Phosphonamidate Flame Retardants for Polyurethane Foam

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Solution Overview

Problem

There is a need for novel flame retardants that can replace halogenated compounds, which are environmentally harmful, and exhibit superior flame retardant properties for polymers, particularly amino derivatives of DOPO that have not been well studied or characterized for their flame retardant efficacy.

Innovation Solution

Development of phosphonamidate compounds such as PB-DOPO, TESPA-DOPO, TMSPA-DOPO, EAB-DOPO, DEA-DDOPO, DEA-TDOPO, EDAB-DOPO, and TDETA-DOPO, which are synthesized using specific reaction procedures and demonstrated to possess flame retardant properties with improved thermal stability, suitable for use in polymeric materials.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If halogenated organic compounds are used as flame retardants, then flame retardant efficiency is improved, but environmental benignity deteriorates

Engineering Contradiction:
Improveflame retardant efficiencyVSAvoidenvironmental harm
Core Design Contradiction:
ReliabilityVSObject-affected harmful factors

Solution Approach 1:

The invention changes the chemical composition parameters by replacing halogen atoms with phosphorus-containing amino derivatives (DOPO structures). This substitution maintains the flame retardant mechanism (radical scavenging) while eliminating the environmental harm associated with halogenated compounds. The phosphonamidate compounds achieve comparable or superior flame retardant efficiency without the toxic byproducts of halogenated systems.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent employs readily available starting materials (DOPO, amino compounds, phosphorus reagents) that can be easily synthesized and replaced. The flame retardant compounds are designed to decompose during combustion to release active species, after which they are consumed - functioning as disposable protective agents that sacrifice themselves to protect the polymer matrix.

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

2Object-affected harmful factors

If novel phosphonamidate compounds are developed to replace halogenated flame retardants, then environmental benignity is improved, but flame retardant performance may deteriorate

Engineering Contradiction:
Improveenvironmental harmVSAvoidflame retardant performance
Core Design Contradiction:
Object-affected harmful factorsVSReliability

Solution Approach 1:

The invention creates composite molecular structures combining DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) core with various amino derivatives and phosphonamidate groups. This composite approach leverages the synergistic effects of different functional groups: the DOPO provides thermal stability and char formation, while the amino and phosphonamidate groups enhance radical scavenging activity. The resulting compounds achieve both environmental benignity and superior flame retardant performance.

Inventive Principle:
Principle #40Composite materials

Solution Approach 2:

The phosphonamidate compounds are designed to perform multiple functions simultaneously: (1) form protective char layers during combustion, (2) scavenge H* and OH* radicals in the gas phase, (3) maintain thermal stability at processing temperatures, and (4) provide long-term durability in polymer matrices. This multi-functionality ensures that environmental benefits are not achieved at the expense of flame retardant effectiveness.

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

3Object-affected harmful factors

If phosphonamidate compounds are used for flame retardancy, then environmental safety is improved, but thermal stability for thermoplastic processing may be insufficient

Engineering Contradiction:
Improveenvironmental safetyVSAvoidthermal stability
Core Design Contradiction:
Object-affected harmful factorsVSTemperature

Solution Approach 1:

The invention systematically varies the substituent parameters on the DOPO core (different amino groups, alkyl chains, aryl groups) to optimize the decomposition temperature and thermal stability. By adjusting these molecular parameters, the compounds are tailored to remain stable at typical thermoplastic processing temperatures (200-300°C) while decomposing at appropriate service temperatures to release flame-retardant active species.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The phosphonamidate compounds are pre-designed with built-in thermal stability features (rigid DOPO core, stable phosphonamidate linkages) that allow them to withstand thermoplastic processing without premature decomposition. This preliminary stabilization ensures the compounds survive manufacturing processes and only activate under fire conditions when flame retardancy is needed.

Inventive Principle:
Principle #10Preliminary action

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

These phosphonamidate compounds effectively enhance the flame resistance of polymeric materials, offering improved thermal stability and flame retardant performance, potentially replacing halogen-based systems and meeting the requirements for thermoplastic processing temperatures.

Implementation Method 1

During combustion they decompose and release low molecular weight phosphorus-containing fragments that are able to scavenge H*- and OH*-radicals

Methodology Applied
Scientific EffectDecomposition: Decomposition (biological)

Implementation Method 2

These halogen radicals act as a scavenger to trap reactive H*- and OH*-radicals so that there is no heat flow to sustain the flame

Methodology Applied
Scientific EffectRadical scavenging: Oxidation

Data Source

PatentEP2557085B1Novel phosphonamidates - synthesis and flame retardant applications
Publication Date: 2014.10.22 FRITZ NAUER AG
  • EP2557085B1 patent drawingFigure 1~2
  • EP2557085B1 patent drawingFigure 3~4
  • EP2557085B1 patent drawingFigure 5~6

AI summary

The invention relates to a group of novel compounds containing one or more amino substituted DOPO (9,10-dihydro-9-oxa-phosphaphenthren-10-oxide) moieties. The compounds were found to have good flame retardant properties and also good thermal stability, which makes them particularly suitable as flame retardant additives for various thermoplastic polymers. In particular, they can be incorporated in a flexible polyurethane foam.