ROMP 3D Inkjet Printing via Segmented Catalyst System

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Solution Overview

Problem

Current 3D inkjet printing technologies face limitations in using Ring-Opening Metathesis Polymerization (ROMP) formulations due to rapid curing at ambient conditions, which restricts their application in 3D inkjet processes requiring specific viscosity ranges for inkjet printing heads.

Innovation Solution

The method involves employing a catalyst system with a pre-catalyst and an activator for ROMP, where at least one formulation contains a Ruthenium-based pre-catalyst and another contains the activator, allowing for controlled polymerization and maintaining suitable viscosity for inkjet printing, using bidentate Schiff base ligands and specific activators like trichlorododecyl silane.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Strength

If ROMP formulations are used in 3D inkjet printing, then high thermal resistance and toughness are achieved, but rapid curing at ambient conditions causes premature polymerization during jetting

Engineering Contradiction:
ImprovetoughnessVSAvoidpremature polymerization
Core Design Contradiction:
StrengthVSReliability

Solution Approach 1:

The catalyst system is segmented into two separate formulations: one containing the pre-catalyst and another containing the activator. These formulations are jetted separately and only mix after deposition on the substrate, preventing premature polymerization during the jetting process while enabling ROMP curing to achieve high toughness in the final object

Inventive Principle:
Principle #1Segmentation

Solution Approach 2:

A dormant pre-catalyst species acts as an intermediary that requires activation by a separate activator component to initiate polymerization. This intermediary state allows the formulation to remain stable during jetting and storage, then activate rapidly after deposition to achieve the desired curing and mechanical properties

Inventive Principle:
Principle #24Intermediary (Mediator)

2Temperature

If ROMP formulations are used in 3D inkjet printing, then high thermal resistance is achieved, but viscosity becomes unsuitable for inkjet printing heads due to rapid curing

Engineering Contradiction:
Improvethermal resistanceVSAvoidviscosity control
Core Design Contradiction:
TemperatureVSEase of manufacture

Solution Approach 1:

The catalyst system is divided into separate pre-catalyst and activator formulations, each maintaining suitable viscosity for inkjet printing individually. This segmentation allows both formulations to be jetted through standard print heads without clogging, then mixed and cured on the substrate to achieve high thermal resistance

Inventive Principle:
Principle #1Segmentation

Solution Approach 2:

The viscosity parameters of the formulations are optimized by controlling the concentration and state of the pre-catalyst and activator components. By maintaining the pre-catalyst in a dormant state and separating it from the activator, the formulations achieve viscosity ranges suitable for inkjet printing while retaining the ability to cure and provide high thermal resistance

Inventive Principle:
Principle #35Parameter changes

3Productivity

If catalyst is added to ROMP monomer before jetting, then polymerization is initiated, but viscosity increases and causes clogging of inkjet printing heads

Engineering Contradiction:
Improvepolymerization initiationVSAvoidviscosity
Core Design Contradiction:
ProductivityVSEase of manufacture

Solution Approach 1:

The catalyst system is segmented into dormant pre-catalyst and activator components that are jetted separately. This prevents the polymerization reaction from occurring during the jetting process, maintaining low viscosity and preventing head clogging, while enabling rapid polymerization initiation after the formulations mix on the substrate

Inventive Principle:
Principle #1Segmentation

Solution Approach 2:

The pre-catalyst is prepared in a dormant, inactive state before jetting, allowing it to be stored and jetted without initiating polymerization. The activation step is performed preliminarily planned but delayed until after deposition, ensuring viscosity remains suitable for printing while polymerization is ready to initiate rapidly when 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

This approach enables the use of ROMP-based materials in 3D inkjet printing, achieving high thermal resistance, toughness, and chemical resistance while preventing premature polymerization during jetting, thus overcoming the viscosity and reactivity challenges.

Implementation Method 1

employing a catalyst system with a pre-catalyst and an activator for ROMP, where at least one formulation contains a Ruthenium-based pre-catalyst and another contains the activator, allowing for controlled polymerization

Methodology Applied
Scientific EffectRing-opening metathesis polymerization (ROMP): Chemical Bonding

Data Source

PatentEP3448661B1Three-dimensional inkjet printing using ring-opening metathesis polymerization
Publication Date: 2024.03.27 STRATASYS LTD
  • EP3448661B1 patent drawingFigure 1
  • EP3448661B1 patent drawingFigure 2
  • EP3448661B1 patent drawingFigure 3A~4

AI summary

Methods for fabricating three-dimensional objects by 3D-inkjet printing technology are provided. The methods utilize curable materials that polymerize via ring- opening metathesis polymerization (ROMP) for fabricating the object, in combination with acid-activatable pre-catalyst and an acid generator activator. Kits containing modeling material formulations usable in the methods are also provided.