Aqueous Polyurethane Dispersion Particle Size Control

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Solution Overview

Problem

Existing processes for preparing aqueous polyurethane dispersions struggle to achieve a balance between small average particle size and high density of COOH and salt groups, which is crucial for effective coating applications.

Innovation Solution

A process involving the reaction of at least one first polyisocyanate with a polyol carrying COOH groups, followed by treatment with another polyol and optionally additional polyisocyanates, to control the reaction index and achieve a composition with a high density of COOH and salt groups, resulting in a polyurethane/poly(meth)acrylate hybrid polymer.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Manufacturing precision

If conventional processes are used to prepare aqueous polyurethane dispersions, then the production is relatively simple, but the particle size is large and the density of COOH and salt groups is low

Engineering Contradiction:
Improveparticle size controlVSAvoidprocess complexity
Core Design Contradiction:
Manufacturing precisionVSDevice complexity

Solution Approach 1:

The patent divides the polyurethane synthesis into multiple sequential stages: Stage 1 forms a prepolymer with controlled NCO content, Stage 2 adds polyol to control molecular weight and particle formation, and Stage 3 optionally adds more polyisocyanate to adjust COOH group density. This staged approach allows precise control of particle size and functional group distribution that cannot be achieved in conventional single-step processes.

Inventive Principle:
Principle #1Segmentation

Solution Approach 2:

The patent performs preliminary formation of NCO-functional prepolymer in Stage 1 before adding polyol in Stage 2. This preliminary action establishes the core structure and functional group distribution early in the process, enabling better control over final particle characteristics and COOH group density.

Inventive Principle:
Principle #10Preliminary action

2Quantity of substance

If the reaction is allowed to proceed to high conversion, then the COOH group density increases, but the particle size also increases

Engineering Contradiction:
ImproveCOOH group densityVSAvoidparticle size
Core Design Contradiction:
Quantity of substanceVSVolume of moving object

Solution Approach 1:

The patent uses periodic addition of reagents across three stages: Stage 1 forms prepolymer, Stage 2 adds polyol to control particle growth, and Stage 3 optionally adds more polyisocyanate. This periodic action allows the system to achieve high COOH group density through controlled, incremental reactions rather than continuous high-conversion processing, thereby limiting particle size increase.

Inventive Principle:
Principle #19Periodic action

Solution Approach 2:

The patent changes key reaction parameters at each stage: Stage 1 uses specific NCO:OH ratios to form prepolymer, Stage 2 adjusts polyol addition rate and NCO content to control particle growth, and Stage 3 modifies polyisocyanate addition to tune COOH density. These parameter changes enable decoupling of COOH group density from particle size, achieving high density with small particles.

Inventive Principle:
Principle #35Parameter changes

3Volume of moving object

If polyol is added to terminate the reaction early, then particle size is reduced, but the density of COOH and salt groups decreases

Engineering Contradiction:
Improveparticle sizeVSAvoidCOOH group density
Core Design Contradiction:
Volume of moving objectVSQuantity of substance

Solution Approach 1:

The patent maintains continuous useful action by adding polyisocyanate in Stage 3 after polyol termination in Stage 2. This additional stage continues the build-up of COOH groups without significant particle growth, as the system is already terminated. This ensures high COOH group density is achieved while maintaining small particle size from the earlier termination.

Inventive Principle:
Principle #20Continuity of useful 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

The process yields aqueous compositions with small average particle sizes and high COOH and salt group densities, enhancing coating performance and stability, including storage stability and resistance to electrolytes.

Implementation Method 1

reacting at least one first polyisocyanate (A1) with at least one polyol carrying at least one COOH group (BX)

Methodology Applied
Scientific EffectChemical reaction (urethane formation): Chemical Bonding

Data Source

PatentUS20240191018A1Aqueous polyurethane and polyurethane/poly(METH)acrylate hybrid dispersions
Publication Date: 2024.06.13 BASF SE

AI summary

The present invention relates a process of the present invention for the preparation of an aqueous composition comprising a polyurethane carrying COOH groups and/or salt groups thereof, comprises the steps of (i) reacting at least one first polyisocyanate (A1) with at least one polyol carrying at least one COOH group (BX) and optionally at least one first polyol carrying no COOH group (B1) to form a first composition (C1), (ii) treating the first composition (C1) obtained in step (i) with at least one second polyol carrying no COOH group (B2), and optionally with at least one second polyisocyanate (A2), to form a second composition (C2), and (iii) optionally treating the second composition (C2) obtained in step (ii) with at least one third-polyisocyanate (A3), to form a third composition (C3), wherein step (i) is stopped at a reaction index in the range of 0.05 to 0.94, wherein reaction index=reaction rate×[mol initial NCO groups of all A1/(mol initial OH groups of all BX and, if present, mol initial OH groups of all B1)] (formula 1) wherein reaction rate=1 minus (mol NCO groups of C1/mol initial NCO groups of all A1), and to an aqueous composition comprising a polyurethane carrying COOH groups and/or salt groups thereof obtainableby this process, to a process for the preparation of an aqueous composition comprising a polyurethane/poly(meth)acrylate hybrid polymer using the aqueous composition comprising a polyurethane carrying COOH groups and/or salt groups thereof of the present invention, to aqueous compositions comprising a polyurethane/poly(meth)acrylate hybrid polymer obtainable by the this process, to coating compositions comprising the aqueous composition comprising a polyurethane carrying COOH groups and/or salt groups thereof or the aqueous compositions comprising a polyurethane/poly(meth)acrylate hybrid polymer, and to substrates coated with these coating compositions.