Photopolymerizable block polymers and methods of producing and using the same

Patent metadata

Field	Value
Publication number	US-12049528-B2
Application number	US-202217728900-A
Country	US
Kind code	B2
Filing date	Apr 25, 2022
Priority date	Apr 23, 2021
Publication date	Jul 30, 2024
Grant date	Jul 30, 2024

Abstract

Provided herein are curable compositions for use in a high temperature lithography-based photopolymerization process, and telechelic block polymers and methods of using such polymers in curable compositions to produce medical devices such as orthodontic appliances comprising the polymeric compositions comprising the telechelic block polymers.

First claim

What is claimed is:

1. A photo-curable resin comprising:
a telechelic polymer, the telechelic polymer comprising a polymer chain including, in a polymerized form, a first monomer and a reactive end functional group located at each terminus of the polymer chain; and
a reactive diluent,
wherein the first monomer comprises a first reactive functional group and has a vapor pressure from 2 Pa to 10 Pa at 60° C. in its monomeric state,
wherein the following conditions are met:
(i) following 2 h heating at 90° C., the first monomer has a mass loss rate of less than 0.25% per hour at 90° C. in its monomeric state;
(ii) a number average molecular weight of the telechelic polymer is not more than 50 kDa; and
(iii) the reactive end functional group and the first reactive functional group independently comprise a photopolymerizable moiety, and

wherein the photo-curable resin is capable of being 3D printed to form an article.

2. The photo-curable resin of claim 1 , wherein the first monomer has a vapor pressure from 2 Pa to 5 Pa at 60° C. in its monomeric state.

3. The photo-curable resin of claim 1 , wherein following the 2 h heating at 90° C., the first monomer has a mass loss from 0.05% to 0.225% per hour at 90° C. in its monomeric state.

4. The photo-curable resin of claim 1 , wherein following the 2 h heating at 90° C., the first monomer has a mass loss rate from 0.025% to 0.125% at 90° ° C. in its monomeric state.

5. The photo-curable resin of claim 1 , wherein the number average molecular weight of the telechelic polymer is from 5 kDa to 40 kDa.

6. The photo-curable resin of claim 5 , wherein the number average molecular weight of the telechelic polymer is from 5 kDa to 30 kDa.

7. The photo-curable resin of claim 5 , wherein the number average molecular weight of the telechelic polymer is from 5 kDa to 20 kDa.

8. The photo-curable resin of claim 5 , wherein the number average molecular weight of the telechelic polymer is from 5 kDa to 15 kDa.

9. The photo-curable resin of claim 1 , wherein the photopolymerizable moiety comprises an acrylate, methacrylate, vinyl acrylate, vinyl methacrylate, allyl ether, silene, alkyne, alkene, vinyl ether, maleimide, fumarate, maleate, itoconate, styrenyl, epoxide, oxetane, or thiol moiety.

10. The photo-curable resin of claim 1 , wherein the photopolymerizable moiety comprises an acrylate or methacrylate moiety.

11. The photo-curable resin of claim 1 , wherein the photopolymerizable moiety is capable of undergoing a photo-induced Diels-Alder click reaction or a photodimerization reaction.

12. The photo-curable resin of claim 1 , wherein the first monomer has a melting point of at least 25° C. when in its monomeric state.

13. The photo-curable resin of claim 1 , wherein the first monomer is a compound according to Formula (I):

wherein,
R 1 is H, substituted or unsubstituted C 1-3 alkyl or halogen; and
R 2 is substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, substituted or unsubstituted C 1-6 carbonyl, substituted or unsubstituted C 1-6 carboxy, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted cyclo(C 3-8 ) alkyl, or substituted or unsubstituted cyclo(C 3-8 ) heteroalkyl.

14. The photo-curable resin of claim 1 , comprising less than 20 wt % hydrogen bonding units.

15. The photo-curable resin of claim 1 , further comprising a crosslinking modifier, a light blocker, a solvent, a glass transition temperature modifier, or a combination thereof.

16. A medical device comprising a polymeric material formed from the photo-curable resin of claim 1 .

17. The photo-curable resin of claim 1 , wherein the telechelic polymer is a compound according to Formula (IV):

wherein:
each instance of R 9 is H, substituted or unsubstituted C 1-3 alkyl, or halogen;
each instance of R 10 is H, substituted or unsubstituted C 1-3 alkyl, or halogen;
R 11 is substituted or unsubstituted bicyclic alkyl; and
p is a positive integer from 1 to 200.

18. The photo-curable resin of claim 17 , wherein R 11 is selected from the group consisting of:

19. The photo-curable resin of claim 13 , further comprising another telechelic polymer, the another telechelic polymer comprising a polymer chain including, in a polymerized form, a second monomer that is different from the first monomer and a reactive end functional group located at each terminus of the polymer chain, wherein the second monomer is a compound according to Formula (II):

wherein,
R 3 is H, substituted or unsubstituted C 1-3 alkyl or halogen; and
R 4 is substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 1-6 heteroalkyl, substituted or unsubstituted C 1-6 carbonyl, substituted or unsubstituted C 1-6 carboxy, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted cyclo(C 3-8 ) alkyl, or substituted or unsubstituted cyclo(C 3-8 ) heteroalkyl.

20. The photo-curable resin of claim 1 , wherein the polymer chain of the telechelic polymer further comprises, in a polymerized form, a second monomer different from the first monomer, wherein the second monomer has a vapor pressure from 2 Pa to 10 Pa at 60° C. in its monomeric state, and following the 2 h heating at 90° C., the second monomer has a mass loss rate from 0.05% to 0.225% per hour at 90° ° C. in its monomeric state, wherein the first monomer, in the polymerized form, constitutes a first block of the polymer chain and the second monomer, in the polymerized form, constitutes a second block of the polymer chain.

21. The photo-curable resin of claim 1 , wherein the article comprises an orthodontic appliance.

22. The photo-curable resin of claim 21 , wherein the orthodontic appliance comprises a dental aligner of a series of dental aligners, an incremental palatal expander of a series of incremental palatal expanders or a retainer.

Assignees

• Align Technology Inc

Inventors

• Choudhary Umesh Upendra
• Su Jessica Kalay
• Cole Michael Christopher
• Chavez Jennifer Marie

Classifications

• C08F2/50

  with sensitising agents · CPC title

• A61C7/00

  Orthodontics, i.e. obtaining or maintaining the desired position of teeth, e.g. by straightening, evening, regulating, separating, or by correcting malocclusions · CPC title

• C08F220/301

  and one oxygen in the alcohol moiety · CPC title

• C08F220/302

  and two or more oxygen atoms in the alcohol moiety · CPC title

• B33Y80/00

  Products made by additive manufacturing · CPC title