invention relates to a method for manufacturing an olefin-based polymer used to produce a polypropylene-based composite material with improved physical properties, such as low-temperature and room-temperature impact strength and shrinkage rate. Generally, compositions for automotive interior and exterior parts have used polypropylene-based resin compositions containing impact modifiers and inorganic fillers, with polypropylene (PP) as the main component. Until the mid-1990s, prior to the development of ethylene/alpha-olefin copolymers polymerized using metallocene catalysts, EPR (Etylene Propylene Rubber) or EPDM (Etylene Propylene Diene Rubber) were primarily used as impact modifiers in polypropylene-based resin compositions for automotive interior and exterior materials, particularly bumper covers. However, since the introduction of ethylene/alpha-olefin copolymers synthesized by metallocene catalysts, ethylene/alpha-olefin copolymers have begun to be used as impact modifiers and currently constitute the mainstream. This is because polypropylene-based composites using these copolymers have many advantages, such as balanced physical properties including impact strength, elastic modulus, and flexural strength, good moldability, and low cost. Polyolefins such as ethylene/alpha-olefin copolymers synthesized by metallocene catalysts have a narrow molecular weight distribution and good mechanical properties because their molecular structure is more uniformly controlled than that produced by Ziegler-Natta catalysts. Low-density ethylene elastomers polymerized by metallocene catalysts also have good mechanical properties while maintaining low-density rubber characteristics because alpha-olefin monomers are inserted relatively uniformly into the polyethylene molecules compared to those produced by Ziegler-Natta catalysts. However, depending on the various usage environments, there is a constant demand for the manufacture of superior products that strike a balance between physical properties and processability. Hereinafter, the present invention will be described in more detail to aid in understanding the invention. Terms and words used in this specification and claims should not be interpreted as being limited to their ordinary or dictionary meanings, but should be interpreted in a meaning and concept consistent with the technical spirit of the invention, based on the principle that the inventor can appropriately define the concept of the terms to best describe his invention. The term “alkyl” as used herein means a straight-chain, cyclic, or branched hydrocarbon residue unless otherwise noted, and includes, but is not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, and hexyl. As used herein, the term “cycloalkyl” refers to a non-aromatic cyclic hydrocarbon radical composed of carbon atoms unless otherwise noted. “Cycloalkyl” includes, by non-limiting example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl. As used herein, the term “aryl” refers to an optionally substituted benzene ring unless otherwise noted, or to a ring system that may be formed by fusing one or more optional substituents. Exemplary optional substituents include a substituted C1-3 alkyl, substituted C2-3 alkenyl, substituted C2-3 alkynyl, heteroaryl, heterocyclic, aryl, alkoxy, aryloxy, aralkoxy, acyl, aroyl, heteroaroyl, acyloxy, aroyloxy, heteroaroyloxy, sulfanyl, sulfinyl, sulfonyl, aminosulfonyl, sulfonylamino, carboxyamide, aminocarbonyl, carboxy, oxo, hydroxy, mercapto, amino, nitro, cyano, halogen, or ureido. Such rings or ring systems may optionally be fused to aryl rings (e.g., benzene rings), carbon ring rings, or heterocyclic rings having one or more optional substituents. Examples of 'aryl' groups include, but are not limited to, phenyl, naphthyl, tetrahydronaphthyl, biphenyl, indanyl, anthracyl, or phenanthyl, and their substituted derivatives. In the present invention, “alkylaryl” means an aryl group substituted by the alkyl group. In the present invention, “arylalkyl” means an alkyl group substituted by the aryl group. In the present invention, “hydrocarbyl” means a monovalent hydrocarbon group having 1 to 20 carbon atoms, consisting only of carbon and hydrogen, regardless of its structure, such as alkyl, aryl, alkenyl, alkynyl, cycloalkyl, alkylaryl, or arylalkyl, unless otherwise noted. In the present invention, “alkylene group” may refer to divalent aliphatic saturated hydrocarbons such as methylene, ethylene, propylene, and butylene. In the present invention, the term “alkoxy group” may include all functional groups, atomic groups, or compounds in which the hydrogen at the terminal end of an alkyl group is substituted with an oxygen atom, such as methoxy, ethoxy, propoxy, and butoxy. In this specification, the term “substitution” means that a hydrogen atom bonded to a carbon atom of a compound is replaced b