Ordered Polyblock Copolymer Synthesis for Uniform Electrolyte Chains
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Solution Overview
Problem
Existing methods for synthesizing block copolymers used in polymer electrolytes are complex, costly, and lack scalability, reproducibility, and efficiency, particularly in controlling lithium ion conductivity and mechanical stability, which are crucial for safe and efficient battery applications.
Innovation Solution
A sequential and convergent process using a Li-organyl initiator with a pKa greater than or equal to 45 for non-polar block polymerization and epoxy functionalization of polar blocks in a non-polar solvent, allowing for the covalent linkage of polar blocks to non-polar blocks in a single step, without solvent or counterion exchange, to achieve uniform chain lengths and controlled ion-conducting properties.
Engineering Contradictions & Design Principles
Engineering Contradiction Analysis
1Ease of manufacture
If conventional methods are used to synthesize block copolymers, then the synthesis process becomes complex and costly, but the manufacturing precision and reproducibility of chain lengths deteriorate
Solution Approach 1:
The synthesis process is divided into two independent segments: (1) preparation of non-polar block anion via living anionic polymerization, and (2) separate preparation of polar block with epoxy functionalization. These segments are then combined in a coupling reaction. This segmentation allows each block to be optimized independently, simplifying the overall process while maintaining high precision in chain length control through living polymerization techniques.
Solution Approach 2:
The polar block is pre-functionalized with epoxy groups before the coupling reaction. This preliminary action ensures that the polar block is ready for immediate coupling with the non-polar block anion, eliminating the need for in-situ functionalization during the main synthesis. This approach simplifies the overall process while ensuring high reproducibility of the final block copolymer structure.
2Productivity
If multiple synthesis steps including solvent and counterion exchange are used, then the synthesis becomes less scalable, but the manufacturing precision improves
Solution Approach 1:
The invention merges the coupling reaction of polar and non-polar blocks with the epoxy functionalization step into a single operation. The polar block is functionalized with epoxy groups in advance, and then directly coupled with the non-polar block anion without requiring separate solvent or counterion exchange steps. This consolidation maintains manufacturing precision while significantly improving scalability and reducing process complexity.
Solution Approach 2:
The invention extracts and eliminates the unnecessary solvent and counterion exchange steps from the conventional synthesis pathway. By designing the reaction to proceed directly from functionalized polar block and non-polar block anion to final block copolymer, the process removes extraneous steps that hinder scalability while preserving the ability to control block copolymer structure through precise living polymerization.
3Productivity
If conventional block copolymer synthesis is used, then the process lacks efficiency, but the ability to control ion-conducting properties is improved
Solution Approach 1:
The invention changes the chemical parameters of the polar block by introducing epoxy functionalization. This parameter change enables direct coupling with the non-polar block anion while maintaining precise control over the polar block's length and structure. The epoxy group serves as a reactive handle that preserves the polar block's ion-conducting properties while enabling efficient synthesis through the coupling reaction, thus improving both productivity and reliability of ion conductivity control.
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
The process enables the production of block copolymers with reproducible and uniform chain lengths, facilitating self-assembled structures for improved lithium ion conduction and mechanical stability, suitable for polymer electrolytes in batteries, with scalable and efficient synthesis.
Implementation Method 1
the non-polar block is built up from specific monomers via a living sequential anionic polymerization by means of a Li-organyl initiator
Implementation Method 2
via an epoxy functionalization of one of the monomers of the polar block, obtained via a reaction of this monomer with epichlorohydrin
Implementation Method 3
the polar polymer block is covalently linked to the non-polar block anion in a single step in a non-polar solvent in the presence of free Li ions
Implementation Method 4
Through interaction of the polymer segments of the individual block polymers, they undergo self-assembly and an ordered network of ion-conducting domains is formed
Data Source
AI summary
The present invention relates to a process for the sequential and convergent preparation of ordered block copolymers comprising at least one non-polar and one polar polymer block, wherein the non-polar block is built up from specific monomers via a living sequential anionic polymerization by means of a Li-organyl initiator having a pKa greater than or equal to 45 and the polar block is a polymer block having a molecular weight greater than or equal to 350 g/mol and less than or equal to 5000 g/mol and being built up from monomers selected from the group consisting of C2-C10 oxacyclo compounds, their derivatives or mixtures of at least two different monomers thereof, wherein the polar polymer block is covalently linked to the non-polar block anion in a single step via an epoxy functionalization of one of the monomers of the polar block, obtained via a reaction of this monomer with epichlorohydrin, in a non-polar solvent in the presence of free Li ions. Furthermore, the present invention relates to specific block copolymers having short polar chains of very uniform chain length, polymer electrolytes, and the use of the block copolymers as polymer electrolytes in secondary alkaline batteries.