Non-solvated Bisphosphite Crystals for Industrial Catalysis

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Solution Overview

Problem

Existing methods for producing 6,6'-[[3,3',5,5'-tetrakis(1,1-dimethylethyl)-[1,1'-biphenyl]-2,2'-diyl]bis(oxy)]bis-dibenzo [d,f] [1,3,2]-dioxaphosphepine result in sticky products that tend to cake or form dust, making them unsuitable for industrial-scale use as ligands in homogeneous catalysis due to the presence of solvates like acetonitrile, which interfere with catalysis.

Innovation Solution

Development of crystalline non-solvated and solvated forms of the compound, specifically toluene-monosolvate, non-solvated, acetone-solvate 'A', acetone-solvate 'B', and acetone-solvate 'C', which are characterized by specific X-ray powder diffraction patterns and prepared through controlled crystallization processes, eliminating the issues of tackiness and dust formation.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If conventional production methods are used to prepare the bisphosphite compound, then the compound can be obtained, but the product is sticky and forms dust due to solvate formation

Engineering Contradiction:
Improvesuitability for industrial useVSAvoidtackiness and dust formation
Core Design Contradiction:
ReliabilityVSObject-generated harmful factors

Solution Approach 1:

The invention changes the physical and chemical parameters of the compound by controlling the crystallization process to obtain specific crystalline modifications (Forms I-VI) with defined X-ray diffraction patterns. This parameter change transforms the compound from a sticky, dust-forming substance into a free-flowing powder with improved handling properties

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The invention utilizes phase transitions during controlled crystallization from different solvents (acetonitrile, toluene, acetone, ethyl acetate) to produce distinct crystalline forms. The phase transition from solution to crystal lattice eliminates solvate formation and produces the desired non-sticky, low-dust product

Inventive Principle:
Principle #36Phase transitions

2Ease of manufacture

If acetonitrile solvate is formed during crystallization, then the compound crystallizes easily, but the solvate interferes with catalytic activity

Engineering Contradiction:
Improvecrystallization easeVSAvoidcatalytic activity
Core Design Contradiction:
Ease of manufactureVSReliability

Solution Approach 1:

The invention extracts the harmful acetonitrile solvent from the crystal lattice by controlling crystallization conditions to favor non-solvate forms or solvates with solvents that do not interfere with catalysis (such as toluene or acetone). This removal of the interfering solvent component preserves catalytic activity while maintaining crystalline structure

Inventive Principle:
Principle #2Taking out (Extraction)

Solution Approach 2:

The invention uses alternative solvents (toluene, acetone, ethyl acetate) as intermediaries during crystallization that do not coordinate with transition metals. These mediator solvents allow easy crystallization while not interfering with the subsequent catalytic function, replacing the harmful acetonitrile role

Inventive Principle:
Principle #24Intermediary (Mediator)

3Productivity

If the compound is produced without controlled crystallization, then the production process is simple, but the product has poor flowability and high dust formation

Engineering Contradiction:
Improveproduction simplicityVSAvoidflowability and dust control
Core Design Contradiction:
ProductivityVSEase of operation

Solution Approach 1:

The invention introduces controlled crystallization parameters (temperature, solvent type, cooling rate) to transform the product from an amorphous or poorly crystalline sticky substance into well-defined crystalline forms. This parameter control improves flowability and reduces dust without significantly complicating the production process

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

The new crystalline forms exhibit low tackiness, reduced dust formation, high bulk density, and high purity, enabling their use as effective ligands in industrial processes without interfering with catalytic activity, and are suitable for transition metal catalysts in hydroformylation, hydrocyanation, or hydrogenation.

Implementation Method 1

6,6'-[[3,3',5,5'-Tetrakis(1,1-dimethylethyl)-[1,1'-biphenyl]-2,2'-diyl]bis(oxy)]bis-dibenzo [d,f] [1,3,2]-dioxaphosphepine is allowed to crystallized at a temperature of above 65°C

Methodology Applied
Scientific EffectCrystallization: Crystallisation

Implementation Method 2

the suspended material is agitated in the suspension at a temperature above the boiling point of toluene at ambient pressure

Methodology Applied
Scientific EffectSolvation: Solvation

Data Source

PatentEP2797937B1Non-solvated crystalline form of 6,6'-[[3,3',5,5'-tetrakis(1,1-dimethylethyl)-[1,1'-biphenyl]-2,2'-diyl]bis(OXY)]bis-dibenzo [d,f][1,3,2]-dioxaphosphepine
Publication Date: 2022.08.31 BASF SE
  • EP2797937B1 patent drawingFigure 1
  • EP2797937B1 patent drawingFigure 2
  • EP2797937B1 patent drawingFigure 3

AI summary

The present invention relates to a crystalline non-solvated form of 6,6'-[[3,3',5,5'-tetrakis(1,1-dimethylethyl)-[1,1'-biphenyl]-2,2'-diyl]bis(oxy)]bis-dibenzo [d,f] [1,3,2]-dioxaphosphepine (compound I) and toluene-solvates and acetone-solvates thereof.