Living Radical Polymerization Initiator with Dual Halogen Reactivity

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Solution Overview

Problem

Conventional radical polymerization methods face challenges in controlling molecular weight and achieving narrow molecular weight distribution in vinyl polymers, limiting their application in advanced fields like nanotechnology.

Innovation Solution

A living radical polymerization initiator with two halogen atoms of different reactivity is used, allowing for distinct polymerization reactions to proceed in two directions, enabling precise control over molecular weight and distribution through a two-step polymerization process.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Manufacturing precision

If conventional radical polymerization method is used, then polymerization reaction can proceed, but molecular weight control is difficult and molecular weight distribution is broad

Engineering Contradiction:
Improvemolecular weight control precisionVSAvoidpolymerization initiator structure complexity
Core Design Contradiction:
Manufacturing precisionVSDevice complexity

Solution Approach 1:

The polymerization initiator is divided into multiple independent initiating groups (first initiating group and second initiating group) with different reactivities. Each initiating group can independently initiate polymerization, allowing separate control of polymerization reactions. This segmentation enables precise molecular weight control by managing each initiating group's contribution to the overall polymer structure.

Inventive Principle:
Principle #1Segmentation

Solution Approach 2:

Different initiating groups are designed with distinct local properties (different reactivities). The first initiating group has higher reactivity while the second has lower reactivity, allowing selective activation under different conditions. This local quality differentiation enables staged polymerization control, where each group contributes differently to molecular weight distribution, achieving narrow PDI.

Inventive Principle:
Principle #3Local quality

2Manufacturing precision

If living radical polymerization method is used, then molecular weight control and narrow molecular weight distribution can be achieved, but reaction system complexity increases

Engineering Contradiction:
Improvemolecular weight distribution controlVSAvoidreaction system complexity
Core Design Contradiction:
Manufacturing precisionVSDevice complexity

Solution Approach 1:

The polymerization system incorporates dynamic control through initiators with different reactivities that can be activated at different stages. The first initiating group activates under initial conditions while the second activates under modified conditions, creating a dynamic, staged polymerization process. This dynamic approach maintains living radical polymerization benefits while managing system complexity through controlled activation sequences.

Inventive Principle:
Principle #15Dynamics

3Adaptability or versatility

If multiple initiating groups with different reactivities are introduced, then different polymerization reactions can proceed in two directions, but initiator structure complexity increases

Engineering Contradiction:
Improvepolymerization reaction direction controlVSAvoidinitiator structure complexity
Core Design Contradiction:
Adaptability or versatilityVSDevice complexity

Solution Approach 1:

The initiator structure employs asymmetry by incorporating two different initiating groups with distinct reactivities rather than identical groups. This asymmetric design allows the initiator to direct polymerization in different directions or at different rates, creating versatility in polymer architecture control while maintaining a relatively simple overall molecular framework.

Inventive Principle:
Principle #4Asymmetry

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 production of polymers with narrow molecular weight distribution and controlled molecular weight, enhancing their suitability for advanced applications such as nanotechnology.

Implementation Method 1

a living radical polymerization initiator which consists of the following general formula (1): having two halogen atoms different from each other in reactivity and enabling different polymerization reactions to proceed in two directions by having each of the halogen atoms as a initiating group

Methodology Applied
Scientific EffectHomolytic bond cleavage:

Implementation Method 2

a first polymerization step in which, for only one halogen atom of the X or Y of the living radical polymerization initiator, a living radical polymerization reaction in which the living radical polymerization reaction initiator is mixed with a monomer with unsaturated bond

Methodology Applied
Scientific EffectRadical polymerization:

Data Source

PatentEP3190131B1Living radical polymerization initiator, method for producing polymer, and polymer
Publication Date: 2020.07.29 GODO SHIGEN
  • EP3190131B1 patent drawingFigure 1
  • EP3190131B1 patent drawingFigure 2
  • EP3190131B1 patent drawingFigure 3(a)~3(e)

AI summary

A living radical polymerization initiator represented by the following general formula (1), which uses a living radical polymerization initiator that contains, as initiating groups for reactions, two halogen atoms different from each other in reactivity, and which enables different living radical polymerization reactions to proceed with respect to the respective initiating groups: herein, R1 represents an organic group which is linkable with two or more other organic groups, and which is selected from an aliphatic group having 1 to 12 carbon atoms, an aromatic group, a carbonyl group, a sulfonyl group and an organic group obtained by combining two or more of these groups, R2 , R3, R4 and R5 are a hydrogen atom or an organic group selected from an aliphatic group having 1 to 12 carbon atoms, an aromatic group, a carbonyl group, a carboxyl group and a sulfonyl group, X and Y are a halogen atom, m and n are an integer of 1 or more, and the X and Y are in a state in which they are different from each other in reactivity with a monomer.