Ionic Oligomer for Water-Removable 3D Printing Supports

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Solution Overview

Problem

Existing 3D printing technologies lack a suitable crosslinkable composition for temporary support materials that can be easily removed with water or a basic aqueous solution, offering both mechanical strength and the ability to form hydrogels for active ingredient delivery, while maintaining dimensional stability and low shrinkage.

Innovation Solution

A crosslinkable oligomer with ammonium carboxylate ionic bonds, comprising aminoacrylate groups and a carboxylic acid compound, which forms a polymerizable and crosslinkable binder suitable for temporary-use materials, enabling water-fragmentable and water-soluble properties for easy removal.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Strength

If a crosslinkable composition is used as temporary support material in 3D printing, then mechanical strength and dimensional stability are improved, but removal difficulty increases

Engineering Contradiction:
Improvemechanical strengthVSAvoidremoval ease
Core Design Contradiction:
StrengthVSEase of operation

Solution Approach 1:

The patent applies parameter changes by modifying the chemical structure of the oligomer to include ammonium carboxylate ionic bonds, which are sensitive to pH and ionic strength changes. This allows the material to maintain strong crosslinked structure during use, then rapidly dissolve when exposed to basic aqueous solutions (pH>7) or saline solutions, achieving easy removal without mechanical force

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent implements dynamics by creating a material with dynamically reversible ionic bonds. The ammonium carboxylate bonds remain stable under neutral conditions providing mechanical strength, but can be dynamically broken by changing the environmental conditions (pH, ionic strength), enabling the support material to transition from a stable structural role to a removable byproduct

Inventive Principle:
Principle #15Dynamics

2Ease of operation

If water-soluble materials are used for temporary support, then removal ease is improved, but mechanical strength deteriorates

Engineering Contradiction:
Improveremoval easeVSAvoidmechanical strength
Core Design Contradiction:
Ease of operationVSStrength

Solution Approach 1:

The patent applies composite materials by combining hydrophilic oligomer chains with ammonium carboxylate ionic crosslinks. The hydrophilic nature ensures water solubility and easy removal, while the ionic crosslinks provide the necessary mechanical strength and dimensional stability during the support function, creating a material that exhibits both properties simultaneously

Inventive Principle:
Principle #40Composite materials

3Ease of manufacture

If conventional solvents are used in crosslinkable compositions, then processing performance is improved, but environmental and health safety deteriorates

Engineering Contradiction:
Improveprocessing performanceVSAvoidoperator health and environmental safety
Core Design Contradiction:
Ease of manufactureVSObject-affected harmful factors

Solution Approach 1:

The patent replaces conventional organic solvent-based processing with a water-based system. The oligomer composition uses water or basic aqueous solutions as the processing medium instead of volatile organic solvents, eliminating health and environmental hazards while maintaining the ability to achieve proper viscosity, curing, and removal functions through the ionic bond mechanism

Inventive Principle:
Principle #28Mechanics substitution (Replace mechanical system)

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 oligomer provides a temporary support material with sufficient mechanical strength, low shrinkage, and dimensional stability, allowing for easy removal in water or a saline solution, suitable for 3D printing and hydrogel applications, while avoiding the use of harmful solvents and ensuring operator and environmental safety.

Implementation Method 1

bearing at least one crosslinkable ethylenic unsaturation and at least one ionic bond in ammonium carboxylate form

Methodology Applied
Scientific EffectIonic bonding: Chemical Bonding

Implementation Method 2

water-fragmentable or water-soluble, thus enabling them to be completely removed with water or in an aqueous medium

Methodology Applied
Scientific EffectWater solubility: Solvation

Implementation Method 3

crosslinkable under radiation, in particular UV radiation, layer by layer

Methodology Applied
Scientific EffectPhotopolymerization: Photopolymerisation

Implementation Method 4

crosslinked from said oligomers according to the invention, with crosslinked products which are water-fragmentable or water-soluble

Methodology Applied
Scientific EffectCrosslinking: Chemical Bonding

Data Source

PatentUS11021619B2Ionic oligomer and polymerizable composition containing same for temporary-use water-fragmentable materials
Publication Date: 2021.06.01 ARKEMA FRANCE SA

AI summary

An oligomer bearing at least one crosslinkable ethylenic unsaturation and at least one ionic bond comprises in its structure at least one aminoacrylate group and at least one tertiary amine in a form salified with at least one carboxylic acid. Also described are a process for preparing a solution of the oligomer in a reactive diluent, a crosslinkable composition comprising the oligomer, the use thereof as binder in crosslinkable compositions for temporary-use water-removable materials in coatings, hydrogels and 3D object printing, and the crosslinked material which results from polymerizing the oligomer. As a temporary-use material, the cured oligomer can be easily removed after a temporary function, by simple cleaning with water and optionally at a suitable temperature greater than the glass transition temperature of the crosslinked product.