Fluorinated Copolymer Functionalization via CTFE Mediator

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Solution Overview

Problem

Fluoropolymers like PVDF and PTrFE face challenges in functionalization due to difficulties in copolymerizing with non-fluorinated monomers such as vinyl ethers, acrylates, and styrenes, limiting their applications and properties like adhesion, anti-corrosion, and hydrophobicity.

Innovation Solution

Development of novel fluorinated copolymers with triads (X-E-X) where X is an electron-acceptor fluorinated monomer and E is an electron-donor monomer with functional or functionalizable groups, specifically using chlorotrifluoroethylene (CTFE) and vinyl ethers, allowing for alternating copolymerization and enhancing functionalization.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Adaptability or versatility

If fluorinated monomers (VDF/TrFE) are copolymerized with non-fluorinated monomers to improve adhesion and surface properties, then functional properties are enhanced, but copolymerization difficulty increases and chemical resistance deteriorates

Engineering Contradiction:

Improvefunctional propertiesVSAvoidcopolymerization difficulty

Core Design Contradiction:

Adaptability or versatilityVSEase of manufacture

Solution Approach 1:

Chlorotrifluoroethylene (CTFE) acts as an intermediary monomer that bridges fluorinated monomers (VDF/TrFE) and non-fluorinated functional monomers (vinyl ethers). CTFE copolymerizes easily with both types of monomers, enabling the incorporation of functional groups while maintaining polymerization feasibility and preserving chemical resistance properties

Inventive Principle:

Principle #24Intermediary (Mediator)

Solution Approach 2:

The invention creates a composite copolymer structure containing three types of monomer units: fluorinated monomers (VDF/TrFE) for chemical resistance, CTFE for structural stability and copolymerization facilitation, and functional monomers (vinyl ethers) for enhanced surface properties. This composite approach allows simultaneous achievement of functional properties and manufacturing feasibility

Inventive Principle:

Principle #40Composite materials

2Adaptability or versatility

If functional monomers are incorporated to enhance adhesion and surface properties, then application versatility improves, but copolymerization compatibility worsens

Engineering Contradiction:

Improveapplication versatilityVSAvoidcopolymerization compatibility

Core Design Contradiction:

Adaptability or versatilityVSReliability

Solution Approach 1:

CTFE serves as a mediator that ensures reliable copolymerization between fluorinated monomers and functional vinyl ether monomers. Its unique electronic structure (electron-deficient double bond) allows it to copolymerize readily with electron-rich vinyl ethers while also copolymerizing with fluorinated monomers, thus ensuring copolymerization compatibility across all three monomer types

Inventive Principle:

Principle #24Intermediary (Mediator)

3Adaptability or versatility

If high proportions of functional monomers are used to maximize functional properties, then adhesion and surface properties improve, but chemical resistance and thermal stability deteriorate

Engineering Contradiction:

Improvesurface propertiesVSAvoidchemical resistance

Core Design Contradiction:

Adaptability or versatilityVSStability of the object's composition

Solution Approach 1:

The invention optimizes the compositional parameters of the copolymer by limiting the functional monomer content to 1-20 mol% and CTFE content to 1-30 mol%, with VDF/TrFE constituting 78-98 mol%. This parameter optimization ensures that functional properties are enhanced while maintaining the chemical resistance and thermal stability characteristic of fluoropolymers

Inventive Principle:

Principle #35Parameter changes

Solution Approach 2:

The composite copolymer structure distributes different functional roles among monomer units: fluorinated monomers provide chemical resistance backbone, CTFE provides structural stability and copolymerization facilitation, and functional monomers (at controlled low concentrations) provide surface properties. This composite approach prevents over-functionalization that would compromise chemical resistance

Inventive Principle:

Principle #40Composite materials

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 resulting copolymers exhibit improved properties like adhesion and chemical resistance, suitable for diverse applications including membranes, coatings, and energy devices, while maintaining the main properties of PVDF and PTrFE.

Implementation Method 1

The publication by Boschet F. and Améduri B. in Chem Rev, 2014, 114, 927-980 describes in detail the various known CTFE-based copolymers, which are classified in two categories: i) copolymers having a low proportion of comonomer, their properties being close to those of poly(chlorotrifluoroethylene) with regard to the thermoplastic nature and the high degree of crystallinity; and ii) copolymers containing electron-donor comonomers, said copolymers being obtained by a polymerization reaction of acceptor-donor type giving predominantly alternating structures.

Methodology Applied

Scientific EffectRadical polymerization:

Data Source

PatentUS10730979B2Functionalised fluorinated copolymers

Publication Date: 2020.08.04 ARKEMA FRANCE SA

AI summary

The invention relates to a fluorinated copolymers which are particularly based on vinylidene fluoride (VDF) or trifluoroethylene (TrFE) and particularly functionalized by functional and/or functionizable vinyl ethers. The invention also relates to methods for producing said copolymers, and to the applications thereof.