Solid Polymethylaluminoxane Catalyst Without Silica Support

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Solution Overview

Problem

Solid polymethylaluminoxane compositions used in olefin polymerization often result in poor morphology and reduced polymer bulk density, particularly when supported on silica, which also leads to reactor fouling and reduced activity compared to homogeneous polymerization.

Innovation Solution

A solid polymethylaluminoxane composition is developed with specific aluminum and Al2O3 content ranges, crystalline structure, and particle size distribution, which is prepared by adjusting heating conditions to enhance activity and morphology, eliminating the need for silica support and improving polymerization performance.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Ease of operation

If silica support is used to prepare solid polymethylaluminoxane composition, then the composition can be handled in solid state, but the polymer morphology deteriorates and bulk density reduces

Engineering Contradiction:
Improvesolid state handlingVSAvoidpolymer morphology
Core Design Contradiction:
Ease of operationVSManufacturing precision

Solution Approach 1:

The invention extracts and eliminates the silica support component from the solid polymethylaluminoxane composition, retaining only the essential polymethylaluminoxane active species. This removal of the harmful support material resolves the contradiction by maintaining solid state handling capabilities while eliminating the negative impact on polymer morphology and bulk density that silica support causes.

Inventive Principle:
Principle #2Taking out (Extraction)

Solution Approach 2:

The invention employs a support-free design where the polymethylaluminoxane itself serves as both the active catalyst component and the solid matrix. This disposable-like approach eliminates the need for permanent silica support structures, allowing the composition to function effectively in solid state without the morphological deterioration that traditional supports cause.

Inventive Principle:
Principle #27Cheap short-living objects (Disposable)

2Ease of operation

If silica support is used in solid polymethylaluminoxane composition, then solid state handling is enabled, but reactor fouling increases

Engineering Contradiction:
Improvesolid state handlingVSAvoidreactor fouling
Core Design Contradiction:
Ease of operationVSObject-generated harmful factors

Solution Approach 1:

The invention removes the silica support material that causes polymer adhesion and reactor fouling. By extracting this harmful component while maintaining the solid state structure through the polymethylaluminoxane itself, the composition enables solid state handling without generating the fouling problems associated with traditional silica-supported systems.

Inventive Principle:
Principle #2Taking out (Extraction)

3Ease of operation

If silica support is used in solid polymethylaluminoxane composition, then solid form is achieved, but polymerization activity decreases compared to homogeneous polymerization

Engineering Contradiction:
Improvesolid formVSAvoidpolymerization activity
Core Design Contradiction:
Ease of operationVSProductivity

Solution Approach 1:

The invention uses the polymethylaluminoxane itself as a self-supporting solid structure, eliminating the need for external silica support that diminishes catalytic activity. This approach maintains the high polymerization activity characteristic of homogeneous systems while achieving solid form handling, as the active species are concentrated without dilution by inert support material.

Inventive Principle:
Principle #27Cheap short-living objects (Disposable)

Solution Approach 2:

The invention changes the structural parameters of the polymethylaluminoxane composition, specifically controlling the Al2O3 content (0.01-10 mol%) and aluminum content (36-43 mass%), to optimize the balance between solid state stability and catalytic activity. This parameter optimization enables the composition to function effectively in solid form while maintaining high polymerization productivity.

Inventive Principle:
Principle #35Parameter changes

4Productivity

If Al2O3 content is increased in solid polymethylaluminoxane composition, then catalytic activity increases, but composition stability may be affected

Engineering Contradiction:
Improvecatalytic activityVSAvoidcomposition stability
Core Design Contradiction:
ProductivityVSStability of the object's composition

Solution Approach 1:

The invention optimizes the Al2O3 content within a specific range (0.01-10 mol%) to achieve the desired balance between catalytic activity and composition stability. This controlled parameter adjustment allows the composition to exhibit enhanced activity while maintaining structural integrity and compositional stability during storage and polymerization processes.

Inventive Principle:
Principle #35Parameter changes

Data Source

PatentEP3480258B1Solid MAO composition containing al2o3 and method for producing same
Publication Date: 2023.12.20 TOSOH FINECHEM CORP
  • EP3480258B1 patent drawingFigure 1
  • EP3480258B1 patent drawingFigure 2
  • EP3480258B1 patent drawingFigure 3

AI summary

Provided is a solid polymethylaluminoxane composition which has higher activity when being used as a co-catalyst in olefin polymerization. The solid polymethylaluminoxane composition contains polymethylaluminoxane, trimethylaluminum, and Al2O3, wherein: (i) the aluminum content is in a range of 36-43 mass%; and (ii) the Al2O3 content is in a range of 0.001-10 mol% represented in terms of aluminum.