Granted Patent B2

US 12,391,780 · App. 17/431,670 · Granted Aug 19, 2025

Inventors: Christopher N. Bowman (Boulder, CO); Matthew K. Mcbride (Boulder, CO); Brady T. Worrell (Englewood, CO); Marvin Dion Alim (Kirkland, WA); Robert R. McLeod (Boulder, CO)

Assignee: The Regents of the University of Colorado, a body corporate

C08F220/301C08G18/3876C08G18/672C08K5/5397G03H1/02C08F2438/03G03H2001/0264G03H2240/54G03H2260/12

Abstract

Claims (95)

1. A composition comprising a support matrix and at least one writing monomer,

wherein the support matrix consists of a covalent adaptable network that is a reaction product of at least one first multifunctional monomer, at least one second multifunctional monomer, and at least one third multifunctional monomer,

wherein:

a) the at least one first multifunctional monomer is selected from the group consisting of:

wherein in (a):

each occurrence of R is independently selected from the group consisting of H and C 1 -C 10 alkyl;

each occurrence of n is independently 1, 2, 3, 4, 5, or 6;

b) the at least one second multifunctional monomer is a compound of Formula (I):

wherein:

A is

R 1 is selected from the group consisting of

 wherein the * denotes the point of attachment to A,

X 1 is OH,

m is an integer from 1 to 100;

and

c) the at least one third multifunctional monomer is selected from the group consisting of a straight chain perfluorocarbon diol, a polycaprolactone diol, a poly (tetrahydrofuran) diol, a poly (caprolactone-co-tetrahydrofuran) diol, a poly (ethylene glycol) diol, and a poly (butadiene) diol;

wherein in the reaction product, the at least one first multifunctional monomer crosslinks at least one second multifunctional monomer and at least one third multifunctional monomer;

wherein the composition further comprises at least one non-reactive counter diffusant;

wherein at least a portion of the support matrix is swollen with at least one writing monomer selected from the group consisting of tribromophenyl (meth) acrylate, pentabromophenyl (meth) acrylate, phenylthioethyl (meth) acrylate, naphthylthioethyl (meth) acrylate, tritylthioethyl (meth) acrylate,

wherein in the at least one writing monomer:

R 1 and R 2 are independently selected from the group consisting of:

x is 1, and R groups marked with ‘*’ and ‘**’ are independently selected from the group consisting of:

 or

x is 2, and

each R group marked with ‘*’ is independently selected from the group consisting of:

 and

each R group marked with ‘**’ is independently selected from the group consisting of:

and a polymerization initiator.

2. The composition of claim 1 , wherein the at least one writing monomer has a refractive index equal to or above about 1.58.

3. The composition of claim 1 , wherein the polymerization initiator is selected from the group consisting of a photoinitiator, a thermal initiator, and a redox initiator, wherein at least one of the following is true:

a) the photoinitiator is selected from the group consisting of acetophenone, benzophenone, 2-phenylacetophenone, 2,2-dimethoxy-2-phenylacetophenone, bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide, 2-hydroxy-4′-(2-hydroxyethoxy)-2-methylpropiophenone, 2-methyl-(4-methylthienyl)-2-morpholinyl-1-propan-1-one, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, ethyl (2,4,6-trimethylbenzoyl) phenyl phosphinate, lithium phenyl-2,4,6-trimethylbenzoylphosphinate,

b) the thermal initiator is selected from the group consisting of tert-Amyl peroxybenzoate, 4,4-azobis (4-cyanovaleric acid), 1,1′-azobis (cyclohexanecarbonitrile), 2,2′-azobisisobutyronitrile (AIBN), benzoyl peroxide, 2,2-bis(tert-butylperoxy) butane, 1,1-bis(tert-butylperoxy) cyclohexane, 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane, 2,5-bis(tert-butylperoxy)-2,5-dimethyl-3-hexyne, bis(1-(tert-butylperoxy)-1-methylethyl) benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, tert-Butyl hydroperoxide, tert-butyl peracetate, tert-butyl peroxide, tert-butyl peroxybenzoate, tert-Butylperoxy isopropyl carbonate, cumene hydroperoxide, cyclohexanone peroxide, dicumyl peroxide, lauroyl peroxide, 2,4-pentanedione peroxide, peracetic acid, and potassium persulfate; or

c) the redox initiator is selected from the group consisting of sodium iodide/hydrogen peroxide, potassium iodide/hydrogen peroxide, benzoyl peroxide/dimethyaniline, benzoyl peroxide/N,N-dimethyl p-toluidine, benzoyl peroxide/4-N,N-dimethylaminophenethyl alcohol, benzoyl peroxide/ethyl 4-dimethylaminobenzoate, glucose oxidase/oxygen/iron (II) sulfate, and copper (II) sulfate/sodium ascorbate.

4. The composition of claim 1 , wherein none of the writing monomers are covalently bound to the support matrix.

5. The composition of claim 1 , wherein at least a portion of the writing monomer is covalently bound to at least a portion of a reversible addition-fragmentation chain transfer (RAFT) functionality in the support matrix.

6. The composition of claim 1 , wherein the non-reactive counter diffusant has a refractive index equal to or less than about 1.5.

7. The composition of claim 1 , wherein the at least one first multifunctional monomer is selected from the group consisting of:

8. The composition of claim 1 , wherein the non-reactive counter diffusant is selected from the group consisting of:

2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorononylbutyl carbamate,

2,2,2-trifluoroethylhexyl carbamate,

bis(1,1,1,3,3,3-hexafluoropropan-2-yl)-(2,2,4-trimethylhexane-1,6-diyl) bis carbamate,

2,2,3,3,4,4,5,5,6,6,7,7-dodeca-fluoroheptylbutyl carbamate,

2,2,3,3,4,4,5,5,6,6,7,7-dodeca-fluoroheptylhexyl carbamate,

2,2,3,3,4,4,5,5,6,6,7,7-dodeca-fluoroheptyl propan-2-yl carbamate,

2,2,3,3,4,4,4-heptafluorobutylhexyl carbamate,

2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorononylhexyl carbamate, and

2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorononylcyclohexyl carbamate.

9. The composition of claim 1 , wherein the at least one second multifunctional monomer is selected from the group consisting of

10. A method of making a holographic material, the method comprising:

(a) forming a reaction mixture consisting of:

(i) at least one first multifunctional monomer selected from the group consisting of

wherein

each occurrence of R is independently selected from the group consisting of H and C1-C10 alkyl;

each occurrence of n is independently 1, 2, 3, 4, 5, or 6;

(ii) at least one second multifunctional monomer of Formula (I):

wherein:

A is

R 1 is selected from the group consisting of

 wherein the * denotes the point of attachment to A,

X 1 is OH,

m is an integer from 1 to 100;

(iii) at least one third multifunctional monomer selected from the group consisting of a straight chain perfluorocarbon diol, a polycaprolactone diol, a poly (tetrahydrofuran) diol, a poly (caprolactone-co-tetrahydrofuran) diol, a poly (ethylene glycol) diol, and a poly (butadiene) diol;

(iv) at least one writing monomer selected from the group consisting of tribromophenyl (meth) acrylate, pentabromophenyl (meth) acrylate, phenylthioethyl (meth) acrylate, naphthylthioethyl (meth) acrylate, tritylthioethyl (meth) acrylate,

wherein in the at least one writing monomer:

R 1 and R 2 are independently selected from the group consisting of:

x is 1, and R groups marked with ‘*’ and ‘**’ are independently selected from the group consisting of:

 or

x is 2, and

each R group marked with ‘*’ is independently selected from the group consisting of:

 and

each R group marked with ‘**’ is independently selected from the group consisting of:

 and

(v) at least one of a non-reactive counter diffusant and a polymerization initiator;

(b) polymerizing the reaction mixture such that the at least one first multifunctional monomer crosslinks the at least one third multifunctional monomer and the at least one second multifunctional monomer to form a covalently bound support matrix,

wherein the at least one writing monomer is unbound and capable of moving freely within the support matrix and wherein at least a portion of the support matrix is swollen with the at least one writing monomer,

wherein the polymerizing is through at least one method selected from the group consisting of thermally initiated polymerization, photopolymerization, and redox initiated polymerization;

(c) optionally, activating the RAFT functionalities in the at least one second multifunctional monomer in order to induce support matrix network rearrangement; and

(d) polymerizing the at least one writing monomer.

11. The method of claim 10 , wherein step (c) is carried out and the RAFT functionalities are activated through at least one means selected from the group consisting of thermal initiation, photoinitiation, and redox initiation.

12. The method of claim 10 , wherein the at least one writing monomer is polymerized with spatial selectivity in step (d).

13. The method of claim 10 , wherein the at least one writing monomer is polymerized through photopolymerization in step (d).

14. The method of claim 10 , wherein the polymerization in step (b) does not induce polymerization of the writing monomer and does not activate any of the RAFT functionalities of the at least one second multifunctional monomer.

15. The method of claim 10 , wherein steps (c) and (d) are carried out simultaneously, wherein the activation of the RAFT functionalities of the at least one second multifunctional monomer also induces polymerization of the at least one writing monomer.

16. The method of claim 10 , wherein the at least one first multifunctional monomer is selected from the group consisting of:

17. The method of claim 10 , wherein the non-reactive counter diffusant is selected from the group consisting of:

2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorononylbutyl carbamate,

2,2,2-trifluoroethylhexyl carbamate,

bis(1,1,1,3,3,3-hexafluoropropan-2-yl)-(2,2,4-trimethylhexane-1,6-diyl) bis carbamate,

2,2,3,3,4,4,5,5,6,6,7,7-dodeca-fluoroheptylbutyl carbamate,

2,2,3,3,4,4,5,5,6,6,7,7-dodeca-fluoroheptylhexyl carbamate,

2,2,3,3,4,4,5,5,6,6,7,7-dodeca-fluoroheptyl propan-2-yl carbamate,

2,2,3,3,4,4,4-heptafluorobutylhexyl carbamate,

2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorononylhexyl carbamate, and

2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorononylcyclohexyl carbamate.

18. The method of claim 10 , wherein the at least one second multifunctional monomer is selected from the group consisting of

Assignments (1)

Continuity (2)

References Cited (95)