Short-Chain Fluoroacrylate Polymer for Low-Bioaccumulation Repellency

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Solution Overview

Problem

Perfluoroalkyl compounds with eight or more carbon atoms have high bioaccumulation potential and environmental toxicity, making them unsuitable for future use in water- and oil-repellents, while compounds with six or less carbon atoms are expected to have low bioaccumulation but lack effective water- and oil-repellency due to the absence of long perfluoroalkyl chains for orientation.

Innovation Solution

A mixture of fluoroalkyl alcohol-unsaturated carboxylic acid derivatives with a perfluoroalkyl group having six or less carbon atoms, which are vulnerable to biodegradation, is used to form a fluorine-containing polymer that maintains water- and oil-repellent properties without converting to toxic perfluorooctanoic acid or perfluorocarboxylic acids, achieved through esterification reactions and polymerization with acrylic or methacrylic acid.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If perfluoroalkyl compounds with eight or more carbon atoms are used, then water- and oil-repellent performance is improved, but bioaccumulation potential and environmental toxicity increase

Engineering Contradiction:
Improvewater- and oil-repellent performanceVSAvoidbioaccumulation potential and environmental toxicity
Core Design Contradiction:
ReliabilityVSObject-affected harmful factors

Solution Approach 1:

The patent changes the carbon atom parameter of the perfluoroalkyl group from 8 or more to 6 or less. This parameter change reduces the chain length below the threshold for high bioaccumulation potential while maintaining water- and oil-repellent performance through optimized molecular structure and orientation in the polymer coating.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent segments the perfluoroalkyl chain into a shorter configuration (6 or less carbon atoms) that can still achieve effective orientation and repellant function. The polymer structure is designed to accommodate this segmented, shorter chain while maintaining the necessary orientation for performance.

Inventive Principle:
Principle #1Segmentation

2Object-affected harmful factors

If perfluoroalkyl compounds with six or less carbon atoms are used, then bioaccumulation potential is reduced, but water- and oil-repellent performance deteriorates due to insufficient chain length for orientation

Engineering Contradiction:
Improvebioaccumulation potentialVSAvoidwater- and oil-repellent performance
Core Design Contradiction:
Object-affected harmful factorsVSReliability

Solution Approach 1:

The patent optimizes parameters including the specific fluorinated cyclic group structure, the number and position of fluorine atoms, and the polymer composition ratios. These parameter changes enable shorter perfluoroalkyl chains (6 or less carbon atoms) to achieve effective orientation and maintain repellant performance despite reduced chain length.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent uses composite polymer structures combining fluorinated cyclic groups with specific perfluoroalkyl chains. This composite material approach allows the shorter chains to work synergistically with the cyclic structures to achieve both low bioaccumulation and effective water- and oil-repellency.

Inventive Principle:
Principle #40Composite materials

3Reliability

If perfluoroalkyl (meth)acrylate with seven or more carbon atoms is used in combination with isocyanate group-containing monomer, then water- and oil-repellent performance is improved, but the complexity of the formulation increases and crosslinking agents are required

Engineering Contradiction:
Improvewater- and oil-repellent performanceVSAvoidformulation complexity
Core Design Contradiction:
ReliabilityVSDevice complexity

Solution Approach 1:

The patent extracts the crosslinking function from separate isocyanate group-containing monomers and integrates it into the fluorinated cyclic group structure itself. This eliminates the need for additional crosslinking agents while maintaining the enhanced water- and oil-repellent performance.

Inventive Principle:
Principle #2Taking out (Extraction)

Solution Approach 2:

The fluorinated cyclic group structure serves multiple functions simultaneously: it provides the necessary molecular orientation for repellant performance, enables crosslinking capability within the polymer chain itself, and maintains compatibility with the shorter perfluoroalkyl chains. This multi-functionality simplifies the overall formulation.

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

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 fluorine-containing polymer exhibits excellent water- and oil-repellency equivalent to conventional polymers, with a static contact angle comparable to homopolymers, while ensuring low bioaccumulation potential due to the degradation of the perfluoroalkyl group, thus addressing environmental concerns.

Implementation Method 1

which are produced by an esterification reaction of a mixture of fluoroalkyl alcohols represented by general formulae (IIa) and (IIb) with acrylic acid or methacrylic acid

Methodology Applied
Scientific EffectEsterification reaction: Chemical Bonding

Implementation Method 2

the expression of water- and oil-repellency of perfluoroalkyl (meth)acrylate is attributable to the orientation of a perfluoroalkyl group (Rf group) on a treated film

Methodology Applied
Scientific EffectSurface orientation effect: Surface Tension

Implementation Method 3

they are suggested to be possibly converted to perfluorooctanoic acid or perfluorocarboxylic acids having more than eight carbon atoms by biodegradation or chemical degradation in the environment

Methodology Applied
Scientific EffectBiodegradation: Decomposition (biological)

Implementation Method 4

they are suggested to be possibly converted to perfluorooctanoic acid or perfluorocarboxylic acids having more than eight carbon atoms by biodegradation or chemical degradation in the environment

Methodology Applied
Scientific EffectChemical degradation: Decomposition (biological)

Data Source

PatentEP2233464B1Mixture of fluoroalkyl alcohol-unsaturated carboxylic acid derivatives, polymer of the derivatives, and water repellent oil repellent agent containing the polymer as active ingredient
Publication Date: 2016.06.08 UNIMATEC CO LTD

AI summary

Disclosed is (1) a mixture of fluoroalkyl alcohol-unsaturated carboxylic acid derivatives represented by the general formulae: CF3(CF2)n(CH=CF)a(CF2CF2)b(CH2CH2)cOCOCR=CH2 and CF3(CF2)n-1(CF=CH)a CF2(CF2CF2)b(CH2CH2)cOCOCR=CH2, wherein R is a hydrogen atom or a methyl group, n is an integer of 1 to 5, a is an integer of 1 to 4, b is an integer of 0 to 3, and c is an integer of 1 to 3; (2) a fluorine-containing polymer containing the mixture as a polymerization unit; and (3) a water- and oil-repellent comprising the fluorine-containing polymer as an active ingredient. The fluoroalkyl alcohol-unsaturated carboxylic acid derivatives are produced by an esterification reaction of a mixture of fluoroalkyl alcohols represented by the general formulae: CF3(CF2)n(CH=CF)a(CF2CF2)b(CH2CH2)cOH and CF3(CF2)n-1(CF=CH)aCF2(CF2CF2)b (CH2CH2)cOH, with acrylic acid or methacrylic acid.