Fluoroelastomer Polymerization Without Fluorinated Emulsifiers

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Solution Overview

Problem

Current methods for producing peroxide curable fluoroelastomers require the use of fluorinated emulsifiers and additives, which increase costs and process complexity, and do not achieve optimal mechanical properties without them.

Innovation Solution

A curable fluoroelastomer composition is developed using repeating units from VDF and HFP with halogen atoms like iodine and bromine, and perfluorinated bisolefinic ethers, polymerized in an aqueous medium without fluorinated emulsifiers, achieving at least 30% by mole of HFP units and suitable for peroxide curing.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Ease of manufacture

If fluorinated emulsifiers and fluorinated additives are used in aqueous emulsion polymerization to produce peroxide curable fluoroelastomers, then the polymerization process can be carried out effectively, but the costs increase and process complexity increases

Engineering Contradiction:
Improvepolymerization process feasibilityVSAvoidprocess complexity
Core Design Contradiction:
Ease of manufactureVSDevice complexity

Solution Approach 1:

The patent removes fluorinated emulsifiers and fluorinated additives from the polymerization process. The invention achieves effective aqueous emulsion polymerization without these problematic substances, thereby reducing costs and process complexity while maintaining manufacturing feasibility

Inventive Principle:
Principle #2Taking out (Extraction)

Solution Approach 2:

The patent replaces expensive fluorinated emulsifiers with non-fluorinated alternatives that are cheaper and do not require removal/recycling processes. This substitution reduces both material costs and process complexity

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

2Ease of manufacture

If fluorinated emulsifiers and fluorinated additives are used in aqueous emulsion polymerization, then the polymerization can proceed, but solvent removal and recycling steps are required which increase costs

Engineering Contradiction:
Improvepolymerization processabilityVSAvoidsolvent removal and recycling costs
Core Design Contradiction:
Ease of manufactureVSLoss of substance

Solution Approach 1:

The patent extracts and eliminates the need for fluorinated emulsifiers that would require solvent removal and recycling. The process uses water as the sole continuous phase without fluorinated substances, eliminating the need for costly solvent recovery operations

Inventive Principle:
Principle #2Taking out (Extraction)

Solution Approach 2:

Instead of recovering and recycling fluorinated solvents and emulsifiers (which is costly and complex), the invention discards them entirely by using a water-based system without fluorinated additives, thereby eliminating the recovery step altogether

Inventive Principle:
Principle #34Discarding and recovering

3Ease of manufacture

If emulsifiers are used in aqueous emulsion polymerization, then the polymerization can be carried out, but the emulsifiers must be removed from the product which leads to increased process steps and costs

Engineering Contradiction:
Improveemulsion polymerization capabilityVSAvoidprocess efficiency
Core Design Contradiction:
Ease of manufactureVSProductivity

Solution Approach 1:

The patent removes the requirement for emulsifier removal from the product purification process. By using non-fluorinated emulsifiers or emulsifier-free polymerization, the invention eliminates the need for additional removal steps, thereby increasing process efficiency

Inventive Principle:
Principle #2Taking out (Extraction)

Solution Approach 2:

Instead of using emulsifiers that need to be removed, the invention inverts the approach by using water-soluble initiators and conditions that allow polymerization without traditional emulsifiers, or uses emulsifiers that naturally decompose or remain in the water phase without contaminating the polymer product

Inventive Principle:
Principle #13The other way round (Inversion)

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

This method allows for the production of fluoroelastomers with improved mechanical properties, such as high elongation at break, tensile strength, and Shore A hardness, without the need for fluorinated emulsifiers, reducing costs and process complexity.

Implementation Method 1

A commonly used cure system is based on a peroxide cure reaction using appropriate curing compounds having or creating peroxides, which in turn are believed to generate free radicals. The fluoroelastomers suitable for use in peroxide curing systems (peroxide curable fluoroelastomers) contain reactive sites which include halogens, such as bromine and/or iodine. It is generally believed that the bromine or iodine atoms are abstracted in the free radical peroxide cure reaction, thereby causing the fluoropolymer molecules to cross-link and to form a three dimensional network.

Methodology Applied
Scientific EffectFree radical mechanism:

Data Source

PatentEP2601226B2Peroxide curable fluoroelastomers containing modifiers and iodine or bromine endgroups
Publication Date: 2023.07.12 3M INNOVATIVE PROPERTIES CO

AI summary

Provided are curable fluoroelastomers. Further provided are methods of making the curable elastomers, curable fluoroelastomer compositions and methods of making them and shaped articles made from the curable fluoroelastomer compositions.