Semi-crystalline Thiourethane Polymers for Additive Manufacturing

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Solution Overview

Problem

Industrial additive manufacturing technologies using polymers face limitations due to low toughness, narrow thermal operating range, and poor mechanical isotropy in 3D printed parts, particularly with resins like polyacrylate polymers which often result in brittle or soft materials with poor interlayer adhesion.

Innovation Solution

Development of semi-crystalline thiourethane polymers synthesized through anionic step-growth polymerization using monomers with thiol and isocyanate functional groups, catalyzed by a non-nucleophilic base generated from a photolatent base, to create impact-resistant materials suitable for 3D printing.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Productivity

If acrylate monomers are used for stereolithography, then rapid reaction and short printing times are achieved, but the end product is brittle or soft with low toughness

Engineering Contradiction:
Improveprinting timeVSAvoidtoughness
Core Design Contradiction:
ProductivityVSStrength

Solution Approach 1:

The patent changes the chemical parameters of the resin system by using thiol-isocyanate chemistry instead of traditional acrylate photopolymerization. This fundamental chemical parameter change enables the formation of semi-crystalline thiourethane polymers with superior toughness while maintaining rapid curing through photolatent base catalysis

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The invention creates a composite polymer structure combining crystalline and amorphous phases within the thiourethane polymer. The semi-crystalline morphology provides both the toughness needed to overcome brittleness and the rapid curing characteristics required for productive printing

Inventive Principle:
Principle #40Composite materials

2Strength

If hybrid resins using acrylates and epoxides are used, then tougher end-polymers with rapid curing are produced, but viscosity increases leading to longer printing time and higher cost

Engineering Contradiction:
ImprovetoughnessVSAvoidprinting time
Core Design Contradiction:
StrengthVSProductivity

Solution Approach 1:

The patent changes the chemical composition parameters by eliminating high-viscosity epoxides and using thiol-isocyanate monomers instead. This parameter change maintains toughness through semi-crystalline structure formation while reducing viscosity to enable rapid printing

Inventive Principle:
Principle #35Parameter changes

3Ease of manufacture

If 3D printed parts are produced using conventional resins, then manufacturing is achieved, but poor interlayer adhesion results in poor mechanical performance perpendicular to printed layers

Engineering Contradiction:
Improvemanufacturing capabilityVSAvoidinterlayer adhesion
Core Design Contradiction:
Ease of manufactureVSStrength

Solution Approach 1:

The patent changes the material parameters by using semi-crystalline thiourethane polymers that exhibit improved layer bonding characteristics. The unique polymer structure enables better interlayer adhesion while maintaining ease of manufacture through additive manufacturing processes

Inventive Principle:
Principle #35Parameter changes

4Ease of manufacture

If amorphous structure polymers are used, then manufacturing is achieved, but performance is restricted compared to semi-crystalline engineering plastics

Engineering Contradiction:
Improvemanufacturing capabilityVSAvoidperformance
Core Design Contradiction:
Ease of manufactureVSReliability

Solution Approach 1:

The patent fundamentally changes the structural parameter by designing monomers that self-assemble into semi-crystalline structures during polymerization. This parameter change delivers engineering plastic-level performance while maintaining additive manufacturing ease through the photopolymerization process

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The invention creates a composite microstructure with both crystalline and amorphous phases. The crystalline regions provide the enhanced performance and thermal stability of engineering plastics, while the amorphous regions maintain processability and ease of manufacture

Inventive Principle:
Principle #40Composite materials

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 semi-crystalline thiourethane polymers exhibit enhanced toughness and mechanical properties, enabling the production of robust 3D printed parts with improved interlayer adhesion and thermal stability, suitable for various applications including bio-implantable materials and protective coatings.

Implementation Method 1

photo-initiated decomposition of a photolatent base

Methodology Applied
Scientific EffectPhoto-initiated decomposition: Photodissociation

Implementation Method 2

anionic step-growth polymerization reaction that is catalyzed by a non-nucleophillic base

Methodology Applied
Scientific EffectAnionic step-growth polymerization: Chemical Bonding

Implementation Method 3

semi-crystalline forms of such polymers

Methodology Applied
Scientific EffectCrystallization: Crystallisation

Data Source

PatentEP3414273B1Thiourethane polymers, method of synthesis thereof and use in additive manufacturing technologies
Publication Date: 2020.12.23 ADAPTIVE 3D TECHNOLOGIES LLC
  • EP3414273B1 patent drawingFigure 1
  • EP3414273B1 patent drawingFigure 2A
  • EP3414273B1 patent drawingFigure 2B

AI summary

A semi-crystalline thiourethane polymer. The semi-crystalline thiourethane polymer comprises a sequential chain of a first type of monomer covalently bonded to a second type of monomer via thiourethane linkages. Each of the first type of monomer includes two or more thiol functional groups and each of the second type of monomer includes two or more isocyanate functional groups. The first and second types of monomers are polymerized together in an anionic step-growth polymerization reaction that is catalyzed by a non-nucleophillic base having a pKa greater than 7, produced by photo-initiated decomposition of a photolatent base. A method of synthesizing, and polymer jetting and stereolithography methods of manufacturing a polymer part, are also disclosed.