Ketone-Containing Dithiocarbamate Iniferters for Polymer Architecture Control

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Solution Overview

Problem

Conventional radical polymerization methods struggle to produce polymers with precise architectural and structural characteristics, limiting the control over molecular weight, polydispersity, topology, and composition.

Innovation Solution

The use of ketone-containing dithiocarbamate or dithiocarbonate compounds as controlled radical initiators, which function as iniferters, allows for the formation of polymeric materials with well-defined architectures through controlled radical polymerization, enabling the formation of homopolymers, random copolymers, or block copolymers, and crosslinkable compositions that undergo chain extension and crosslinking upon exposure to actinic radiation.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Manufacturing precision

If conventional radical polymerization methods are used, then the polymerization process is simple and fast, but the molecular architecture and structural characteristics cannot be precisely controlled

Engineering Contradiction:
Improvemolecular architecture controlVSAvoidpolymerization method complexity
Core Design Contradiction:
Manufacturing precisionVSDevice complexity

Solution Approach 1:

The patent employs a chain transfer agent as an intermediary substance that mediates between the propagating radical and the monomer. This chain transfer agent temporarily captures the radical, forms a dormant species, and then releases it to continue polymerization, enabling controlled radical polymerization with precise molecular architecture while maintaining relative process simplicity

Inventive Principle:
Principle #24Intermediary (Mediator)

Solution Approach 2:

The patent controls polymerization parameters including the concentration of chain transfer agent, temperature, and monomer feed rate to achieve precise control over molecular weight, polydispersity, and composition. By adjusting these parameters, the molecular architecture can be precisely tailored without requiring overly complex polymerization systems

Inventive Principle:
Principle #35Parameter changes

2Manufacturing precision

If controlled radical polymerization methods are used, then polymers with well-defined molecular weight and polydispersity can be obtained, but the polymerization process becomes more complex

Engineering Contradiction:
Improvemolecular weight controlVSAvoidpolymerization system complexity
Core Design Contradiction:
Manufacturing precisionVSDevice complexity

Solution Approach 1:

The chain transfer agent serves as a mediator that reversibly transforms propagating radicals into dormant species, enabling controlled radical polymerization. This intermediary mechanism allows precise molecular weight control through the equilibrium between active and dormant chains, achieving narrow polydispersity without requiring complex multi-component systems

Inventive Principle:
Principle #24Intermediary (Mediator)

Solution Approach 2:

The chain transfer agent enables the polymerization system to self-regulate by automatically establishing an equilibrium between propagation and chain transfer reactions. This self-service mechanism controls molecular weight and polydispersity through intrinsic reaction dynamics rather than requiring external control systems

Inventive Principle:
Principle #25Self-service

3Manufacturing precision

If iniferter methods are used for controlled radical polymerization, then reversible chain transfer is achieved, but the initiator must serve multiple functions as initiator, chain transfer agent, and terminator

Engineering Contradiction:
Improvereversible chain transfer controlVSAvoidinitiator functionality flexibility
Core Design Contradiction:
Manufacturing precisionVSAdaptability or versatility

Solution Approach 1:

The patent employs an iniferter that universally performs three functions: initiating polymerization by generating radicals, acting as a chain transfer agent through reversible deactivation, and terminating chains when needed. This multi-functional iniferter achieves reversible chain transfer control while consolidating multiple roles into a single reagent, enhancing versatility

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

This approach enables the production of polymeric materials with controlled architectures and properties, facilitating the formation of crosslinked compositions and articles with tailored molecular structures.

Implementation Method 1

The controlled radical initiators are ketone-containing dithiocarbamate or dithiocarbonate compounds... exposure to actinic radiation

Methodology Applied
Scientific EffectPhotodissociation: Photodissociation

Implementation Method 2

controlled radical polymerization methods have been developed that allow the preparation of polymers with well-defined molecular weight, polydispersity, topology, composition, and microstructure

Methodology Applied
Scientific EffectControlled radical polymerization:

Implementation Method 3

crosslinkable compositions that undergo chain extension and crosslinking upon exposure to actinic radiation

Methodology Applied
Scientific EffectPhotopolymerization: Photopolymerisation

Data Source

PatentEP3755732B1Ketone-containing controlled radical initiators for polymerization reactions
Publication Date: 2025.09.03 3M INNOVATIVE PROPERTIES CO
  • EP3755732B1 patent drawingFigure 1
  • EP3755732B1 patent drawingFigure 2
  • EP3755732B1 patent drawing

AI summary

Controlled radical initiators that are ketone-containing dithiocarbamate or ketone-containing dithiocarbonate compounds are used to form polymeric materials that have a single polymeric block or multiple polymeric blocks. Reaction mixtures containing controlled radical initiators and various ethylenically unsaturated monomers, polymeric materials formed from the reaction mixtures, crosslinkable compositions containing the polymeric materials, crosslinked compositions formed from the crosslinkable compositions, and articles containing the polymeric materials, the crosslinkable compositions, or the crosslinked compositions are provided.