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US-12617751-B2 - Visible light active biomass derived photoinitiators

US12617751B2US 12617751 B2US12617751 B2US 12617751B2US-12617751-B2

Abstract

Biomass derived benzoin derivatives, and methods of making and using the same, are described. Benzoin derivatives may be used as visible light photoinitiators.

Inventors

  • Jayaraman Sivaguru
  • Ravichandranath Singathi
  • Sruthy Baburaj

Assignees

  • BOWLING GREEN STATE UNIVERSITY

Dates

Publication Date
20260505
Application Date
20210518

Claims (20)

  1. 1 . A composition comprising Formula Bz-1: wherein: dashed lines indicate optional bonds; X is O, S, NH, Ge, NC(O)—O—R C , N—O—C(O)R C , or NO—R C , wherein R C is alkyl, aryl, or heteroaryl; each of A and B is a phenyl ring; Z is OH or H; Y is OH, alkoxy, halo, SH, S-alkyl, carboxy, aryloxy, or a hetero-atom; and substituents R A1 to R A5 and R B1 to R B5 are any combination of H, alkyl, alkene, alkynes, aryl, heterocyclic, alkenyl halides, unsaturated enones, unsaturated ketones, unsaturated amides, unsaturated alcohols, unsaturated amines, unsaturated thiols, phosphonates, carboxylates, sulfonates, nitriles, thioethers, thioketones, azides, sulfides, disulfides, ethers, epoxides, nitrates, nitrites, nitro compounds, nitroso compounds, alkyl ketoesters, acylgermanes, metallocenes, organosilanes, oximes, imides, cyanates, isocyanates, thiocyanates, isothiocyanates, sulfoxides, sulfones, sulfites, phosphites, thial, phosphines, and aldehydes; provided that one of A or B has two methoxy substituents.
  2. 2 . The composition of claim 1 , wherein the composition comprises bis-(dimethoxy)-benzoin 1a, para-chlorobenzyl-(dimethoxy)-benzoin 1b, para-cyanobenzyl-(dimethoxy)-benzoin 1c, para-trifluoromethylbenzyl-(dimethoxy)-benzoin 1d, para-chlorobenzoyl-(dimethoxy)-benzoin 1e, para-thiomethylbenzoyl-(dimethoxy)-benzoin 1f, para-thiomethylbenzoyl-(dimethoxy)-benzoin 1g, para-fluorobenzyl-(dimethoxy)-benzoin 1i, or para-fluorobenzyl-(dimethoxy)-benzoin 1j:
  3. 3 . A composition comprising Formula Bz-2 or Formula Bz-3: wherein: dashed lines indicate optional bonds; X is O, S, NH, Ge, NC(O)—O—R C , N—O—C(O)R C , or NO—R C , wherein R C is alkyl, aryl, or heteroaryl; each of A and B is a phenyl ring; Z is OH or H; Y is OH, alkoxy, halo, SH, S-alkyl, carboxy, aryloxy, or a hetero-atom; substituents R A1 to R A5 and R B1 to R B5 are any combination of H, alkyl, alkene, alkynes, aryl, heterocyclic, alkenyl halides, unsaturated enones, unsaturated ketones, unsaturated amides, unsaturated alcohols, unsaturated amines, unsaturated thiols, phosphonates, carboxylates, sulfonates, nitriles, thioethers, thioketones, azides, sulfides, disulfides, ethers, epoxides, nitrates, nitrites, nitro compounds, nitroso compounds, alkyl ketoesters, acylgermanes, metallocenes, organosilanes, oximes, imides, cyanates, isocyanates, thiocyanates, isothiocyanates, sulfoxides, sulfones, sulfites, phosphites, thial, phosphines, and aldehydes; and the polymer unit is vinyl, stryl, acryl, or cyclic monomers selected from lactones, epoxides, lactides, lactams, silicon-containing cyclic monomers, and cyclic carbonates; provided that one of A or B has two methoxy substituents.
  4. 4 . The composition of claim 3 , wherein the composition comprises Bz-2a, Bz-2a-I, Bz-2b, Bz-2b-I, Bz-2c, Bz-2d, Bz-3a, Bz-3a-I, Bz-3b, Bz-3c, or Bz-3d: wherein R M is alkyl, aryl, or heteroaryl; wherein m and n each integers and R M is alkyl, aryl, or heteroaryl; wherein m and n are each integers; wherein R M is alkyl, aryl, or heteroaryl; wherein m and n are each integers;
  5. 5 . A composition comprising Formula Bz-4, Formula Bz-5, Formula Bz-6, or Formula Bz-7: wherein: dashed lines indicate optional bonds; X is O, S, NH, Ge, NC(O)—O—R C , N—O—C(O)R C , or NO—R C , wherein R C is alkyl, aryl, or heteroaryl; each of A and B is a phenyl ring; Z is OH or H; Y is OH, alkoxy, halo, SH, S-alkyl, carboxy, aryloxy, or a hetero-atom; substituents R A1 to R A5 and R B1 to R B5 are any combination of H, alkyl, alkene, alkynes, aryl, heterocyclic, alkenyl halides, unsaturated enones, unsaturated ketones, unsaturated amides, unsaturated alcohols, unsaturated amines, unsaturated thiols, phosphonates, carboxylates, sulfonates, nitriles, thioethers, thioketones, azides, sulfides, disulfides, ethers, epoxides, nitrates, nitrites, nitro compounds, nitroso compounds, alkyl ketoesters, acylgermanes, metallocenes, organosilanes, oximes, imides, cyanates, isocyanates, thiocyanates, isothiocyanates, sulfoxides, sulfones, sulfites, phosphites, thial, phosphines, and aldehydes; the co-initiating unit is an amine, a thiol, or any hydrogen atom donor; and the polymer unit is vinyl, stryl, acryl, or cyclic monomers selected from lactones, epoxides, lactides, lactams, silicon-containing cyclic monomers, and cyclic carbonates.
  6. 6 . The composition of claim 5 , wherein the composition comprises compound Bz-4a, Bz-5a, Bz-6a, Bz-6b, Bz-6c, Bz-6d, Bz-7a, Bz-7b, Bz-7c, or Bz-7d: wherein m is an integer; wherein n is an integer;
  7. 7 . A method for making a polymer, the method comprising exposing a photoinitiator and a monomer to light to produce a polymer, wherein the photoinitiator is a biomass derived benzoin derivative having two methoxy substituents on one phenyl ring.
  8. 8 . The method of claim 7 , wherein the photoinitiator comprises Formula Bz-1: wherein: dashed lines indicate optional bonds; X is O, S, NH, Ge, NC(O)—O—R C , N—O—C(O)R C , or NO—R C , wherein R C is alkyl, aryl, or heteroaryl; each of A and B is a phenyl ring; Z is OH or H; Y is OH, alkoxy, halo, SH, S-alkyl, carboxy, aryloxy, or a hetero-atom; A or B is a ring derived from biomass; and substituents R A1 to R A5 and R B1 to R B5 are any combination of H, alkyl, alkene, alkynes, aryl, heterocyclic, alkenyl halides, unsaturated enones, unsaturated ketones, unsaturated amides, unsaturated alcohols, unsaturated amines, unsaturated thiols, phosphonates, carboxylates, sulfonates, nitriles, thioethers, thioketones, azides, sulfides, disulfides, ethers, epoxides, nitrates, nitrites, nitro compounds, nitroso compounds, alkyl ketoesters, acylgermanes, metallocenes, organosilanes, oximes, imides, cyanates, isocyanates, thiocyanates, isothiocyanates, sulfoxides, sulfones, sulfites, phosphites, thial, phosphines, and aldehydes.
  9. 9 . The method of claim 7 , wherein the photoinitiator has Formula A: wherein: A and B each independently represent a carbocycle optionally substituted with one or more electron withdrawing or electron donating substituents; and X comprises OH, an alkoxy, halo, SH, S-alkyl, carboxy, aryloxy, or hetero-atom attached to a carbocycle or a heterocycle.
  10. 10 . The method of claim 7 , wherein the polymer is colorless or transparent.
  11. 11 . The method of claim 7 , wherein the photoinitiator comprises bis-(dimethoxy)-benzoin 1a, para-chlorobenzyl-(dimethoxy)-benzoin 1b, para-cyanobenzyl-(dimethoxy)-benzoin 1c, para-trifluoromethylbenzyl-(dimethoxy)-benzoin 1d, para-chlorobenzoyl-(dimethoxy)-benzoin 1e, para-thiomethylbenzoyl-(dimethoxy)-benzoin 1f, para-thiomethylbenzoyl-(dimethoxy)-benzoin 1g, para-fluorobenzyl-(dimethoxy)-benzoin 1i, or para-fluorobenzyl-(dimethoxy)-benzoin 1j:
  12. 12 . The method of claim 7 , wherein the photoinitiator comprises Formula Bz-2 or Formula Bz-3: wherein: dashed lines indicate optional bonds; X is O, S, NH, Ge, NC(O)—O—R C , N—O—C(O)R C , or NO—R C , wherein R C is alkyl, aryl, or heteroaryl; each of A and B is a phenyl ring; Z is OH or H; Y is OH, alkoxy, halo, SH, S-alkyl, carboxy, aryloxy, or a hetero-atom; A or B is a ring derived from biomass; substituents R A1 to R A5 and R B1 to R B5 are any combination of H, alkyl, alkene, alkynes, aryl, heterocyclic, alkenyl halides, unsaturated enones, unsaturated ketones, unsaturated amides, unsaturated alcohols, unsaturated amines, unsaturated thiols, phosphonates, carboxylates, sulfonates, nitriles, thioethers, thioketones, azides, sulfides, disulfides, ethers, epoxides, nitrates, nitrites, nitro compounds, nitroso compounds, alkyl ketoesters, acylgermanes, metallocenes, organosilanes, oximes, imides, cyanates, isocyanates, thiocyanates, isothiocyanates, sulfoxides, sulfones, sulfites, phosphites, thial, phosphines, and aldehydes; and the polymer unit is vinyl, stryl, acryl, or cyclic monomers selected from lactones, epoxides, lactides, lactams, silicon-containing cyclic monomers, and cyclic carbonates.
  13. 13 . The method of claim 7 , wherein the photoinitiator comprises Bz-2a, Bz-2a-I, Bz-2b, Bz-2b-I, Bz-2c, Bz-2d, Bz-3a, Bz-3a-I, Bz-3b, Bz-3c, or Bz-3d: wherein R M is alkyl, aryl, or heteroaryl; wherein m and n each integers and R M is alkyl, aryl, or heteroaryl; wherein m and n are each integers; wherein R M is alkyl, aryl, or heteroaryl; wherein m and n are each integers;
  14. 14 . The method of claim 7 , wherein the photoinitiator comprises Formula Bz-4, Formula Bz-5, Formula Bz-6, or Formula Bz-7: wherein: dashed lines indicate optional bonds; X is O, S, NH, Ge, NC(O)—O—R C , N—O—C(O)R C , or NO—R C , wherein R C is alkyl, aryl, or heteroaryl; each of A and B is a phenyl ring; Z is OH or H; Y is OH, alkoxy, halo, SH, S-alkyl, carboxy, aryloxy, or a hetero-atom; A or B is a ring derived from biomass; substituents R A1 to R A5 and R B1 to R B5 are any combination of H, alkyl, alkene, alkynes, aryl, heterocyclic, alkenyl halides, unsaturated enones, unsaturated ketones, unsaturated amides, unsaturated alcohols, unsaturated amines, unsaturated thiols, phosphonates, carboxylates, sulfonates, nitriles, thioethers, thioketones, azides, sulfides, disulfides, ethers, epoxides, nitrates, nitrites, nitro compounds, nitroso compounds, alkyl ketoesters, acylgermanes, metallocenes, organosilanes, oximes, imides, cyanates, isocyanates, thiocyanates, isothiocyanates, sulfoxides, sulfones, sulfites, phosphites, thial, phosphines, and aldehydes; the co-initiating unit is an amine, a thiol, or any hydrogen atom donor; and the polymer unit is vinyl, stryl, acryl, or cyclic monomers selected from lactones, epoxides, lactides, lactams, silicon-containing cyclic monomers, and cyclic carbonates.
  15. 15 . The method of claim 7 , wherein the photoinitiator comprises compound Bz-4a, Bz-5a, Bz-6a, Bz-6b, Bz-6c, Bz-6d, Bz-7a, Bz-7b, Bz-7c, or Bz-7d: wherein m is an integer; or wherein n is an integer;
  16. 16 . The method of claim 7 , wherein the photoinitiator is prepared from biomass.
  17. 17 . The method of claim 7 , wherein the light is visible light.
  18. 18 . The method of claim 7 , wherein the light is purple light or blue light.
  19. 19 . The method of claim 7 , wherein the monomer is methylmethacrylate 4 or polymer 5: wherein n is an integer.
  20. 20 . The method of claim 7 , wherein a co-initiator is exposed to the light with the photoinitiator and the monomer.

Description

RELATED APPLICATIONS This is the national phase application of international application PCT/US2021/032893, filed under the authority of the Patent Cooperation Treaty on May 18, 2021, published; which claims priority to U.S. Provisional Application No. 63/026,970 filed under 35 U.S.C. § 111(b) on May 19, 2020. The entire disclosure of each of the aforementioned applications is incorporated herein by reference in its entirety for all purposes. STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH This invention was made with no government support. The government has no rights in this invention. BACKGROUND Photoinitiators are widely used for various applications that involves UV curing. These include automobile parts manufacturing, automobile parts, 3D printing, contact lenses, resin curing, silicones, epoxies, dental composites, aircraft parts, and composites. Most conventional photoinitiators require UV light. There is a need in the art for new and improved photoinitiators have features that will be compatible to existing formulations but will have the ability to work under visible light conditions. SUMMARY Provided herein is a composition comprising Formula Bz-1: where dashed lines indicate optional bonds; X=O, S, NH, Ge, NC(O)—O—RC, N—O—C(O)RC, or NO—RC, wherein RC is alkyl, aryl, or heteroaryl; A or B is a ring derived from biomass; and substituents RA1 to RA5 and RB1 to RB5 can be any combination of H, alkyl, alkene, alkynes, aryl, heterocyclic, alkenyl halides, unsaturated enones, unsaturated ketones, unsaturated amides, unsaturated alcohols, unsaturated amines, unsaturated thiols, phosphonates, carboxylates, sulfonates, nitriles, thioethers, thioketones, azides, sulfides, disulfides, ethers, epoxides, nitrates, nitrites, nitro compounds, nitroso compounds, alkyl ketoesters, acylgermanes, metallocenes, organosilanes, oximes, imides, cyanates, isocyanates, thiocyanates, isothiocyanates, sulfoxides, sulfones, sulfites, phosphites, thial, phosphines, and aldehydes. In certain embodiments, the composition comprises Formula A: where units A and B represent an alkyl chain, a carbocycle, a heterocyclic moiety, or a combination of C—C or C-heteroatom bonds, optionally substituted with one or more electron withdrawing (e.g., alkoxy) or electron donating substituents (e.g., halogens). X can feature an alkoxy, halo, SH, S-alkyl, carboxy, aryloxy, or hetero-atom attached to a carbocycle or a heterocycle. In certain embodiments, at least one of the units A, B, or X is derived from bio-mass. In certain embodiments, the composition comprises bis-(dimethoxy)-benzoin 1a: In certain embodiments, the composition comprises para-chlorobenzyl-(dimethoxy)-benzoin 1b: In certain embodiments, the composition comprises para-cyanobenzyl-(dimethoxy)-benzoin 1c: In certain embodiments, the composition comprises para-trifluoromethylbenzyl-(dimethoxy)-benzoin 1d: In certain embodiments, the composition comprises para-chlorobenzoyl-(dimethoxy)-benzoin 1e: In certain embodiments, the composition comprises para-thiomethylbenzyl-(dimethoxy)-benzoin 1f: In certain embodiments, the composition comprises para-thiomethylbenzoyl-(dimethoxy)-benzoin 1g: In certain embodiments, the composition comprises compound para-fluorobenzyl-(dimethoxy)-benzoin 1i: In certain embodiments, the composition comprises compound para-fluorolbenzoyl-(dimethoxy)-benzoin 1j: Further provided is a composition comprising Formula Bz-2 or Formula Bz-3: wherein dashed lines indicate optional bonds; X=O, S, NH, Ge, NC(O)—O—RC, N—O—C(O)RC, or NO—RC, wherein RC is alkyl, aryl, or heteroaryl; A or B is a ring derived from biomass; substituents RA1 to RA5 and RB1 to RB5 can be any combination of H, alkyl, alkene, alkynes, aryl, heterocyclic, alkenyl halides, unsaturated enones, unsaturated ketones, unsaturated amides, unsaturated alcohols, unsaturated amines, unsaturated thiols, phosphonates, carboxylates, sulfonates, nitrites, thioethers, thioketones, azides, sulfides, disulfides, ethers, epoxides, nitrates, nitrites, nitro compounds, nitroso compounds, alkyl ketoesters, acylgermanes, metallocenes, organosilanes, oximes, imides, cyanates, isocyanates, thiocyanates, isothiocyanates, sulfoxides, sulfones, sulfites, phosphites, thial, phosphines, and aldehydes; and the polymer unit is vinyl, stryl, acryl, or cyclic monomers selected from lactones (cyclic esters), epoxides, lactides, lactams, silicon-containing cyclic monomers, and cyclic carbonates. In certain embodiments, the composition comprises Bz-2a: where RM is alkyl, aryl, or heteroaryl. In particular embodiments, the composition comprises Bz-2a-I: wherein m and n are each integers. In certain embodiments, the composition comprises compound Bz-2b: In certain embodiments, the composition comprises Bz-2b-I: wherein m and n are each integers. In certain embodiments, the composition comprises compound Bz-2b: In certain embodiments, the composition comprises compound Bz-2d: In certain embodiments, the composition comprises Bz-3a