Self-immolative polymers, articles thereof, and methods of making and using same

Patent metadata

Field	Value
Publication number	US-10662274-B2
Application number	US-201715830864-A
Country	US
Kind code	B2
Filing date	Dec 4, 2017
Priority date	Dec 2, 2016
Publication date	May 26, 2020
Grant date	May 26, 2020

Abstract

Self-immolative polymers and compositions comprising such polymers are described. The polymers are copolymers of phthalaldehyde and one or more additional aldehydes and can degrade/decompose upon exposure to a desired stimulus, like light, heat, sound, or chemical trigger. The copolymers can be linear or cyclic, and can be crosslinked or uncrosslinked. Polymer compositions, including multilayered and multiregioned compositions, containing the copolymers are disclosed. These compositions can contain agents such as crosslinking agents, crosslinking catalysts, photocatalysts, thermocatalyst, sensitizers, chemical amplifiers, freezing point depressing agent, photo-response delaying agents, and the like. Methods of making and using the copolymers are also described.

First claim

What is claimed is:

1. A copolymer, comprising: a repeating unit as shown in Formula I:

wherein R is substituted or unsubstituted C 1 -C 20 alkyl, C 1 -C 20 alkoxyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 6 -C 10 heteroaryl, C 3 -C 10 cycloalkyl, C 3 -C 10 cycloalkenyl, C 3 -C 10 heterocycloalkyl, or C 3 -C 10 heterocycloalkenyl; and, when substituted, R is substituted with C 1 -C 20 alkyl, C 1 -C 20 alkoxy, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 6 -C 10 aryl, C 6 -C 10 heteroaryl, aldehyde, amino, sulfonic acid, sulfinic acid, fluoroacid, phosphonic acid, ether, halide, hydroxy, ketone, nitro, cyano, azido, silyl, sulfonyl, sulfinyl, or thiol.

2. The copolymer of claim 1 , wherein the copolymer is linear or branched.

3. The copolymer of claim 1 , wherein the copolymer is cyclic and has Formula II:

wherein n is an integer from 1 to 100,000;

and is a backbone of the copolymer and comprises any one or any combination of the following repeating units:

where m is an integer from 1 to 100,000; p is an integer from 1 to 100,000; and q is an integer from 1 to 100,000.

4. The copolymer of claim 1 , wherein the copolymer is cyclic and has Formula III:

wherein R and R′ are different; and R′ is chosen from substituted or unsubstituted C 1 -C 20 alkyl, C 1 -C 20 alkoxyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 6 -C 10 aryl, C 6 -C 10 heteroaryl, C 3 -C 10 cycloalkyl, C 3 -C 10 cycloalkenyl, C 3 -C 10 heterocycloalkyl, or C 3 -C 10 heterocycloalkenyl; and, when substituted, R′ can be substituted with C 1 -C 20 alkyl, C 1 -C 20 alkoxy, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 6 -C 10 aryl, C 6 -C 10 heteroaryl, aldehyde, amino, carboxylic acid, sulfonic acid, sulfinic acid, fluoroacid, phosphonic acid, ester, ether, halide, hydroxy, ketone, nitro, cyano, azido, silyl, sulfonyl, sulfinyl, or thiol; and

is a backbone of the copolymer and comprises any one or any combination of the following repeating units:

wherein m is an integer from 1 to 100,000; p is an integer from 1 to 100,000; q is an integer from 1 to 100,000; r is an integer from 1 to 100,000; s is an integer from 1 to 100,000; and t is an integer from 1 to 100,000.

5. The copolymer of claim 1 , wherein R is C 1 -C 10 alkyl, C 2 -C 10 alkenyl, or C 2 -C 10 alkynyl, or cycloalkenyl, or heterocycloalkenyl.

6. The copolymer of claim 1 , wherein R is an unsubstituted C 2 -C 20 alkenyl, unsubstituted C 2 -C 20 alkynyl, unsubstituted, cycloalkenyl, unsubstituted heterocycloalkenyl, C 6 -C 10 heteroaryl; or R is C 1 -C 20 alkyl, C 3 -C 10 cycloalkyl, or C 3 -C 10 heterocycloalkyl substituted with amino, sulfonic acid, sulfinic acid, fluoroacid, phosphonic acid, ester, halide, hydroxyl, ketone, nitro, cyano, azido, thiol, sulfonic acid, or fluoroacid.

7. The copolymer of claim 1 , wherein the copolymer is a copolymer of phthalaldehyde monomers and one or more of acetaldehyde, propanal, butanal, pentanal, hexanal, heptanal, octanal, nonanal, decanal, undecanal, propenal, butenal, pentenal, hexenal, heptenal, octenal, nonenal, decenal, and undecenal.

8. The copolymer of claim 1 , wherein the copolymer has a ratio of phthalaldehyde units to other aldehyde units of from about 1:50 to about 50:1.

9. The copolymer of claim 1 , wherein the copolymer has from 30 mol % to 99 mol % phthalaldehyde units based on the total monomer content.

10. The copolymer of claim 1 , wherein the copolymer has from 90 mol % to 99 mol % phthalaldehyde units based on the total monomer content.

11. The copolymer of claim 1 , wherein the copolymer has a molecular weight of from 2,000 g/mol to 80,000 g/mol.

12. The copolymer of claim 1 , wherein the copolymer has a ceiling temperature of ambient temperature to −50° C.

13. A composition, comprising: the copolymer of claim 1 .

14. A composition, comprising: the cyclic copolymer of claim 2 .

15. The composition of claim 13 , further comprising a photocatalyst.

16. The composition of claim 15 , wherein the photocatalyst is a diaryliodonium salt, a triarylsulfonium salt, tetraphenylborate salt, an onium salt or sulfonium salt having perfluorinated anions, a bissulfonyldiazomethane compound, an N-sulfonyloxydicarboximide compound, an O-arylsulfonyloxime compound, tetrakis-(pentafluorophenyl)borate-4-methylphenyl[4-(1-methylethyl)phenyl]iodonium (Rhodorsil-FABA), tris(4-tert-butylphenyl)sulfonium tetrakis-(pentafluorophenyl) borate (TTBPS-FABA), triphenylsulfonium tetrakis-(pentafluorophenyl) borate (TPS-FABA), bis(4-tert-butylphenyl)iodonium triflate (BTBPI-TF), tert-(butoxycarbonylmethoxynaphthyl)-diphenylsulfonium triflate (TBOMDS-TF), N-hydroxynaphthalimide triflate (NHN-TF), diphenyliodonium perfluoro-1-butanesulfonate (DPI-NF), tris(4-tert-butylphenyl)sulfonium perfluoro-1-butanesulfonate (TTBPS-NF), N-hydroxynaphthalimide perfluoro-1-butanesulfonate (NHN-NF), N-hydroxy-5-norbornene-2,3-dicarboximide perfluoro-1-butanesulfonate (NHNDC-NF), bis(4-tert-butylphenyl)iodonium tris(perfluoromethanesulfonyl) methide, (BTBPI-TMM), bis(4-tert-butylphenyl)iodonium bis(perfluorobutanesulfonyl) imide (BTBPI-BBI), diphenyliodonium 9,10-dimethoxyanthracene-2-sulfonate (DPI-DMOS), bis(4-tert-butylphenyl) iodonium p-toluenesulfonate (BTBPI-PTS), (1Z,1′Z)-1,1′-((ethane-1,2-diylbis(oxy))bis(4,1-phenylene))bis(2,2,2-trifluoroethan-1-one) O,O-dipropylsulfonyl dioxime, bis(4-tert-butylphenyl)iodonium perfluoro-1-octanesulfonate (BTBPI-HDF), or any combination thereof.

17. The composition of claim 13 , further comprising a thermocatalyst.

18. The composition of claim 13 , further comprising a photosensitizer.

19. The composition of claim 18 , wherein the photosensitizer is a modified acene.

20. The composition of claim 18 , wherein the photosensitizer is anthracene, 1,8-dimethoxy-9,10-bis(phenylethynyl)anthracene (DMBA), 6,13-bis(3,4,5-trimethoxyphenylethynyl)pentacene (BTMP), 5,12-bis(phenylethynyl)tetracene (BPET), 1-Chloro-4-propoxythioxanthone (CPTX), 4-methylphenyl[4-(1-methylethyl) phenyl] tetrakis(pentafluorophenyl) borate (FABA-PAG), 1,5,7 triaza-bicyclo [4.4.0] dec-5-ene tetraphenylborate (TBD-PBG), or any combination thereof.

21. The composition of claim 13 , further comprising a freezing point depressing agent.

22. The composition of claim 21 , wherein the freezing point depressing agent is an adipate, azelate, citrate, ether-ester, glutarate, isobutyrate, phosphate, sebacate, tertiary amine, quaternary ammonium compound, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, tripropylene glycol dibenzoate, butyl benzyl phthalate, phosphonium compound, sulfonium compound, or any combination thereof.

23. The composition of claim 13 , further comprising a plasticizer.

24. The composition of claim 13 , furt

Assignees

• Georgia Tech Res Inst

Inventors

• Kohl Paul A
• Phillips Oluwadamilola
• Schwartz Jared
• Gourdin Gerald
• Engler Anthony
• Jiang Jisu

Classifications

• C08K5/0016

  Plasticisers · CPC title

• C08K5/55

  Boron-containing compounds {(C08K5/0091 takes precedence)} · CPC title

• C08K5/0008

  Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59 · CPC title

• B32B2307/716

  Degradable · CPC title

• C08G2/20

  with other aldehydes or ketones · CPC title