Three-dimensional inkjet printing using ring-opening metathesis polymerization

Patent metadata

Field	Value
Publication number	US-11655386-B2
Application number	US-202117241169-A
Country	US
Kind code	B2
Filing date	Apr 27, 2021
Priority date	Feb 5, 2016
Publication date	May 23, 2023
Grant date	May 23, 2023

Abstract

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) in combination with toughening agents for fabricating the object. Systems suitable for performing these methods and kits containing modeling material formulations usable in the methods are also provided.

First claim

What is claimed is:

1. A method of fabricating a three-dimensional object, the method comprising sequentially forming a plurality of layers in a configured pattern corresponding to the shape of the object, thereby forming the object,
wherein said formation of each layer comprises:
dispensing by at least two inkjet printing head nozzle arrays at least two modeling material formulations, each nozzle array jetting one of said at least two modeling material formulations, wherein at least one of said at least two modeling material formulations comprises an unsaturated cyclic monomer polymerizable by ring opening metathesis polymerization (ROMP), at least one of said at least two modeling material formulations comprises a catalyst for initiating ROMP of said monomer, at least one of said at least two of said modeling material formulations comprises at least one material polymerizable or curable via a non-ROMP reaction, and at least one of said at least two modeling material formulations further comprises a toughening agent; and
exposing the dispensed at least two modeling material formulations to a condition for inducing initiation of ROMP of said unsaturated cyclic monomer polymerizable by ROMP by said catalyst for initiating ROMP of said monomer and to a condition for inducing polymerization or curing of said at least one material polymerizable or curable via a non-ROMP reaction, to thereby obtain a cured modeling material,
wherein said toughening agent is or comprises an elastomeric material characterized by at least one of:
a molecular weight lower than 30,000 Daltons;
being non-reactive towards ROMP;
being dissolvable or dispersible in said at least one modeling material formulation that comprises said toughening agent; and
being capable of forming a multiphase structure when blended with said cured modeling material.

2. The method of claim 1 , wherein said elastomeric material is hydrophobic.

3. The method of claim 1 , wherein said elastomeric material is a saturated polymeric material.

4. The method of claim 1 , wherein said catalyst does not initiate ROMP of said monomer prior to exposing to said condition and is activatable upon exposing to said condition.

5. The method of claim 4 , wherein at least one of said at least two modeling material formulations further comprises an activator for chemically activating said catalyst for initiating ROMP towards initiating ROMP of said monomer polymerizable by ROMP, wherein said activator is activatable upon exposure to said condition, such that exposing to said condition activates said activator, thereby activating said catalyst for initiating ROMP towards initiating ROMP of said monomer polymerizable by ROMP.

6. The method of claim 4 , wherein at least one of said at least two modeling material formulations further comprises an activator for chemically activating said catalyst for initiating ROMP towards initiating ROMP of said monomer polymerizable by ROMP, wherein one of said at least two modeling material formulations comprises said unsaturated cyclic monomer polymerizable by ROMP and said activator, and another one of said at least two modeling material formulations comprises said catalyst for initiating ROMP.

7. The method of claim 4 , wherein at least one of said at least two modeling material formulations further comprises an activator for chemically activating said catalyst for initiating ROMP towards initiating ROMP of said monomer polymerizable by ROMP, wherein one of said at least two modeling material formulations comprises said unsaturated cyclic monomer polymerizable by ROMP, and said catalyst for initiating ROMP, and another one of said at least two modeling material formulations comprises said activator.

8. The method of claim 1 , wherein said catalyst is active towards initiating ROMP of said unsaturated cyclic monomer polymerizable by ROMP prior to exposing to said condition, and wherein one of said at least two modeling material formulations comprises said unsaturated cyclic monomer polymerizable by ring opening metathesis polymerization and is devoid of said catalyst for initiating ROMP of said monomer polymerizable by ROMP and another one of said at least two modeling material formulations comprises said catalyst for initiating ROMP of said monomer polymerizable by ROMP.

9. The method of claim 1 , wherein said at least one material polymerizable or curable via a non-ROMP reaction comprises at least one material that is a monomer and/or an oligomer polymerizable by free-radical polymerization, cationic polymerization, anionic polymerization, or polycondensation.

10. The method of claim 1 , wherein said at least one material polymerizable or curable via a non-ROMP reaction and said unsaturated cyclic monomer polymerizable by said ROMP are included in the same modeling material formulation.

11. The method of claim 1 , wherein said at least one material polymerizable or curable by said non-ROMP reaction is comprised in at least one modeling material formulation of said at least two modeling material formulations which is devoid of said monomer polymerizable by said ROMP.

12. The method of claim 1 , wherein at least one of said at least two modeling material formulations further comprises an initiator of said non-ROMP reaction.

13. The method of claim 12 , wherein said initiator is comprised in at least one of said at least two modeling material formulations which is devoid of said at least one material polymerizable or curable via said non-ROMP reaction.

14. The method of claim 1 , wherein said condition for inducing ROMP of said unsaturated cyclic monomer polymerizable by ROMP and said condition for inducing polymerization or curing of said at least one material polymerizable or curable via a non-ROMP reaction are the same.

15. The method of claim 14 , wherein at least one of said at least two modeling material formulations comprises said monomer polymerizable by ROMP and said initiator of said non-ROMP reaction and at least one other modeling material formulation of said at least two modeling material formulations comprises said at least one material polymerizable or curable via a non-ROMP reaction and said catalyst for initiating said ROMP.

Assignees

• Stratasys Ltd

Inventors

• Vidavsky Yuval
• Kuno Lev

Classifications

• B33Y10/00

  Processes of additive manufacturing · CPC title

• B29C64/393

  for controlling or regulating additive manufacturing processes · CPC title

• B33Y70/00

  Materials specially adapted for additive manufacturing · CPC title

• C08G61/08

  of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring · CPC title

• C08G2261/418

  Ring opening metathesis polymerisation [ROMP] · CPC title