Vanadium Pyridine-Imine Complex for Diene Polymerization

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Solution Overview

Problem

Current vanadium-based catalytic systems for the polymerization of conjugated dienes face challenges in achieving high catalytic activity and yield, particularly for producing linear or branched polybutadiene and polyisoprene, with existing systems often resulting in low molecular weight polymers and instability at elevated temperatures.

Innovation Solution

A vanadium pyridine-imine complex is developed, combined with specific co-catalysts such as aluminum derivatives and aluminoxanes, to form a catalytic system that enhances the polymerization of conjugated dienes, achieving high yields and stability across a range of temperatures.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Stability of the object's composition

If conventional vanadium-based catalytic systems are used for polymerization of conjugated dienes, then trans-1,4 structure polymers can be obtained, but the molecular weight is low and catalytic activity decreases at elevated temperatures

Engineering Contradiction:
Improvecatalytic stabilityVSAvoidcatalytic activity
Core Design Contradiction:
Stability of the object's compositionVSProductivity

Solution Approach 1:

The patent modifies the ligand structure by introducing electron-donating groups (such as methoxy, methyl, or halogen substituents on the pyridine and imine rings) to change the electronic properties of the vanadium center. This parameter change in ligand electronics enhances catalytic activity while maintaining stability across a broader temperature range, directly resolving the contradiction between catalytic stability and productivity

Inventive Principle:
Principle #35Parameter changes

2Manufacturing precision

If homogeneous catalytic systems like VCl3(THF)3/AlEt2Cl are used, then high trans-1,4 content polymers are obtained, but the molecular weight remains lower compared to heterogeneous systems

Engineering Contradiction:
Improvepolymer structure controlVSAvoidmolecular weight
Core Design Contradiction:
Manufacturing precisionVSWeight of moving object

Solution Approach 1:

The patent creates a composite catalytic system by combining the organometallic vanadium pyridine-imine complex with specific co-catalysts (aluminum alkyls or aluminoxanes). This composite approach allows the homogeneous catalyst to achieve molecular weights comparable to heterogeneous systems while maintaining the advantage of well-defined polymer structure and high trans-1,4 content, thus resolving the contradiction between manufacturing precision and molecular weight

Inventive Principle:
Principle #40Composite materials

3Ease of manufacture

If the ligand structure is simplified for easier synthesis, then manufacturing cost decreases, but catalytic activity and polymer yield are reduced

Engineering Contradiction:
Improveligand synthesisVSAvoidpolymer yield
Core Design Contradiction:
Ease of manufactureVSProductivity

Solution Approach 1:

The ligand is designed as a modular structure consisting of a pyridine ring connected to an imine ring through a flexible linker. This segmentation allows independent optimization of each fragment: the pyridine portion can be substituted with electron-donating groups to enhance activity, while the imine portion provides structural stability. The modular nature enables easier synthesis through sequential condensation reactions, resolving the contradiction between ease of manufacture and productivity

Inventive Principle:
Principle #1Segmentation

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 vanadium pyridine-imine complex catalytic system achieves high yields of linear or branched polybutadiene and polyisoprene with improved molecular weight and stability, addressing the limitations of existing systems by maintaining activity and efficiency across a broader temperature range.

Implementation Method 1

The vanadium pyridine-imine complex catalytic system achieves high yields of linear or branched polybutadiene and polyisoprene with improved molecular weight and stability

Methodology Applied
Scientific EffectCatalysis: Catalysis

Data Source

PatentEP3374081B1Vanadium pyridine-imine complex, catalytic system comprising said vanadium pyridine-immine complex and a (CO) polymerization process of conjugated dienes
Publication Date: 2021.06.16 VERSALIS SPA
  • EP3374081B1 patent drawingFigure 1~2
  • EP3374081B1 patent drawingFigure 3~4
  • EP3374081B1 patent drawingFigure 5~6

AI summary

Vanadium pyridine-imine complex having general formula (I), wherein : - R1, R2, R3, R4, R5 and R6, equal to or different from each other, represent a hydrogen atom; or are selected from linear or branched C1-C20 alkyl groups, preferably C1-C15, optionally halogenated, cycloalkyl groups optionally substituted, aryl groups optionally substituted; - X1, X2 and X3, equal to or different from each other, represent a halogen atom such as, for example, chlorine, bromine, iodine, preferably chlorine; or are selected from linear or branched C1-C20 alkyl groups, preferably C1-C15, -OCOR7 groups or -OR7 groups wherein R7 is selected from linear or branched C1-C20 alkyl groups, preferably C1-C15; - Y is selected from ethers such as, for example, diethylether, tetrahydrofuran (THF), dimethoxyethane, preferably is etrahydrofuran (THF); - n is 0 or 1. Said vanadium pyridine-imine complex having general formula (I) can be advantageously used in a catalytic system for the (co) polymerization of conjugated dienes.