High-Molecular Polysilane Synthesis via Ether Solvent

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Solution Overview

Problem

Current methods for producing silicon carbide fibers from polysilane result in low yield, low molecular weight polysilane, and high porosity due to excess carbon, which affects mechanical stability and processing efficiency, requiring additional costly steps like sintering additives or annealing.

Innovation Solution

A method involving the reaction of silane monomers with an alkali metal in an ether-containing solvent, specifically dioxane, to produce high molecular weight polysilane with a stoichiometric silicon to carbon ratio, eliminating the need for additional processing steps and reducing free carbon content.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Quantity of substance

If conventional Wurtz coupling is used to produce polysilane, then the polysilane can be obtained, but the molecular weight is low and the yield is low

Engineering Contradiction:
Improvepolysilane yieldVSAvoidmolecular weight
Core Design Contradiction:
Quantity of substanceVSLength of moving object

Solution Approach 1:

The patent changes the reaction parameters by using a different solvent system (ether-containing solvent with at least two oxygen atoms) and adding a reaction initiator to the Wurtz coupling process. These parameter changes enable the production of polysilane with both high molecular weight (Mn ≥ 5000 Da) and high yield (≥ 80%), resolving the contradiction between yield and molecular weight that plagues conventional methods.

Inventive Principle:
Principle #35Parameter changes

2Ease of manufacture

If polysilane with high carbon content is used, then the polysilane can be produced, but the resulting silicon carbide fibers have high porosity and reduced mechanical stability

Engineering Contradiction:
Improvepolysilane productionVSAvoidmechanical stability
Core Design Contradiction:
Ease of manufactureVSReliability

Solution Approach 1:

The patent modifies the chemical composition parameters of the polysilane by controlling the ratio of silane monomers and using specific ether solvents that influence the polymerization process. This results in polysilane with a near-stoichiometric silicon-to-carbon ratio, which eliminates excess carbon and produces silicon carbide fibers with low porosity and high mechanical stability after pyrolysis.

Inventive Principle:
Principle #35Parameter changes

3Object-generated harmful factors

If additional processing steps like sintering additives or annealing are used, then free carbon content can be reduced, but the process complexity and cost increase

Engineering Contradiction:
Improvefree carbon contentVSAvoidprocessing steps
Core Design Contradiction:
Object-generated harmful factorsVSDevice complexity

Solution Approach 1:

The patent performs the carbon control action in advance during the polysilane synthesis stage itself, rather than requiring subsequent treatment steps. By using ether-containing solvents and reaction initiators in the Wurtz coupling, the polysilane is produced with the correct silicon-to-carbon ratio from the beginning, eliminating the need for later sintering additive additions or annealing processes to remove excess carbon.

Inventive Principle:
Principle #10Preliminary action

4Productivity

If polysilane with low molecular weight is used, then the polysilane can be produced, but the processability for melt spinning is poor

Engineering Contradiction:
Improvepolysilane productionVSAvoidprocessability
Core Design Contradiction:
ProductivityVSEase of operation

Solution Approach 1:

The patent changes the physical parameters of the polysilane by controlling the molecular weight through the use of ether-containing solvents and reaction initiators. The resulting high molecular weight (Mn ≥ 5000 Da) provides the necessary viscosity and melt strength for effective melt spinning and fiber formation, while maintaining high production yield through the optimized reaction conditions.

Inventive Principle:
Principle #35Parameter changes

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 increases polysilane yield and molecular weight, enhances processability, and results in silicon carbide fibers with low porosity and excellent mechanical stability, simplifying the production process and reducing costs.

Implementation Method 1

The polysilane is produced via a Wurtz coupling, in which an organohalogenated silane, such as dichlorodimethylsilane, is reacted with molten sodium to form a polydimethylsilane.

Methodology Applied
Scientific EffectWurtz coupling: Chemical Bonding

Implementation Method 2

the reaction step takes place in an ether-containing solvent, wherein the ether has at least two oxygen atoms

Methodology Applied
Scientific EffectSolvation: Solvation

Implementation Method 3

The fibers are then hardened and pyrolyzed to form ceramic silicon carbide fibers

Methodology Applied
Scientific EffectPyrolysis: Pyrolysis

Data Source

PatentEP2945977B1High-molecular polysilane and method for the production thereof for producing pre-cermanic molded bodies
Publication Date: 2020.04.01 BJS CERAMICS
  • EP2945977B1 patent drawingFigure 1
  • EP2945977B1 patent drawingFigure 2
  • EP2945977B1 patent drawingFigure 3

AI summary

A method for producing a polysilane comprises the step of reacting (i) at least two silane monomers and (ii) at least one alkali metal, the silane monomers having the following structural units: - at least one aryl group, - at least one alkyl group, - at least one alkenyl group and - at least three halogen atoms, wherein at least three of the halogen atoms are bonded to a silicon atom of one of the silane monomers, characterized in that the reaction step takes place in an ether-containing solvent, particularly preferably dioxane. The obtained polysilane has a high molecular mass and, at 100°C, a viscosity of 1500 to 3000 Pa·s. The polysilane is very suitable for being processed to form silicon carbide fibers and fiber composites.