VDF-TrFE Copolymers with Functional Termonomers

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Solution Overview

Problem

There is a need for new fluorinated copolymers, particularly those based on vinylidene fluoride (VDF) and trifluoroethylene (TrFE), as existing methods for controlled radical copolymerization are costly and pose explosion risks due to the use of borane compounds, and there is a lack of diversity in terpolymers with improved properties.

Innovation Solution

Copolymers are formed through conventional copolymerization of VDF, TrFE, and a third monomer with a molar mass greater than 100 g/mol, such as 2,3,3,3-tetrafluoropropene, 2-chloro-3,3,3-trifluoropropene, or α-β-difluoroacrylic acid, without the use of chain transfer agents, resulting in terpolymers with broadened polymolecularity indices and specific functional groups.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Manufacturing precision

If controlled radical copolymerization is used with borane compounds, then molar mass and polydispersity control is improved, but cost increases and explosion risks are generated

Engineering Contradiction:
Improvemolar mass controlVSAvoidexplosion risks
Core Design Contradiction:
Manufacturing precisionVSObject-affected harmful factors

Solution Approach 1:

The invention extracts and removes the harmful borane compounds from the polymerization system while maintaining controlled polymerization capabilities through alternative initiators and conditions, thereby eliminating explosion risks while preserving molar mass control

Inventive Principle:
Principle #2Taking out (Extraction)

Solution Approach 2:

The patent employs conventional, inexpensive initiators that can be easily handled and disposed of safely, replacing the expensive and hazardous borane compounds with readily available alternatives that achieve similar polymerization control without the safety risks

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

2Manufacturing precision

If borane compounds are used as chain transfer agents, then polymerization control is improved, but cost increases

Engineering Contradiction:
Improvepolydispersity controlVSAvoidmanufacturing cost
Core Design Contradiction:
Manufacturing precisionVSEase of manufacture

Solution Approach 1:

The invention substitutes expensive borane compounds with conventional, low-cost initiators and chain transfer agents that are readily available and economically viable for industrial production, while maintaining adequate control over polydispersity

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

Solution Approach 2:

The patent optimizes polymerization parameters such as temperature, pressure, and monomer ratios to achieve effective polymerization control using economical reagents, compensating for the lower cost of materials through precise process parameter management

Inventive Principle:
Principle #35Parameter changes

3Ease of manufacture

If conventional copolymerization methods are used, then cost and safety are improved, but diversity of terpolymer properties is limited

Engineering Contradiction:
Improvemanufacturing costVSAvoidterpolymer property diversity
Core Design Contradiction:
Ease of manufactureVSAdaptability or versatility

Solution Approach 1:

The invention employs a universal copolymerization methodology that can accommodate multiple different third monomers (CTFE, HFP, VF, and others) using the same basic process framework, thereby achieving diverse terpolymer properties through a single versatile platform

Inventive Principle:
Principle #6Universality (Multi-functionality)

Solution Approach 2:

The patent achieves property diversity by systematically varying composition parameters (monomer ratios, feed sequences) and process parameters (temperature, pressure, initiator type) within the conventional copolymerization framework, enabling tailoring of terpolymer properties without requiring fundamentally different synthesis approaches

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 process produces terpolymers with enhanced properties suitable for piezoelectric, ferroelectric, and pyroelectric applications, offering improved material characteristics and reducing production costs by eliminating the need for expensive and hazardous reagents.

Implementation Method 1

The invention relates to copolymers based on vinylidene fluoride (VDF), trifluoroethylene (TrFE) and at least one third monomer, as well as a process for preparing these copolymers

Methodology Applied
Scientific EffectCopolymerization: Chemical Bonding

Data Source

PatentEP2981561B1Copolymers containing vinylidene fluoride and trifluoroethylene
Publication Date: 2017.08.16 ARKEMA FRANCE SA
  • EP2981561B1 patent drawingFigure 1a~1b
  • EP2981561B1 patent drawingFigure 2a~2b
  • EP2981561B1 patent drawingFigure 3a~3b

AI summary

The subject matter of the invention is a copolymer obtained by free-radical copolymerization of vinylidene fluoride with trifluoroethylene and of at least a third monomer, the third monomer having a molar mass greater than 0 g/mol and corresponding to the formula: in which R1 is a hydrogen atom or a fluorine atom, and R2 and R3 are chosen, independently of one another, from Cl, F and CF3, and the functional groups are selected from phosphonate, carboxylic acid, SO2X (where X is F, OK, ONa or OH) or Si(OR)3 (R being a methyl, ethyl or isopropyl group) groups. The invention also relates to a process for preparing this copolymer.