Fluoropolymer Emulsion Polymerization Particle Size Control

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Solution Overview

Problem

Current aqueous emulsion polymerization methods for fluoropolymers often result in small particle sizes due to the use of doping agents, which is undesirable for applications requiring thicker coatings or bimodal particle size distributions, and are costly due to the use of expensive fluorinated emulsifiers.

Innovation Solution

Incorporating a doping agent with a melting point ≤30°C and boiling point ≥100°C, selected from fluorinated cyclic hydrocarbons, polyoxyalkenes, or polyoxyalkanes, in a weight ratio of 1:2 to 1:20 with respect to the emulsifier, to increase particle sizes of fluoropolymers during emulsion polymerization.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Productivity

If doping agents are used to accelerate reaction rate and reduce emulsifier amounts, then reaction rate is improved and emulsifier cost is reduced, but particle sizes become too small (80 nm or less)

Engineering Contradiction:
Improvereaction rateVSAvoidparticle size
Core Design Contradiction:
ProductivityVSLength of moving object

Solution Approach 1:

The patent changes the chemical structure parameters of the doping agent by introducing fluorinated alkyl groups with specific chain lengths (C3-C10) and fluorine substitution patterns. This parameter modification allows the doping agent to maintain its ability to accelerate polymerization while reducing its tendency to form excessive nucleation sites, thereby achieving larger particle sizes (100-500 nm) compared to conventional doping agents.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent uses composite fluorinated compounds that combine characteristics of both emulsifiers and doping agents. These composite materials contain hydrophilic groups for emulsification and fluorinated hydrophobic groups for doping activity, allowing them to simultaneously stabilize larger particles and accelerate reaction without requiring separate emulsifier and doping agent components.

Inventive Principle:
Principle #40Composite materials

2Stability of the object's composition

If fluorinated emulsifiers are used to stabilize polymer particles, then particle stability is improved, but production cost increases due to expensive materials

Engineering Contradiction:
Improveparticle stabilityVSAvoidemulsifier cost
Core Design Contradiction:
Stability of the object's compositionVSQuantity of substance

Solution Approach 1:

The fluorinated compounds used in the patent perform multiple functions simultaneously: they act as emulsifiers to stabilize particles, as doping agents to accelerate polymerization, and as solvents for the monomers. This multi-functionality eliminates the need for separate expensive fluorinated emulsifiers and doping agents, reducing overall material costs while maintaining particle stability.

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

Solution Approach 2:

The patent employs fluorinated compounds with optimized molecular weights and structures that provide sufficient emulsification and doping activity at lower concentrations. By reducing the required amount of these specialized fluorinated materials through structural optimization, the overall cost of emulsifier and doping agent combinations is reduced.

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

3Manufacturing precision

If small particle sizes are achieved using conventional doping agents, then coating density is improved, but applications requiring thick coatings or bimodal distributions cannot be achieved

Engineering Contradiction:
Improvecoating densityVSAvoidapplication range
Core Design Contradiction:
Manufacturing precisionVSAdaptability or versatility

Solution Approach 1:

The patent creates a dynamic particle size distribution system where the fluorinated doping agent allows particles to grow to larger sizes during polymerization. This dynamic control enables the system to adapt to different application requirements by adjusting the doping agent concentration and molecular structure, producing particles in the 100-500 nm range that can form thick coatings or achieve bimodal distributions when needed.

Inventive Principle:
Principle #15Dynamics

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 approach allows for the generation of larger fluoropolymer particles, achieving particle sizes of >100 nm without the need for additional processes like seed polymerization, while reducing emulsifier usage and maintaining high dispersion stability.

Implementation Method 1

Incorporating a doping agent with a melting point ≤30°C and boiling point ≥100°C

Methodology Applied
Scientific EffectPhase change: Phase Change

Implementation Method 2

In aqueous emulsion polymerizations the polymerization is carried out in the presence of a fluorinated emulsifier, which is generally used to accelerate the reaction rate and to stabilize the polymer particles formed

Methodology Applied
Scientific EffectEmulsion: Emulsion

Data Source

PatentUS8623957B2Method of preparing fluoropolymers by aqueous emulsion polymerization
Publication Date: 2014.01.07 3M INNOVATIVE PROPERTIES CO

AI summary

Method of making fluoropolymers by emulsion polymerization of one or more fluorinated monomers in an aqueous phase in the presence of a fluorinated emulsifier, said method comprises adding a doping agent in a weight ratio with respect to the emulsifier of from about 1:2 to about 1:20, said doping agent has a melting point of equal or less than 30° C. and a boiling point of at least about 100° C. and is selected from the group consisting of fluorinated cyclic hydrocarbons, fluorinated polyoxyalkenes, fluorinated alkenes and fluorinated polyoxyalkenes.