Centrally Functionalizable Living Cationic Polymer Synthesis

Resolve Bottlenecks,
Find Innovative SolutionsGenerate Solutions

Solution Overview

Problem

There is a lack of development in centrally-functionalizable polymers or copolymers with a centrally-substituted tetraene group that can be used to produce PIB-based materials with combined useful properties, despite advancements in living carbocationic polymerizations and the use of bi-directional initiators.

Innovation Solution

A method is developed to synthesize a centrally-functionalizable living cationic polymer or copolymer with a centrally-substituted tetraene group by initiating living cationic polymerization using a bi-directional initiator and subsequent thermolysis, allowing for further functionalization and utilization in producing amphiphilic polyurethanes and other materials.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If a bi-directional initiator is used for polyisobutylene polymerization, then cost is reduced compared to using HDCCl, but centrally-functionalizable polymers with reactive groups cannot be produced

Engineering Contradiction:

Improvepolymer functionalityVSAvoidsynthesis complexity

Core Design Contradiction:

ReliabilityVSEase of manufacture

Solution Approach 1:

The patent introduces a preliminary action step where the central bBCB fragment is thermally decomposed to generate a reactive tetraene group before the polymerization is complete. This preliminary modification of the initiator fragment enables subsequent functionalization reactions while maintaining the cost advantage of using bi-directional initiators like bBCB-diCL

Inventive Principle:

Principle #10Preliminary action

Solution Approach 2:

The patent applies parameter changes by utilizing thermal energy to transform the central bBCB fragment into a reactive tetraene group. This change in the chemical state of the central fragment enables it to function as a reactive site for subsequent functionalization while maintaining the overall polymer structure and the advantages of using bi-directional initiators

Inventive Principle:

Principle #35Parameter changes

2Manufacturing precision

If living carbocationic polymerization is used to achieve well-defined polymers with narrow molecular weight distributions, then polymer quality is improved, but centrally-functionalizable polymers with reactive groups cannot be produced

Engineering Contradiction:

Improvemolecular weight distributionVSAvoidfunctionalization capability

Core Design Contradiction:

Manufacturing precisionVSAdaptability or versatility

Solution Approach 1:

The patent applies preliminary action by introducing a thermal decomposition step that creates a reactive tetraene group at the center of the polymer chain before final functionalization. This allows the polymer to maintain its well-defined characteristics from living carbocationic polymerization while gaining the versatility to undergo various functionalization reactions

Inventive Principle:

Principle #10Preliminary action

Solution Approach 2:

The patent uses the tetraene group as an intermediary reactive species that bridges the well-defined polymer structure and the desired functionalization. This intermediary reactive group can participate in various reactions (epoxidation, hydrosulfuration, hydrosilation) while maintaining the narrow molecular weight distribution achieved through living carbocationic polymerization

Inventive Principle:

Principle #24Intermediary (Mediator)

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 creation of polymers with central reactive groups, facilitating various functionalizations and polymerizations, such as epoxidation, hydrosulfuration, and hydrosilation, leading to the production of materials with enhanced properties suitable for drug delivery and biocompatible applications.

Implementation Method 1

Living carbocationic polymerizations (LC+Ps) proceed in the absence of chain transfer and termination (collectively termed chain breaking) and lead to well-defined designed useful polymers

Methodology Applied

Scientific EffectLiving carbocationic polymerization:

Implementation Method 2

thermolyzing the formed non-centrally functionalizable living cationic polymer or copolymer such that a centrally-functionalizable living cationic polymer or copolymer having a centrally-substituted tetraene group is formed

Methodology Applied

Scientific EffectThermolysis: Thermolysis

Implementation Method 3

the step of epoxodizing the centrally-functionalizable living cationic polymer or copolymer having a centrally-substituted tetraene group

Methodology Applied

Scientific EffectEpoxidation: Oxidation

Implementation Method 4

the step of performing hydrosulfuration on the centrally-functionalizable living cationic polymer or copolymer having a centrally-substituted tetraene group

Methodology Applied

Scientific EffectHydrosulfuration: Hydrogenation

Implementation Method 5

the step of performing hydrosilation on the centrally-functionalizable living cationic polymer or copolymer having a centrally-substituted tetraene group

Methodology Applied

Scientific EffectHydrosilation: Chemical Bonding

Data Source

PatentUS10774185B2Centrally functionalizable living cationic polymer or copolymer and methods of synthesizing the same

Publication Date: 2020.09.15 THE UNIVERSITY OF AKRON

AI summary

In various embodiments, the present invention is directed to a centrally-functionalizable living cationic polymer or copolymer having a centrally-substituted tetraene group having the formulawherein each R is selected from the group consisting of a polymer or a copolymer, such as a polyisobutylene polymer or a poly(isobutylene-b-styrene) copolymer.