Oxidoreductase-Catalyzed Curing of Unsaturated Polyester Resins

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Solution Overview

Problem

Current accelerators used in the curing of unsaturated polyester resins, such as cobalt salts, are hazardous to the environment and non-biodegradable, and existing enzyme-based methods are limited to aqueous coating compositions, necessitating the development of non-carcinogenic, biodegradable alternatives for non-aqueous thermosetting resins.

Innovation Solution

A composition comprising a curable resin with ethylenically unsaturated polymerizable groups, an ethylenically unsaturated polymerizable monomer, an oxidoreductase, and at least one of an organic peroxide or hydrogen peroxide, with a water content of 0.0 to 20.0% by weight, which utilizes enzymes like horseradish peroxidase to initiate radical polymerization, providing a biobased acceleration mechanism.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Productivity

If cobalt salts are used as accelerators for curing unsaturated polyester resins, then curing efficiency is improved, but environmental harm increases due to carcinogenicity and non-biodegradability

Engineering Contradiction:
Improvecuring efficiencyVSAvoidenvironmental harm
Core Design Contradiction:
ProductivityVSObject-affected harmful factors

Solution Approach 1:

The patent changes the chemical nature of the accelerator from inorganic cobalt salts to biological enzymes (oxidoreductases). This parameter change maintains the catalytic function for polymerization while eliminating the harmful properties of cobalt. The enzyme catalysts operate through different mechanistic parameters (oxidoreduction reactions) compared to traditional metal salts, achieving curing without environmental harm.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent replaces the chemical mechanism of metal salt acceleration with a biological mechanism. Instead of using cobalt salts that initiate polymerization through single-electron transfer, the invention employs oxidoreductase enzymes that catalyze the reaction through enzymatic oxidation-reduction processes. This substitution maintains curing functionality while removing toxicological concerns.

Inventive Principle:
Principle #28Mechanics substitution (Replace mechanical system)

2Object-affected harmful factors

If enzyme-based accelerators are used for curing polymers, then environmental friendliness is improved, but applicability is limited to aqueous coating compositions

Engineering Contradiction:
Improveenvironmental friendlinessVSAvoidapplicability range
Core Design Contradiction:
Object-affected harmful factorsVSAdaptability or versatility

Solution Approach 1:

The patent makes the enzyme-based acceleration system universal by demonstrating its effectiveness across multiple substrate types and formulation environments. The oxidoreductase catalysts can function in aqueous coating compositions, non-aqueous thermosetting resins, and other diverse systems. This multi-functionality is achieved by selecting enzymes with broad substrate specificity and optimizing their performance across different chemical environments.

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

Solution Approach 2:

The patent introduces water-soluble mediators or co-factors that enable the enzyme-based acceleration system to operate effectively in non-aqueous systems. These intermediaries facilitate the transfer of electrons or reactive species between the enzyme active site and the polymerizable groups in non-aqueous environments, bridging the gap between enzymatic catalysis and diverse application media.

Inventive Principle:
Principle #24Intermediary (Mediator)

3Reliability

If traditional peroxide initiators are used for polymerization, then curing is achieved, but the process lacks environmental sustainability

Engineering Contradiction:
Improvecuring reliabilityVSAvoidenvironmental sustainability
Core Design Contradiction:
ReliabilityVSLoss of substance

Solution Approach 1:

The patent employs oxidoreductase enzymes that can be easily separated from the polymerization system and recovered for reuse. Unlike metal salts that remain in the cured product and pose environmental risks, the enzymatic catalysts can be removed through filtration or centrifugation and potentially reused. This approach eliminates the need to discard harmful substances while maintaining reliable curing through the enzyme's catalytic activity.

Inventive Principle:
Principle #34Discarding and recovering

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 solution enables efficient curing of thermosetting resins while being environmentally friendly, as it uses biodegradable enzymes and reduces the environmental impact associated with traditional accelerators, and is applicable in both aqueous and non-aqueous systems, offering a broader range of applications.

Implementation Method 1

The radical initiator, usually a peroxide, decomposes into highly reactive peroxide radicals that start the radical polymerisation of the unsaturated polyesters with the vinyl functional monomers

Methodology Applied
Scientific EffectRadical polymerization: Photopolymerisation

Implementation Method 2

certain enzymes can act as biobased accelerators for the crosslinking of certain kinds of polymers

Methodology Applied
Scientific EffectEnzyme catalysis: Enzyme

Implementation Method 3

The radical initiator, usually a peroxide, decomposes into highly reactive peroxide radicals

Methodology Applied
Scientific EffectPeroxide decomposition: Hydrogen Peroxide

Implementation Method 4

a composition comprising a curable resin or prepolymer component having ethylenically unsaturated polymerizable groups, an ethylenically unsaturated polymerizable monomer, an oxidoreductase, and at least one of an organic peroxide or hydrogen peroxide

Methodology Applied
Scientific EffectOxidation-reduction: Redox Reactions

Data Source

PatentEP3997166B1Curable composition
Publication Date: 2023.09.06 BYK CHEMIE GMBH

AI summary

A composition comprising a) a curable resin or prepolymer component having ethylenically unsaturated polymerizable groups, b) an ethylenically unsaturated polymerizable monomer, c) an oxidoreductase and d) at least one of an organic peroxide and hydrogen peroxide, wherein the composition comprises between 0.0 and 20.0 % by weight of water, calculated on the total weight of the composition.