Ansametallocene Catalysts for Low Long Chain Branching Polyethylene

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Solution Overview

Problem

Current olefin polymerization catalysts, particularly metallocene-based systems, struggle to control long-chain branching (LCB) in polyethylene, which is undesirable for many applications due to increased elasticity and performance issues in films and resins.

Innovation Solution

Development of a catalyst composition comprising tightly-bridged ansa-metallocenes with pendant alkenyl groups and specific aryl substitutions, combined with organoaluminum compounds and electron-withdrawing anion-treated solid oxide activators, to control LCB levels and enhance catalytic activity.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Productivity

If metallocene-based catalysts are used for polymerization, then catalytic activity is enhanced, but long chain branching (LCB) levels increase which is undesirable for many applications

Engineering Contradiction:
Improvecatalytic activityVSAvoidlong chain branching (LCB) levels
Core Design Contradiction:
ProductivityVSObject-generated harmful factors

Solution Approach 1:

The patent applies parameter changes by modifying the metallocene catalyst structure with specific substituents (aryl groups, alkyl groups, heteroatom-containing groups) at defined positions on the cyclopentadienyl rings. These structural parameter changes alter the catalyst's electronic and steric properties, enabling control over LCB levels while maintaining high catalytic activity. The patent specifically identifies catalysts with substituents at the 2-position and 4-position of the cyclopentadienyl rings as producing polymers with reduced LCB.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent employs local quality by placing specific functional groups at particular positions on the metallocene ligand structure. The cyclopentadienyl rings are substituted at specific locations (2-position, 4-position, etc.) with groups having different electronic and steric characteristics. This localized modification allows precise control over the polymerization process and LCB formation while preserving the overall catalytic function.

Inventive Principle:
Principle #3Local quality

2Reliability

If LCB levels are increased to improve bubble stability during film blowing, then film processing is enhanced, but resin elasticity increases which is undesirable for many uses

Engineering Contradiction:
Improvebubble stability during film blowingVSAvoidresin elasticity
Core Design Contradiction:
ReliabilityVSObject-generated harmful factors

Solution Approach 1:

The patent utilizes parameter changes by optimizing the catalyst structure to achieve specific LCB levels within a controlled range. By adjusting substituent types, positions, and quantities on the metallocene ligand, the patent enables production of polymers with LCB levels tailored to achieve adequate bubble stability without excessive resin elasticity. The patent identifies optimal LCB ranges of 0-50 branches per 1000 carbons for many applications.

Inventive Principle:
Principle #35Parameter changes

Applied Scientific Principles

This section explains which scientific principles are used to turn an abstract innovation direction into a practical engineering solution.

Function Achieved in This Case

The catalyst composition achieves high molecular weight polyethylene with low LCB levels, improving film stability and processability while maintaining desired resin properties.

Implementation Method 1

catalyst compositions employing titanium, zirconium, vanadium, chromium, or other metals... These catalyst compositions can be useful for both homopolymerization of ethylene, as well as copolymerization of ethylene with comonomers

Methodology Applied
Scientific EffectCatalysis: Catalysis

Data Source

PatentEP3239190B1Polymerization catalysts for producing polymers with low levels of long chain branching
Publication Date: 2020.01.29 CHEVRON PHILLIPS CHEMICAL COMPANY LP
  • EP3239190B1 patent drawingFigure 1
  • EP3239190B1 patent drawingFigure 2
  • EP3239190B1 patent drawingFigure 3

AI summary

This invention relates to catalyst compositions, methods, and polymers encompassing at least one Group 4 metallocene compound comprising bridging η5-cyclopentadienyl-type ligands, typically in combination with at least one cocatalyst, and at least one activator. The compositions and methods disclosed herein provide ethylene polymers with low levels of long chain branching.