Thiourethane polymers, method of synthesis thereof and use in additive manufacturing technologies

Patent metadata

Field	Value
Publication number	US-10899072-B2
Application number	US-201715458220-A
Country	US
Kind code	B2
Filing date	Mar 14, 2017
Priority date	Mar 15, 2016
Publication date	Jan 26, 2021
Grant date	Jan 26, 2021

Abstract

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.

First claim

What is claimed is:

1. A polymer jetting method of manufacturing a polymer part, comprising:
exposing a deposited mixture to light to photo-initiate decomposition of a photolatent base in the mixture to form a non-nucleophillic base catalyst having a pKa greater than 7 to thereby initiate step-growth polymerization of a first type of monomer with a second type of monomer in the mixture to thereby form a semi-crystalline thiourethane polymer part, wherein the first type of monomer includes two or more thiol functional groups and the second type of monomer includes two or more isocyanate functional groups.

2. The method of claim 1 , further including:
adding the first type of monomer to a first container and adding the second type of monomer to a second container; and
depositing the first type of monomer from the first container on a substrate surface, and depositing the second type of monomer from the second container on the substrate surface to thereby form the deposited mixture.

3. The method of claim 1 , further including:
forming a mixture of a first type of monomer, a second type of monomer and a photolatent base in a container; and
depositing the mixture on a surface of the substrate to thereby form the deposited mixture.

4. The method of claim 1 , wherein the first type of monomer is free of -ene or isocyanate functional groups and the second type of monomer is free of -ene or thiol functional groups.

5. The method of claim 1 , wherein the semi-crystalline thiourethane polymer part is a thermoset semi-crystalline thiourethane polymer part, or, the semicrystalline thiourethane polymer part is a thermoplastic semi-crystalline thiourethane polymer part.

6. The method of claim 1 , wherein:
the first type of monomer includes di-thiol functionalized monomers and tri-thiol or higher functionalized monomers, wherein the di-thiol functionalized monomers equals from 25 to 90 mole percent, and the tri-thiol or higher functionalized monomers equals from 75 to 10 mole percent of thiols, of the first type of monomer, or,
the second type of monomer includes di-isocyanate functionalized monomers and tri-isocyanate or higher functionalized monomers, wherein the di-isocyanate functionalized monomers equals from 25 to 90 mole percent, and the tri-isocyanate or higher functionalized monomers equals from 75 to 10 mole percent, of isocyanates of the second type of monomer.

7. The method of claim 1 , wherein the first type of monomer is one or more of 2,2′-(ethylenedioxy)diethanethiol or pentaerythritol tetrakis(3-mercaptopropionate).

8. The method of claim 1 , wherein:
the first type of monomer includes di-thiol functionalized monomers and tri-thiol or higher functionalized monomers, wherein the di-thiol functionalized monomers equals from about 90 to 97 mole percent, and the tri-thiol or higher functionalized monomers equals from about 10 to 3 mole percent of thiols, of the first type of monomer, and,
the second type of monomer including di-isocyanate functionalized monomers equals about 100 mole percent, of isocyanates of the second type of monomer.

9. The method of claim 1 , wherein the polymer part has a toughness greater than or equal to about 10 MJ/m 3 .

10. The method of claim 1 , wherein the mixture has a viscosity similar to water in the range of about 0.3 to about 10 mPa·s.

11. The method of claim 1 , wherein the polymer part has a degree of crystallinity between 20% and 60%.

12. A stereolithography method of manufacturing a polymer part, comprising:
forming a mixture of a first type of monomer, a second type of monomer, and a photolatent base, wherein the first type of monomer include two or more thiol functional groups and the second type of monomer include two or more isocyanate functional groups; and
exposing portions of the mixture to light to photo-initiate decomposition of the photolatent base to form a non-nucleophillic base catalyst having a pKa greater than 7 to thereby initiate step-growth polymerization of the first type of monomer with the second type of monomers to thereby form a semi-crystalline thiourethane polymer part.

13. The method of claim 12 , wherein the first type of monomer is free of -ene or isocyanate functional groups and the second type of monomer is free of -ene or thiol functional groups.

14. The method of claim 12 , wherein the semi-crystalline thiourethane polymer part is a thermoset semi-crystalline thiourethane polymer part, or, the semicrystalline thiourethane polymer part is a thermoplastic semi-crystalline thiourethane polymer part.

15. The method of claim 12 , wherein:
the first type of monomer includes di-thiol functionalized monomers and tri-thiol or higher functionalized monomers, wherein the di-thiol functionalized monomers equals from 25 to 90 mole percent, and the tri-thiol or higher functionalized monomers equals from 75 to 10 mole percent of thiols, of the first type of monomer, or,
the second type of monomer includes di-isocyanate functionalized monomers and tri-isocyanate or higher functionalized monomers, wherein the di-isocyanate functionalized monomers equals from 25 to 90 mole percent, and the tri-isocyanate or higher functionalized monomers equals from 75 to 10 mole percent, of isocyanates of the second type of monomer.

16. The method of claim 12 , wherein the first type of monomer is one or more of 2,2′-(ethylenedioxy)diethanethiol or pentaerythritol tetrakis(3-mercaptopropionate).

17. The method of claim 12 , wherein:
the first type of monomer includes di-thiol functionalized monomers and tri-thiol or higher functionalized monomers, wherein the di-thiol functionalized monomers equals from about 90 to 97 mole percent, and the tri-thiol or higher functionalized monomers equals from about 10 to 3 mole percent of thiols, of the first type of monomer, and,
the second type of monomer including di-isocyanate functionalized monomers equals about 100 mole percent, of isocyanates of the second type of monomer.

18. The method of claim 12 , wherein the polymer part has a toughness greater than or equal to about 10 MJ/m 3 .

19. The method of claim 12 , wherein the mixture has a viscosity similar to water in the range of about 0.3 to about 10 mPa·s.

20. The method of claim 12 , wherein the polymer part has a degree of crystallinity between 20% and 60%.

Assignees

• Univ Texas
• Adaptive 3D Tech
• Board Of Resents The Univ Of Texas System

Inventors

• Ellson Gregory T
• Lund Benjamin R
• Voit Walter

Classifications

• B33Y70/00

  Materials specially adapted for additive manufacturing · CPC title

• B29C64/124 Primary

  using layers of liquid which are selectively solidified · CPC title

• C08G18/7621

  being toluene diisocyanate including isomer mixtures · CPC title

• B33Y10/00

  Processes of additive manufacturing · CPC title

• B29K2075/00

  Use of {PU, i.e.} polyureas or polyurethanes {or derivatives thereof}, as moulding material · CPC title