Oxo-nitrogenated Iron Complex for Diene Polymerization Microstructure Control

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Solution Overview

Problem

Current catalytic systems for the polymerization of conjugated dienes, such as polybutadiene and polyisoprene, struggle to produce polymers with specific mixed structures, particularly those with high 1,4-cis and 1,2 unit content or 1,4-cis and 3,4 unit content, which are desirable for industrial applications like tire production.

Innovation Solution

An oxo-nitrogenated iron complex with a specific general formula is used in a catalytic system that includes a co-catalyst, typically an aluminum compound, to achieve high selectivity for 1,4-cis and 1,2 or 1,4-cis and 3,4 units in the polymerization of conjugated dienes, ensuring a prevalent content of these units in the resulting polymers.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Manufacturing precision

If conventional catalytic systems (Ti, Co, Ni, Nd based) are used for polymerization, then high catalytic activity is achieved, but the ability to produce polymers with specific mixed structures (high 1,4-cis and 1,2 unit content) is limited

Engineering Contradiction:
Improvepolymer microstructure controlVSAvoidcatalyst system flexibility
Core Design Contradiction:
Manufacturing precisionVSAdaptability or versatility

Solution Approach 1:

The invention changes the chemical parameters of the catalyst system by introducing an oxo-nitrogenated iron complex with specific ligand structures (combining pyridine and amine moieties). This parameter change in catalyst composition enables selective production of polymers with high 1,4-cis and 1,2 unit content, resolving the contradiction between manufacturing precision and catalyst versatility

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The catalyst system employs a composite structure where the iron complex is combined with specific organic ligands (pyridine-amine hybrid ligands). This composite approach creates a catalyst with tailored electronic and steric properties, enabling precise control over polymer microstructure while maintaining catalytic activity

Inventive Principle:
Principle #40Composite materials

2Ease of manufacture

If iron-based catalysts with simple ligands are used, then the catalytic system is easier to manufacture, but the selectivity for specific polymer structures (1,4-cis and 1,2 units) is insufficient

Engineering Contradiction:
Improvecatalyst synthesis simplicityVSAvoidpolymer microstructure control
Core Design Contradiction:
Ease of manufactureVSManufacturing precision

Solution Approach 1:

The ligand structure is segmented into distinct functional modules: a pyridine moiety that coordinates to iron and an amine moiety that provides steric control. This segmentation allows systematic modification of catalyst properties while maintaining a relatively simple synthesis pathway, balancing ease of manufacture with microstructure control

Inventive Principle:
Principle #1Segmentation

Solution Approach 2:

The oxo-nitrogenated ligand acts as an intermediary between the iron center and the diene substrate. The specific arrangement of nitrogen atoms in the ligand mediates the interaction, directing the polymerization to produce high 1,4-cis and 1,2 unit content while keeping the catalyst synthesis accessible

Inventive Principle:
Principle #24Intermediary (Mediator)

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 catalytic system effectively produces polymers with the desired mixed structures, achieving a content of 1,4-cis and 1,2 units or 1,4-cis and 3,4 units of at least 90%, meeting the requirements for industrial applications such as tire production with high efficiency.

Implementation Method 1

an oxo-nitrogenated iron complex having general formula (I) or (II)... in a catalytic system for the (co)polymerization of conjugated dienes

Methodology Applied
Scientific EffectCatalysis: Catalysis

Data Source

PatentEP3464393B1Oxo-nitrogenated iron complex, catalytic system comprising said oxo-nitrogenated iron complex and process for the (CO)polymerization of conjugated dienes
Publication Date: 2020.08.26 VERSALIS SPA
  • EP3464393B1 patent drawingFigure 1
  • EP3464393B1 patent drawingFigure 2
  • EP3464393B1 patent drawingFigure 3

AI summary

An oxo-nitrogenated iron complex having general formula (I) or (II) wherein: R1 and R2 identical or different, represent a hydrogen atom; or are selected from linear or branched, optionally halogenated C1-C20, preferably C1-C15, alkyl groups, optionally substituted cycloalkyl groups, optionally substituted aryl groups; R3, identical or different, represent a hydrogen atom; or are selected from linear or branched, optionally halogenated C1-C20, preferably C1-C15, alkyl groups, optionally substituted cycloalkyl groups, optionally substituted aryl groups; X1 and X2, identical or different, represent a halogen atom such as, for example, chlorine, bromine, iodine; or are selected from linear or branched C1-C20, preferably C1-C15, alkyl groups, -OCOR4 groups or -OR4 groups wherein R4 is selected from linear or branched C1-C20, preferably C1-C15, alkyl groups. Said oxo-nitrogenated iron complex having general formula (I) or (II) can be advantageously used in a catalytic system for the (co)polymerization of conjugated dienes.