Degradable Conjugated Polymers for SWNT Separation

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Solution Overview

Problem

Current methods for separating semiconducting single-walled carbon nanotubes (s-SWNTs) from mixtures with metallic single-walled carbon nanotubes (m-SWNTs) are not suitable for large-scale technological processes and are costly due to the high price of conjugated polymers used as dispersants, which also leave residues on the s-SWNTs and are difficult to remove.

Innovation Solution

A process using degradable conjugated polymers, specifically polyimines, to disperse and separate s-SWNTs from m-SWNTs through dispersion in a solvent, followed by centrifugation and hydrolysis to degrade the polymers into small units, allowing for the recycling of the polymers and reducing costs.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Manufacturing precision

If conventional conjugated polymers are used as dispersants for SWNT separation, then selectivity and dispersion quality are improved, but cost increases and polymer removal becomes difficult

Engineering Contradiction:
Improveseparation selectivityVSAvoidpolymer contamination
Core Design Contradiction:
Manufacturing precisionVSObject-generated harmful factors

Solution Approach 1:

The polymer chain is segmented into repeating units containing imine bonds that can be hydrolyzed. This segmentation allows the polymer to function as an effective dispersant while providing cleavage points that enable complete degradation into small soluble fragments that can be easily removed from the SWNTs.

Inventive Principle:
Principle #1Segmentation

Solution Approach 2:

The chemical stability parameter of the polymer is changed by incorporating hydrolyzable imine bonds in the polymer backbone. This parameter change allows the polymer to transition from a stable, hard-to-remove state during dispersion to a labile, easily degradable state during purification, resolving the contradiction between effective dispersion and easy removal.

Inventive Principle:
Principle #35Parameter changes

2Manufacturing precision

If conventional conjugated polymers are used as dispersants, then separation quality is improved, but production cost increases due to polymer price

Engineering Contradiction:
Improveseparation qualityVSAvoidproduction cost
Core Design Contradiction:
Manufacturing precisionVSEase of manufacture

Solution Approach 1:

The polymer is designed to be sacrificial and disposable after performing its dispersion function. Through hydrolysis, the polymer degrades into small water-soluble fragments that can be easily washed away, eliminating the need for expensive polymer recovery and purification processes. The low cost of the imine-based polymer compared to conventional dispersants further reduces overall production costs.

Inventive Principle:
Principle #34Discarding and recovering

Solution Approach 2:

The imine-based polymer acts as a cheap, short-living dispersant that performs its function effectively during separation and then degrades completely. This disposable approach eliminates the need for expensive, reusable polymers and simplifies the overall manufacturing process by converting a permanent contaminant into a temporary, easily removable agent.

Inventive Principle:
Principle #27Cheap short-living objects (Disposable)

3Reliability

If conventional conjugated polymers are used for SWNT separation, then dispersion effectiveness is improved, but scalability for large-scale processes is limited

Engineering Contradiction:
Improvedispersion effectivenessVSAvoidscalability
Core Design Contradiction:
ReliabilityVSProductivity

Solution Approach 1:

The mechanical process of polymer removal through filtration and centrifugation is replaced by a chemical process—hydrolysis—that automatically degrades the polymer into small soluble fragments. This substitution simplifies the scalability pathway by replacing complex mechanical separation steps with a straightforward chemical treatment that can be easily scaled up for large-scale SWNT production.

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

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 method achieves high selectivity (>99%) for large-diameter s-SWNTs with minimal polymer contamination, enabling a low-cost, scalable, and environmentally friendly separation of high-purity s-SWNTs for electronic devices.

Implementation Method 1

dispersing semiconducting SWNTs and metallic SWNTs with polymer

Methodology Applied
Scientific EffectPolymer wrapping: Adsorption

Implementation Method 2

Poly(9,9-diocyl-fluorenyl-2,7-diyl) (PFO) as dispersant shows the highest selectivity

Methodology Applied
Scientific EffectSelective dispersion: Adsorption

Implementation Method 3

followed by centrifugation

Methodology Applied
Scientific EffectCentrifugal separation: Centrifugal Separation

Implementation Method 4

Chemical treatment with a base or an acid or water leads to degradation of the polymer into small units

Methodology Applied
Scientific EffectHydrolysis: Hydrolysis

Data Source

PatentEP3380541B1Degradable conjugated polymers
Publication Date: 2020.04.29 THE BOARD OF TRUSTEES OF THE LELAND STANFORD JUNIOR UNIV
  • EP3380541B1 patent drawingFigure 1
  • EP3380541B1 patent drawingFigure 2a~2b
  • EP3380541B1 patent drawingFigure 3

AI summary

A polymer comprising at least one unit of the formula (1) wherein T1 is a carbon atom or a nitrogen atom, T2 is a carbon atom if T1 is a nitrogen atom, or is a nitrogen atom if T1 is a carbon atom,r is 1, 2, 3 or 4, s is 1, 2, 3, or 4, M1 is preferably selected from the group consisting of M2 is preferably The polymers are prepared by reacting monomers (1a) with monomers (2a) H2N-[-M1-]r -NH2 (1a) OHC-[-M2-]s -CHO (2a) or the step of reacting monomers (1b) with monomers (2b) OHC-[-M1-]r -CHO (1b) H2N-[-M2-]s -NH2 (2b).