Linear Siloxanes via Lithium Organosilanolate Condensation

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Solution Overview

Problem

Current methods for producing linear polysiloxanes with organotrifunctional units are inefficient, complex, and result in undesirable by-products, particularly due to incompatibility with SiH compounds and limited industrial viability, leading to unsuitable properties for optical and electronic applications.

Innovation Solution

A process involving the reaction of lithium or sodium salts of organosilanols with halosilanes to produce linear siloxanes, which are highly reactive and suitable for crosslinking applications, using a specific molar ratio and conditions to achieve high selectivity and industrial feasibility.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Stability of the object's composition

If anionic or cationic ring-opening polymerization of monosilyl-substituted cyclotrisiloxanes is used to produce polysiloxanes with trifunctional units, then the polysiloxane backbone contains organotrifunctional siloxane units, but the method is complex to prepare and only every third siloxane unit is trifunctional

Engineering Contradiction:
Improvebackbone compositionVSAvoidpreparation complexity
Core Design Contradiction:
Stability of the object's compositionVSDevice complexity

Solution Approach 1:

The invention extracts the essential requirement (trifunctional siloxane units in backbone) from the complex ring-opening polymerization process and achieves it through a simpler direct condensation reaction of organosilanetriol with itself or with halosilanes, eliminating the need for cyclotrisiloxane intermediates and complex polymerization processes

Inventive Principle:
Principle #2Taking out (Extraction)

Solution Approach 2:

Instead of building up polysiloxane chains through ring-opening polymerization (adding units to a growing chain), the invention uses condensation of trifunctional siloxane units where three reactive groups per unit can form bonds in all directions, creating the backbone structure through a different mechanistic approach that directly yields the desired composition

Inventive Principle:
Principle #13The other way round (Inversion)

2Ease of manufacture

If anionic ring-opening polymerization is used to produce polysiloxanes with T units backbone, then the polysiloxanes are accessible, but the method is incompatible with SiH compounds and requires complex preparation of T ring

Engineering Contradiction:
Improveaccessibility of polysiloxanesVSAvoidcompatibility with SiH compounds
Core Design Contradiction:
Ease of manufactureVSAdaptability or versatility

Solution Approach 1:

The invention changes the reaction parameters by using condensation conditions (acid or base catalysis, controlled temperature, specific solvent systems) that are compatible with SiH compounds, replacing the anionic polymerization conditions that cause incompatibility. The use of controlled molar ratios and catalyst selection enables versatility with SiH-containing monomers

Inventive Principle:
Principle #35Parameter changes

3Productivity

If potassium salts of organosilanols are reacted with monochloroorganosilanes, then cyclic siloxane structures are formed, but linear siloxanes with desired properties are not produced

Engineering Contradiction:
Improvereaction efficiencyVSAvoidmolecular structure
Core Design Contradiction:
ProductivityVSShape

Solution Approach 1:

The invention applies local quality control by using organosilanetriol units with three reactive hydroxyl groups that can form linear chains through controlled condensation, rather than the symmetric potassium salt structure that favors cyclic formation. The local arrangement of three reactive groups per silicon atom directs the reaction toward linear topology

Inventive Principle:
Principle #3Local quality

Solution Approach 2:

The invention changes the cation parameter from potassium to lithium or sodium, which alters the reaction mechanism and product distribution. The use of lithium or sodium salts with specific molar ratios (1.5:1 metal to silicon) and controlled reaction conditions shifts the product from cyclic to linear structures with the desired molecular architecture

Inventive Principle:
Principle #35Parameter changes

4Temperature

If polysiloxanes with high molar mass are produced to meet viscosity requirements, then the 38% solution in toluene has at least 100 mPas viscosity, but the chain length is limited to at most 17 and pure TM polysiloxane may have limited applicability

Engineering Contradiction:
Improveviscosity at 25°CVSAvoidapplication range
Core Design Contradiction:
TemperatureVSAdaptability or versatility

Solution Approach 1:

The invention creates polysiloxane units with universal applicability by incorporating three reactive organotrifunctional units per backbone segment, enabling these polymers to serve multiple functions: as crosslinkers for optical and electronic applications, as starting materials for functional fluids including surface-active compounds, and as units for siloxane resins, extending beyond the limited application range of conventional polysiloxanes

Inventive Principle:
Principle #6Universality (Multi-functionality)

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 yields linear siloxanes with improved reactivity and properties, suitable for optical and electronic applications, as well as functional fluids and siloxane resins, overcoming the limitations of existing methods by providing high selectivity and accessibility to industrially viable products.

Implementation Method 1

The invention relates to a process for producing linear siloxanes of the general formula (1) by reacting lithium or sodium salts of organosilanols consisting of units of the general formula (2) of condensation products thereof

Methodology Applied
Scientific EffectCondensation reaction:

Data Source

PatentUS10934396B2Reactive siloxanes and process for the production thereof
Publication Date: 2021.03.02 WACKER CHEMIE AG

AI summary

Linear organopolysiloxanes of the structure M-(T-M)n-M are prepared by reaction of lithium and/or sodium silanolates with chlorosilanes. The products contain at least two groups selected from silicon-bonded hydrogen and aliphatically unsaturated groups.