Metathesis polymerization methods

Patent metadata

Field	Value
Publication number	US-10907010-B2
Application number	US-201916351383-A
Country	US
Kind code	B2
Filing date	Mar 12, 2019
Priority date	Sep 3, 2014
Publication date	Feb 2, 2021
Grant date	Feb 2, 2021

Abstract

The present disclosure is directed to methods of making a polymer, including exposing a reaction mixture including a strained cyclic unsaturated monomer and an organic initiator to a stimulus to provide an activated organic initiator, whereby the activated organic initiator is effective to polymerize the strained cyclic unsaturated monomer via a 4-membered carbocyclic intermediate to provide a polymer having constitutional units derived from the strained cyclic unsaturated monomer.

First claim

The invention claimed is:

1. An additive manufacturing process, comprising:
exposing a first layer of a reaction mixture comprising a strained cyclic unsaturated monomer and an organic initiator to light to provide a polymerized first layer of the reaction mixture;
exposing the reaction mixture, in a second layer adjacent to the first layer, to light to provide a polymerized second layer of the reaction mixture; and
continuing to expose the reaction mixture in subsequent adjacent layers relative to an immediately preceding layer to polymerize the reaction mixture in a layer-by-layer manner to provide a three-dimensional object,
wherein exposing the reaction mixture to light provides an activated organic initiator, whereby the activated organic initiator is effective to polymerize the strained cyclic unsaturated monomer via a 4-membered carbocyclic intermediate, to provide a polymer having constitutional units derived from the strained cyclic unsaturated monomer.

2. The method of claim 1 , wherein the organic initiator is metal-free or is an organic unsaturated initiator.

3. The method of claim 2 , wherein the organic unsaturated initiator comprises one or more electron-donating substituents in electronic conjugation with an unsaturated bond, and the electron-donating substituent is selected from C 1-20 alkoxy, aryloxy, C 1-20 alkyl-NH—, aryl-NH—, C 1-20 alkyl-S—, and aryl-S—.

4. The method of claim 2 , wherein the organic unsaturated initiator is a compound of Formula (I)

wherein
R 1 is selected from hydrogen, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, aryl, and heteroaryl groups; and
R 2 is selected from C 1 -C 20 alkyl, cycloalkyl, aryl, and heteroaryl groups.

5. The method of claim 2 , wherein the organic unsaturated initiator is selected from

6. The method of claim 1 wherein the organic, initiator is an organic photoinitiator selected from

7. The method of claim 1 , further comprising oxidizing the organic initiator.

8. The method of claim 1 , wherein the reaction mixture further comprises an oxidizing agent, a mediator, or both an oxidizing agent and a mediator.

9. The method of claim 8 , wherein the mediator is selected from pyrylium salts, acridinium salts, thiopyrylium salts, and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone.

10. The method of claim 1 , wherein the polymerization is conducted under ambient atmosphere.

11. The method of claim 1 , wherein the stimulus is selected from ultraviolet light or visible light.

12. The method of claim 1 , wherein the strained cyclic unsaturated monomer has a ring strain of at least 20 kcal/mol.

13. The method of claim 12 wherein the strained cyclic unsaturated monomer is a strained cycloalkene selected from norbornene, cyclobutene, cyclooctene, cyclodecene, and cyclododecatriene.

14. The method of claim 13 , wherein the strained cycloalkene is selected from

15. The method of claim 1 , further comprising crosslinking the polymer.

16. The method of claim 15 , wherein crosslinking the polymer comprises reacting the polymer with a crosslinker selected from

17. An additive manufacturing process, comprising:
exposing a first layer of a reaction mixture comprising a strained cyclic unsaturated monomer, an organic unsaturated initiator, and a co-initiator to light to provide a polymerized first layer of the reaction mixture;
exposing the reaction mixture, in an adjacent layer to the first layer, to light to provide a polymerized second layer of the reaction mixture; and
continuing to expose the reaction mixture in subsequent adjacent layers relative to an immediately preceding layer to polymerize the reaction mixture in a layer-by-layer manner to provide a three-dimensional object,
wherein exposing the reaction mixture to light provides an activated co-initiator which activates the organic unsaturated initiator, whereby the activated organic unsaturated initiator is effective to polymerize the strained cyclic unsaturated monomer via a 4-membered carbocyclic intermediate, to provide a polymer having constitutional units derived from the strained cyclic unsaturated monomer.

18. The method of claim 17 , wherein the co-initiator is selected from pyrylium salts, acridinium salts, thiopyrylium salts, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, persulfate salts.

19. The method of claim 17 , wherein the co-initiator is selected from

wherein R 3 and R 4 is each independently selected from H, C 1-6 alkyl, C 1-6 alkoxy, and aryl.

20. The method of claim 17 , wherein the co-initiator is selected from Na 2 SO 5 , KHSO 5 , Na 2 S 2 O 8 , and (NH 4 ) 2 S 2 O 8 .

21. A three-dimensional object, comprising a metal-free polymer comprising an alkenyl substituted with a C 1 -C 20 alkoxy moiety at a polymer terminus.

22. The three-dimensional object of claim 21 , wherein the object is made according to the method of claim 1 .

23. The three-dimensional object of claim 21 , wherein the object is made according to the method of claim 17 .

Assignees

• Univ Washington

Inventors

• Boydston Andrew J
• Ogawa Kelli
• Goetz Adam E
• Dunford Damian
• Murphy Pascual Laura Marie

Classifications

• C08G61/12

  Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule · CPC title

• C08G2261/142

  Side-chains containing oxygen · CPC title

• C08G2261/44

  Electrochemical polymerisation, i.e. oxidative or reductive coupling · CPC title

• C08G2261/3324

  derived from norbornene · CPC title

• C08G2261/76

  crosslinking · CPC title