Holographic recording material and method for making same

Abstract

Provided herein are compositions suitable for recording holograms, containing thiol and / or thioether functional groups and optionally containing additional allyl and / or propargyl functional groups. These monomers can be used to synthesize holographic polymers with high Δn values. Also provided herein are methods for making holographic polymers and using these polymers to record holograms.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Patent Application No. 63 / 037,296, filed June 10, 2020, entitled "Holographic Recording Materials and Methods of Making Same," the disclosure of which is incorporated herein by reference in its entirety. [Background technology]

[0002] background Holographic photopolymers are an attractive and often desired materials platform for applications including heads-up displays, data storage, and diffractive optical elements due to the ease of processing these polymers and their ability to be recorded in a single step. For all of these applications, a key performance specification that directly correlates to device quality and performance is the achievable index modulation depth (Δn). Efforts to improve the index modulation depth have focused on increasing the refractive index contrast between the write monomer and the matrix while maintaining high monomer solubility, which allows for high write monomer loading in non-phase-separating polymers.

[0003] There is a need in the art for new holographic recording materials and methods for making same, and the present invention addresses this need. Summary of the Invention

[0004] In various aspects, compositions are provided. In certain aspects, the compositions are at least one polymer; a polymeric binder containing a plurality of allyl groups; and Formula (I): At least one monomer of TIFF0007823896000001.tif14128 and formula (II): At least one monomer of TIFF0007823896000002.tif14128 Including, During the ceremony X in each occurrence is independently H or optionally substituted C 6~14 is aryl; each Y is independently -S-, -CH2-, -CH2CH2-, -CH(CH3)CH2-, -CH2CH(CH3)-, -CH(SH)-, -CH[O-CH2-CH=CH2]-, or -CH[O-CH2-C≡CH]-; Each Y T are independently H, -SH, -CH=CH2, -C≡CH, or optionally substituted C 6~14 is aryl; each Z is independently -S-, -CH2, -CH2CH2-, -CH(CH3)CH2-, -CH2CH(CH3)-, or -CH(SH)-; each Z T are independently H, -SH, or -CHSH; m is an integer ranging from 0 to 100; and n is an integer ranging from 0 to 100.

[0005] Advantageously, in various aspects, the compositions may be used to form holographic materials. [Brief explanation of the drawings]

[0006] The drawings illustrate generally, by way of example, but not by way of limitation, various aspects of the present application.

[0007] [Figure 1] Figures 1A-1D show schematic diagrams of holographic film preparation and hologram formation. Figure 1A shows a formulation of a writing monomer and a linear binder with pendant allyl side chains. Figure 1B shows hologram formation and flood curing. Figure 1C shows a formulation of an alcohol-isocyanate linear binder. Figure 1D is a photograph of a typical hologram taken under the illumination of the PC monitor in the foreground on the right. The formulation used contains 43 wt% thiol-ene writing monomer and 30 mol% allyl in the binder. [Figure 2]Figures 2A-2D show hologram performance in terms of dynamic range (Δn). Figure 2A shows the angular reconstruction spectrum of a representative hologram, showing good agreement with a fit to the Kogelnik equation. (The holographic pitch is Λ = 1 μm; the formulation has 30 mol% allyl and 43 wt% thiol-ene.) Figure 2B shows the dynamic range of holograms for various loadings of thiol-ene writing monomer at a pitch of Λ = 0.5 μm. Figure 2C shows the effect of grating period on the dynamic range of various formulations. Figure 2D shows an atomic force microscopy (AFM) image of a sample containing 20 wt% thiol-ene writing monomer and 30 mol% allyl in a polymer binder. [Figure 3] Figure 3 shows the spectrum of the recorded reflection hologram (30 mol % allyl, 43 wt % thiol-ene writing monomer in a polymer binder). [Figure 4] Figure 4 shows a graph of diffraction efficiency (DE) versus production over time (43 wt % thiol-ene monomer and 30 mol % allyl). [Figure 5] FIG. 5 shows the profile characteristics of the same hologram recording film as FIG. [Figure 6] FIG. 6 shows the profile characteristics of a thick holographic film for recording reflection holograms. [Figure 7] Figures 7A-7B show the dynamic range of transmission holograms recorded at a pitch size of 1 μm. Figure 7A shows the dynamic range of holograms for various loadings of thiol-ene writing monomers. Figure 7B shows the effect of allyl content on the dynamic range of various formulations. [Figure 8] Figures 8A-8B show the effect of grating period on the dynamic range of various formulations (Λ is the spatial period). Figure 8A shows the effect of 20 wt% thiol-ene write monomer loading. Figure 8B shows the effect of 33 wt% thiol-ene write monomer loading. [Figure 9]9A-9B show the tunability of the dynamic range of thiol-ene based holograms at pitch sizes of either 0.5 μm (FIG. 9A) or 1 μm (FIG. 9B). [Figure 10] FIG. 10 shows the GPC (gel permeation chromatography) curves of linear matrices with various amounts of allyl content. [Figure 11] Figure 11 shows the optical layout for transmission hologram exposure and reconstruction. Component labels: L1, 633 nm He-Ne laser; L2, 405 nm diode laser; M, mirror; D, power detector; HW, half-wave plate; HF, holographic film; PBS, polarizing beam splitter; S, rotation stage. [Figure 12] Figure 12 shows the optical layout for reflection hologram exposure. Component labels: L1, 633 nm He-Ne laser; M, mirror; D, power detector; HW, half-wave plate; HF, holographic film; PBS, polarizing beam splitter; S, rotation stage. [Figure 13] Figures 13A-13B show AFM images of holograms. Figure 13A has 30 mol% allyl content and 30 wt% thiol-ene writing monomer. Figure 13B has 43 wt% thiol-ene writing monomer and 30 mol% allyl content. [Figure 14] Figures 14A-14B show the dynamic range as a function of the weight percent of thiol-yne photopolymer at a 1 μm pitch (Figure 14A) or a 0.5 μm pitch (Figure 14B). The alkyne used is indicated in the figure, and the thiol is 1,3-bis(2-mercaptoethylthio)-2-mercaptopropane. [Figure 15]Figures 15A-15B show the properties of thiol-yne photopolymers. Figure 15A shows the dynamic range as a function of the writing monomer weight percent using thiol-yne photopolymers at a 0.5 μm pitch. The thioalkyne used is indicated in the figure, with the thiol being 1,3-bis(2-mercaptoethylthio)-2-mercaptopropane. Figure 15B shows the conversion as a function of time upon photopolymerization of 1,3-bis(2-mercaptoethylthio)-2-mercaptopropane and the indicated alkyne. [Figure 16A] Figures 16A-16C show FTIR transform versus time plots for Formulations A1 (Figure 16A), B1 (Figure 16B), and C1 (Figure 16C). The mixtures consisted of an initial stoichiometry of 2:1 thiol to alkyne functional group concentration. Each sample was allowed to stabilize in the dark for 1 minute and then irradiated with 30 mW / cm² of 405 nm wavelength light at ambient temperature. [Figure 16B] See legend to Figure 16A. [Figure 16C] See legend to Figure 16A. [Figure 17A] Figures 17A-17C show the thermochemical properties of the thiol-yne photopolymers. Plots of storage modulus and tan δ versus temperature for each thiol-yne photopolymer film are characteristic of step-growth networks. DMA experiments were performed on samples after post-curing at 70 °C overnight. [Figure 17B] See legend to Figure 17A. [Figure 17C] See legend to Figure 17A. [Figure 18] FIG. 18 is a plot of refractive index as a function of thiol conversion observed for Formulation B2 upon irradiation with 405 nm light at 30 mW / cm 2 . [Figure 19] Figures 19A-19B show the properties of holograms recorded in thiol-yne photopolymers according to some embodiments. Figure 19A shows the angular reconstruction spectrum of a hologram recorded using 2d as the writing monomer, which shows a good fit to coupled-wave theory. Figure 19B is a table summarizing the dynamic range and haze measured for holograms using various alkyne writing monomers. [Figure 20] FIG. 20 shows two-dimensional micrometer-scale refractive index structures recorded on a two-stage poly(urethane-thiourethane) (stage 1) / thiol-yne resin B2 (stage 2) matrix by irradiation through a photomask. [Figure 21A] Figures 21A-21C are real-time FTIR plots showing the formation and conversion of vinyl sulfides for Formulations A (1-4) (Figure 21A), B (1-4) (Figure 21B), and C (1-4) (Figure 21C) upon irradiation with 405 nm light at 30 mW / cm. The mixtures consisted of an initial stoichiometry of 2:1 thiol to vinyl functional group concentration. Each sample was allowed to stabilize in the dark for 1 minute and then irradiated. [Figure 21B] See legend to Figure 21A. [Figure 21C] See legend to Figure 21A. [Figure 22] Figure 22 shows the structures of model thiol-yne monomers used to determine the reactivity of 1° and 2° thiols toward monoalkynes, and their resin formulations with a 2:1 molar ratio of thiol and alkyne reactive groups. [Figure 23A] Figures 23A-23B show real-time FTIR data for formulations M1 and M2 demonstrating the reactivity of 1° and 2° thiols toward monoalkynes as a function of thiol conversion (Figure 23A) and yne / vinyl conversion (Figure 23B). The mixtures consisted of an initial stoichiometry of 2:1 thiol to vinyl functional group concentration. Each sample was allowed to stabilize in the dark for 1 minute and then irradiated. [Figure 23B] See legend to Figure 23A. DETAILED DESCRIPTION OF THE INVENTION

[0008] Detailed Description of the Invention In one aspect, described herein are high-performance holographic recording media based on the combination of photoinitiated thiol-ene click chemistry and functional linear polymers used as binders, which have resulted in holographic materials with significantly improved and stable average refractive index contrast (Δn).

[0009] Reference will now be made in detail to certain aspects of the disclosed subject matter, examples of which are illustrated in part in the accompanying drawings. While the disclosed subject matter will be described in conjunction with the enumerated claims, it will be understood that the exemplified subject matter is not intended to limit the claims to the disclosed subject matter.

[0010] Throughout this document, values ​​expressed in range format should be interpreted flexibly to include not only the numerical values ​​explicitly stated as the limits of that range, but also all individual numerical values ​​or subranges within that range, as if each numerical value and subrange were explicitly stated. For example, a range such as "about 0.1% to about 5%" or "about 0.1% to 5%" should be interpreted to include not only about 0.1% to about 5%, but also individual values ​​(e.g., 1%, 2%, 3%, and 4%) and subranges (e.g., 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%) within the stated range. The phrase "about X to Y" has the same meaning as "about X to about Y" unless otherwise indicated. Similarly, the phrase "about X, Y, or about Z" has the same meaning as "about X, about Y, or about Z" unless otherwise indicated.

[0011] As used herein, the terms "a," "an," or "the" are used to include one or more unless the context clearly dictates otherwise. The term "or" is used to refer to a non-exclusive "or" unless otherwise indicated. The phrases "at least one of A and B" or "at least one of A or B" have the same meaning as "A, B, or A and B." Additionally, any expressions or terms employed herein and not specifically defined should be understood to be for illustrative purposes only, not limiting. Any use of section headings is intended to aid in the reading of the document and should not be construed as limiting; information associated with a section heading may be found within or outside that particular section. All publications, patents, and patent documents mentioned herein are incorporated by reference in their entirety, as if individually incorporated by reference.

[0012] In the methods described herein, acts may be performed in any order unless a temporal or operational order is explicitly recited. Furthermore, specified acts may be performed simultaneously unless the claim language expressly recites them as being performed separately. For example, a claimed act of performing X and a claimed act of performing Y may be performed simultaneously in a single operation, and the resulting process would be encompassed within the process language of the claim.

[0013] definition As used herein, the term "about" allows for some variation in a value or range, for example, within 10%, within 5%, or within 1% of a stated value or stated range limit, and includes that stated value or range.

[0014] As used herein, the term "substantially" refers to a majority or majority of, such as at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.9%, 99.99%, or at least about 99.999% or more, or 100%. As used herein, the term "substantially free" can mean completely free of, or having such an insignificant amount of material that the amount of material present does not affect the material properties of a composition containing the material, such as from about 0 wt% to about 5 wt%, or from about 0 wt% to about 1 wt%, or not more than about 5 wt%, or less than, equal to, or more than about 4.5 wt%, 4, 3.5, 3, 2.5, 2, 1.5, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.01, or not more than about 0.001 wt% of the composition. The term "substantially free" can mean that a material has an insignificant amount, such as from about 0 wt% to about 5 wt% of the composition, or from about 0 wt% to about 1 wt%, or less than or equal to about 5 wt%, or less than, equal to, or more than about 4.5 wt%, 4, 3.5, 3, 2.5, 2, 1.5, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.01, or less than or equal to about 0.001 wt%, or about 0 wt%.

[0015] As used herein, the term "organic group" refers to any carbon-containing functional group. Examples may include oxygen-containing groups such as alkoxy groups, aryloxy groups, aralkyloxy groups, and oxo (carbonyl) groups; carboxyl groups, including carboxylic acids, carboxylates, and esters; sulfur-containing groups, such as alkyl and aryl sulfide groups; and other heteroatom-containing groups. Non-limiting examples of organic groups include OR, OOR, OC(O)N(R), CN, CF, OCF, R, C(O), methylenedioxy, ethylenedioxy, N(R), SR, SOR, SO, SO, N(R), SO, R, C(O)R, C(O)C(O)R, C(O)CHC(O)R, C(S)R, C(O)OR, OC(O)R, C(O)N(R), OC(O)N(R), C(S)N(R), (CH) 0~2N(R)C(O)R, (CH2) 0~2 N(R)N(R)2, N(R)N(R)C(O)R, N(R)N(R)C(O)OR, N(R)N(R)CON(R)2, N(R)SO2R, N(R)SO2N(R)2, N(R)C(O)OR, N(R)C(O)R, N( R)C(S)R, N(R)C(O)N(R)2, N(R)C(S)N(R)2, N(COR)COR, N(OR)R, C(=NH)N(R)2, C(O)N(OR)R, C(=NOR)R, and substituted or unsubstituted (C1~C 100 ) hydrocarbyl, where R can be hydrogen (in examples containing other carbon atoms) or a carbon-based moiety, where the carbon-based moiety can be substituted or unsubstituted.

[0016] The term "substituted" as used herein in conjunction with a molecule or organic group defined herein refers to a state in which one or more hydrogen atoms contained therein are replaced with one or more non-hydrogen atoms. As used herein, the term "functional group" or "substituent" refers to a group that can or does substitute for a molecule or organic group. Examples of substituents or functional groups include, but are not limited to, halogens (e.g., F, Cl, Br, and I); oxygen atoms in groups such as hydroxyl groups, alkoxy groups, aryloxy groups, aralkyloxy groups, oxo(carbonyl) groups, carboxylic acids, carboxylic acid salts, and carboxylic acid esters; sulfur atoms in groups such as thiol groups, alkyl and aryl sulfide groups, sulfoxide groups, sulfone groups, sulfonyl groups, and sulfonamide groups; nitrogen atoms in groups such as amines, hydroxylamine, nitriles, nitro groups, N-oxides, hydrazides, azides, and enamines; and other heteroatoms in various other groups. Non-limiting examples of substituents that may be attached to a substituted carbon (or other) atom include F, Cl, Br, I, OR, OC(O)N(R), CN, NO, NO, ONO, azido, CF, OCF, R, O(oxo), S(thiono), C(O), S(O), methylenedioxy, ethylenedioxy, N(R), SR, SOR, SO, SO, N(R), SO, R, C(O)R, C(O)C(O)R, C(O)CHC(O)R, C(S)R, C(O)OR, OC(O)R, C(O)N(R), OC(O)N(R), C(S)N(R), (CH) 0~2 N(R)C(O)R, (CH2) 0~2 N(R)N(R), N(R)N(R)C(O)R, N(R)N(R)C(O)OR, N(R)N(R)CON(R), N(R)SOR, N(R)SON(R), N(R)C(O)OR, N(R)C(O)R, N(R)C(S)R, N(R)C(O)N(R), N(R)C(S)N(R), N(COR)COR, N(OR)R, C(=NH)N(R), C(O)N(OR)R, and C(=NOR)R, where R can be hydrogen or a carbon-based moiety; for example, R can be hydrogen, (C1-C 100) hydrocarbyl, alkyl, acyl, cycloalkyl, aryl, aralkyl, heterocyclyl, heteroaryl, or heteroarylalkyl; or where two R groups attached to a nitrogen atom or adjacent nitrogen atoms can be taken together with the nitrogen atom or atoms to form a heterocyclyl.

[0017] As used herein, the term "alkyl" refers to straight-chain and branched alkyl and cycloalkyl groups having 1 to 40 carbon atoms, 1 to about 20 carbon atoms, 1 to 12 carbon atoms, or in some embodiments, 1 to 8 carbon atoms. Examples of straight-chain alkyl groups include those having 1 to 8 carbon atoms, such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl groups. Examples of branched alkyl groups include, but are not limited to, isopropyl, isobutyl, sec-butyl, t-butyl, neopentyl, isopentyl, and 2,2-dimethylpropyl groups. As used herein, the term "alkyl" encompasses n-alkyl, isoalkyl, and anteisoalkyl groups, as well as other branched forms of alkyl. Representative substituted alkyl groups may be substituted one or more times with any of the groups enumerated herein, such as amino, hydroxy, cyano, carboxy, nitro, thio, alkoxy, and halogen groups.

[0018] The term "alkenyl," as used herein, refers to straight- and branched-chain and cyclic alkyl groups, as defined herein, except that there is at least one double bond between two carbon atoms. Thus, alkenyl groups have from 2 to 40 carbon atoms, or from 2 to about 20 carbon atoms, or from 2 to 12 carbon atoms, or in some embodiments, from 2 to 8 carbon atoms. Examples include, but are not limited to, vinyl, -CH=C=CCH2, -CH=CH(CH3), -CH=C(CH3)2, -C(CH3)=CH2, -C(CH3)=CH(CH3), -C(CH2CH3)=CH2, cyclohexenyl, cyclopentenyl, cyclohexadienyl, butadienyl, pentadienyl, and hexadienyl, among others.

[0019] The term "alkynyl," as used herein, refers to straight- and branched-chain alkyl groups, except that there is at least one triple bond between two carbon atoms. Thus, alkynyl groups have from 2 to 40 carbon atoms, from 2 to about 20 carbon atoms, or from 2 to 12 carbon atoms, or in some embodiments, from 2 to 8 carbon atoms. Examples include, but are not limited to, -C≡CH, -C≡C(CH), -C≡C(CHCH), -CHC≡CH, -CHC≡C(CHCH), and -CHC≡C(CHCH), among others.

[0020] The term "acyl," as used herein, refers to a group containing a carbonyl moiety and bonded through the carbonyl carbon atom. The carbonyl carbon atom is bonded to a hydrogen atom forming a formyl group or to another carbon atom, which may be part of an alkyl, aryl, aralkyl, cycloalkyl, cycloalkylalkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, heteroarylalkyl group, etc. The acyl group may contain 0 to about 12, 0 to about 20, or 0 to about 40 additional carbon atoms bonded to the carbonyl group. Acyl groups may contain double or triple bonds within the meaning herein. An acryloyl group is an example of an acyl group. Acyl groups may also contain heteroatoms within the meaning herein. A nicotinoyl group (pyridyl-3-carbonyl) is an example of an acyl group within the meaning herein. Other examples include acetyl, benzoyl, phenylacetyl, pyridylacetyl, cinnamoyl, and acryloyl groups, etc. When the group containing the carbon atom bonded to the carbonyl carbon atom contains a halogen, the group is called a "haloacyl" group. An example is a trifluoroacetyl group.

[0021] As used herein, the term "cycloalkyl" refers to cyclic alkyl groups, including, but not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. In some embodiments, cycloalkyl groups can have from 3 to about 8-12 ring members, while in other embodiments, the number of ring carbon atoms ranges from 3 to 4, 5, 6, or 7. Cycloalkyl groups further include polycyclic cycloalkyl groups, including, but not limited to, norbornyl, adamantyl, bornyl, camphenyl, isocamphenyl, and carenyl groups, as well as fused rings, including, but not limited to, decalinyl. Cycloalkyl groups also include rings substituted with straight- or branched-chain alkyl groups, as defined herein. Representative substituted cycloalkyl groups can be mono- or more than one substituted, including, but not limited to, 2,2-, 2,3-, 2,4-, 2,5-, or 2,6-disubstituted cyclohexyl groups or mono-, di-, or tri-substituted norbornyl or cycloheptyl groups, which can be substituted with, for example, amino, hydroxy, cyano, carboxy, nitro, thio, alkoxy, and halogen groups. The term "cycloalkenyl," alone or in combination, refers to a cyclic alkenyl group.

[0022] As used herein, the term "aryl" refers to a cyclic aromatic hydrocarbon group that does not contain heteroatoms within the ring. Thus, aryl groups include, but are not limited to, phenyl, azulenyl, heptalenyl, biphenyl, indacenyl, fluorenyl, phenanthrenyl, triphenylenyl, pyrenyl, naphthacenyl, chrysenyl, biphenylenyl, anthracenyl, and naphthyl groups. In some embodiments, aryl groups contain from about 6 to about 14 carbon atoms in the ring portion of the group. Aryl groups can be unsubstituted or substituted as defined herein. Representative substituted aryl groups can be mono-substituted or substituted more than once, and include, but are not limited to, phenyl groups substituted at any one or more of positions 2, 3, 4, 5, or 6 of the phenyl ring, or naphthyl groups substituted at any one or more of positions 2 through 8.

[0023] The term "aralkyl" as used herein refers to an alkyl group, as defined herein, in which a hydrogen or carbon bond of the alkyl group is replaced with a bond to an aryl group, as defined herein. Representative aralkyl groups include benzyl and phenylethyl groups, as well as fused (cycloalkylaryl)alkyl groups such as 4-ethyl-indanyl. An aralkenyl group is an alkenyl group, as defined herein, in which a hydrogen or carbon bond of the alkyl group is replaced with a bond to an aryl group, as defined herein.

[0024] As used herein, the term "heterocyclyl" refers to aromatic and non-aromatic ring compounds containing three or more ring members, one or more of which are heteroatoms, including, but not limited to, N, O, and S. Thus, heterocyclyl can be cycloheteroalkyl or heteroaryl, or, if polycyclic, any combination thereof. In some embodiments, heterocyclyl groups contain from 3 to about 20 ring members, while other heterocyclyl groups contain from 3 to about 15 ring members. A heterocyclyl group designated as a C2-heterocyclyl can be a 5-membered ring with 2 carbon atoms and 3 heteroatoms, a 6-membered ring with 2 carbon atoms and 4 heteroatoms, etc. Similarly, a C4-heterocyclyl can be a 5-membered ring with 1 heteroatom, a 6-membered ring with 2 heteroatoms, etc. The sum of the number of carbon atoms and the number of heteroatoms equals the total number of ring atoms. A heterocyclyl ring can also contain one or more double bonds. A heteroaryl ring is an embodiment of a heterocyclyl group. The term "heterocyclyl group" includes fused ring species, including those containing fused aromatic and non-aromatic groups. For example, dioxolanyl and benzodioxolanyl ring systems (methylenedioxyphenyl ring systems) are both heterocyclyl groups within the meaning herein. The term also includes polycyclic ring systems containing heteroatoms, such as, but not limited to, quinuclidyl. Heterocyclyl groups can be unsubstituted or substituted as defined herein. Heterocyclyl groups include, but are not limited to, pyrrolidinyl, piperidinyl, piperazinyl, morpholinyl, pyrrolyl, pyrazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, thiazolyl, pyridinyl, thiophenyl, benzothiophenyl, benzofuranyl, dihydrobenzofuranyl, indolyl, dihydroindolyl, azaindolyl, indazolyl, benzimidazolyl, azabenzimidazolyl, benzoxazolyl, benzothiazolyl, benzothiadiazolyl, imidazopyridinyl, isoxazolopyridinyl, thianaphthalenyl, purinyl, xanthinyl, adeninyl, guaninyl, quinolinyl, isoquinolinyl, tetrahydroquinolinyl, quinoxalinyl, and quinazolinyl groups.Representative substituted heterocyclyl groups can be mono-substituted or substituted more than once, including, but not limited to, piperidinyl or quinolinyl groups that are 2-, 3-, 4-, 5-, or 6-substituted or di-substituted with groups such as those listed herein.

[0025] As used herein, the term "heteroaryl" refers to an aromatic ring compound containing five or more ring members, one or more of which are heteroatoms, including, but not limited to, N, O, and S; by way of example, a heteroaryl ring can have from five to about eight to twelve ring members. Heteroaryl groups are a variety of heterocyclyl groups having an aromatic electronic structure. A heteroaryl group designated as C2-heteroaryl can be a five-membered ring with two carbon atoms and three heteroatoms, a six-membered ring with two carbon atoms and four heteroatoms, etc. Similarly, a C4-heteroaryl can be a five-membered ring with one heteroatom, a six-membered ring with two heteroatoms, etc. The sum of the number of carbon atoms and heteroatoms equals the total number of ring atoms. Heteroaryl groups include, but are not limited to, pyrrolyl, pyrazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, thiazolyl, pyridinyl, thiophenyl, benzothiophenyl, benzofuranyl, indolyl, azaindolyl, indazolyl, benzimidazolyl, azabenzimidazolyl, benzoxazolyl, benzothiazolyl, benzothiadiazolyl, imidazopyridinyl, isoxazolopyridinyl, thianaphthalenyl, purinyl, xanthinyl, adeninyl, guaninyl, quinolinyl, isoquinolinyl, tetrahydroquinolinyl, quinoxalinyl and quinazolinyl groups.Heteroaryl groups can be unsubstituted or substituted with the groups discussed herein.Representative substituted heteroaryl groups can be substituted one or more times with groups such as those listed herein.

[0026] Additional examples of aryl and heteroaryl groups are phenyl, biphenyl, indenyl, naphthyl (1-naphthyl, 2-naphthyl), N-hydroxytetrazolyl, N-hydroxytriazolyl, N-hydroxyimidazolyl, anthracenyl (1-anthracenyl, 2-anthracenyl, 3-anthracenyl), thiophenyl (2-thienyl, 3-thienyl), furyl (2-furyl, 3-furyl), indolyl, oxadiazolyl, isoxazolyl, quinazolinyl, fluorenyl, oxane, and the like. Thenyl, isoindanyl, benzhydryl, acridinyl, thiazolyl, pyrrolyl (2-pyrrolyl), pyrazolyl (3-pyrazolyl), imidazolyl (1-imidazolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl), triazolyl (1,2,3-triazol-1-yl, 1,2,3-triazol-2-yl, 1,2,3-triazol-4-yl, 1,2,4-triazol-3-yl), oxazolyl (2-oxazolyl, 4-oxazolyl, 5-oxazolyl), Thiazolyl (2-thiazolyl, 4-thiazolyl, 5-thiazolyl), pyridyl (2-pyridyl, 3-pyridyl, 4-pyridyl), pyrimidinyl (2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 6-pyrimidinyl), pyrazinyl, pyridazinyl (3-pyridazinyl, 4-pyridazinyl, 5-pyridazinyl), quinolyl (2-quinolyl, 3-quinolyl, 4-quinolyl, 5-quinolyl, 6-quinolyl, 7-quinolyl, 8-quinolyl), isoquinolyl (1-isoquinolyl, 3-isoquinolyl, 4-isoquinolyl, 5-isoquinolyl, 6-isoquinolyl, 7-isoquinolyl, 8-isoquinolyl), benzo[b]furanyl (2-benzo[b]furanyl, 3-benzo[b]furanyl, 4-benzo[b]furanyl, 5-benzo[b]furanyl, 6-benzo[b]furanyl, 7-benzo[b]furanyl), 2,3-dihydro-benzo[b]furanyl (2-(2,3-dihydro-benzo[b]furanyl), 3-(2,3-dihydro-benzo[b]furanyl), 4-(2,3-dihydro-benzo[b]furanyl), 5-(2,3-dihydro-benzo[b]furanyl), 6-(2,3-dihydro-benzo[b]furanyl), 7-(2,3-Dihydro-benzo[b]furanyl), benzo[b]thiophenyl (2-benzo[b]thiophenyl, 3-benzo[b]thiophenyl, 4-benzo[b]thiophenyl, 5-benzo[b]thiophenyl, 6-benzo[b]thiophenyl, 7-benzo[b]thiophenyl), 2,3-dihydro-benzo[b]thiophenyl, (2-(2,3-dihydro-benzo[b]thiophenyl), 3-(2,3-dihydro-benzo[b]thiophenyl), 4-(2,3-dihydro-benzo[b]thiophenyl), 5-(2,3-dihydro-benzo[b]thiophenyl) nyl), 6-(2,3-dihydro-benzo[b]thiophenyl), 7-(2,3-dihydro-benzo[b]thiophenyl), indolyl (1-indolyl, 2-indolyl, 3-indolyl, 4-indolyl, 5-indolyl, 6-indolyl, 7-indolyl), indazole (1-indazolyl, 3-indazolyl, 4-indazolyl, 5-indazolyl, 6-indazolyl, 7-indazolyl), benzimidazolyl (1-benzimidazolyl, 2-benzimidazolyl, 4-benzimidazolyl, 5-benzimidazolyl, 6-benzimidazolyl zolyl, 7-benzimidazolyl, 8-benzimidazolyl), benzoxazolyl (1-benzoxazolyl, 2-benzoxazolyl), benzothiazolyl (1-benzothiazolyl, 2-benzothiazolyl, 4-benzothiazolyl, 5-benzothiazolyl, 6-benzothiazolyl, 7-benzothiazolyl), carbazolyl (1-carbazolyl, 2-carbazolyl, 3-carbazolyl, 4-carbazolyl), 5H-dibenzo[b,f]azepine (5H-dibenzo[b,f]azepin-1-yl, 5H-dibenzo[b,f]azepin-2-yl, 5 H-dibenzo[b,f]azepin-3-yl, 5H-dibenzo[b,f]azepin-4-yl, 5H-dibenzo[b,f]azepin-5-yl), 10,11-dihydro-5H-dibenzo[b,f]azepine (10,11-dihydro-5H-dibenzo[b,f]azepin-1-yl, 10,11-dihydro-5H-dibenzo[b,f]azepin-2-yl, 10,11-dihydro-5H-dibenzo[b,f]azepin-3-yl, 10,11-dihydro-5H-dibenzo[b,f]azepin-4-yl, 10,11-dihydro-5H-dibenzo[b,f]azepin-5-yl) and the like.

[0027] The term "heterocyclylalkyl" as used herein refers to an alkyl group, as defined herein, in which a hydrogen or carbon bond of the alkyl group, as defined herein, is replaced with a bond to a heterocyclyl group, as defined herein. Representative heterocyclylalkyl groups include, but are not limited to, furan-2-ylmethyl, furan-3-ylmethyl, pyridin-3-ylmethyl, tetrahydrofuran-2-ylethyl, and indol-2-ylpropyl.

[0028] The term "heteroarylalkyl," as used herein, refers to an alkyl group, as defined herein, in which a hydrogen or carbon bond of the alkyl group is replaced with a bond to a heteroaryl group, as defined herein.

[0029] The term "alkoxy," as used herein, refers to an oxygen atom connected to an alkyl group, including a cycloalkyl group, as defined herein. Examples of linear alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, and the like. Examples of branched alkoxy groups include, but are not limited to, isopropoxy, sec-butoxy, tert-butoxy, isopentyloxy, isohexyloxy, and the like. Examples of cyclic alkoxy groups include, but are not limited to, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, and the like. An alkoxy group can contain about 1 to about 12, about 1 to about 20, or about 1 to about 40 carbon atoms bonded to the oxygen atom, and can further contain double or triple bonds and heteroatoms. For example, an allyloxy group or a methoxyethoxy group is an alkoxy group within the meaning herein, as is a methylenedioxy group in the context of two adjacent atoms of a structure being replaced thereby.

[0030] The term "amine" as used herein refers to primary, secondary, and tertiary amines, e.g., having the formula N(group), where each group can independently be H or other than H, e.g., alkyl, aryl, etc. Amines include, but are not limited to, R-NH, e.g., alkylamines, arylamines, alkylarylamines; RNH where each R is independently selected, e.g., dialkylamines, diarylamines, aralkylamines, heterocyclylamines, etc.; and RN where each R is independently selected, e.g., trialkylamines, dialkylarylamines, alkyldiarylamines, triarylamines, etc. The term "amine" as used herein also includes ammonium ions.

[0031] As used herein, the term "amino group" refers to -NH2, -NHR, -NR2, -NR3, where each R is independently selected. + Substituents of the form -NR3, and -NR3 cannot be protonated + " refers to the respective protonated forms except for the following: ##STR1## Thus, any compound substituted with an amino group may be considered an amine. An "amino group" within the meaning herein may be a primary, secondary, tertiary, or quaternary amino group. An "alkylamino" group includes monoalkylamino, dialkylamino, and trialkylamino groups.

[0032] The terms "halo," "halogen," or "halide" group as used herein, by themselves or as part of another substituent, mean, unless otherwise stated, a fluorine, chlorine, bromine, or iodine atom.

[0033] As used herein, the term "haloalkyl" includes monohaloalkyl groups, polyhaloalkyl groups in which all halo atoms may be the same or different, and perhaloalkyl groups in which all hydrogen atoms are replaced with halogen atoms such as fluoro. Examples of haloalkyl include trifluoromethyl, 1,1-dichloroethyl, 1,2-dichloroethyl, 1,3-dibromo-3,3-difluoropropyl, perfluorobutyl, and the like.

[0034] As used herein, the term "epoxy-functional" or "epoxy-substituted" refers to a functional group in which the oxygen atoms of the epoxy substituents are directly bonded to two adjacent carbon atoms of a carbon chain or ring system. Examples of epoxy-substituted functional groups include, but are not limited to, 2,3-epoxypropyl, 3,4-epoxybutyl, 4,5-epoxypentyl, 2,3-epoxypropoxy, epoxypropoxypropyl, 2-glycidoxyethyl, 3-glycidoxypropyl, 4-glycidoxybutyl, 2-(glycidoxycarbonyl)propyl, 3-(3,4-epoxycyclohexyl)propyl, 2-(3,4-epoxycyclohexyl)ethyl, 2-(2,3-epoxycyclopentyl)ethyl, 2-(4-methyl-3,4-epoxycyclohexyl)propyl, 2-(3,4-epoxy-3-methylcyclohexyl)-2-methylethyl, and 5,6-epoxyhexyl.

[0035] The term "monovalent" as used herein refers to a substituent that is connected to the substituted molecule via a single bond. When a substituent is monovalent, such as F or Cl, it is attached to the atom it replaces by a single bond.

[0036] As used herein, the term "hydrocarbon" or "hydrocarbyl" refers to a molecule or functional group that contains carbon and hydrogen atoms. The term usually contains both carbon and hydrogen atoms, but can also refer to a molecule or functional group in which all hydrogen atoms have been replaced with other functional groups.

[0037] As used herein, the term "hydrocarbyl" refers to a functional group derived from a straight-chain, branched, or cyclic hydrocarbon, and may be alkyl, alkenyl, alkynyl, aryl, cycloalkyl, acyl, or any combination thereof. A hydrocarbyl group is (C a ~C bFor example, (C1-C4)hydrocarbyl means that the hydrocarbyl group can be methyl (C1), ethyl (C2), propyl (C3), or butyl (C4), and (C0-C4)hydrocarbyl means that the hydrocarbyl group can be methyl (C1), ethyl (C2), propyl (C3), or butyl (C4). b ) Hydrocarbyl means that in certain embodiments, no hydrocarbyl groups are present.

[0038] As used herein, the term "solvent" refers to a liquid that can dissolve a solid, liquid, or gas. Non-limiting examples of solvents are silicones, organic compounds, water, alcohols, ionic liquids, and supercritical fluids.

[0039] As used herein, the term "independently selected from" means that the referenced groups are the same, different, or a combination thereof, unless the context clearly indicates otherwise. Thus, under this definition, "X 1 , X 2 , and X 3 are independently selected from the noble gases" is intended to mean, for example, 1 , X 2 , and X 3 are all the same or X 1 , X 2 , and X 3 are all different or X 1 and X 2 is the same but X 3 There may be different scenarios and other types.

[0040] As used herein, the term "room temperature" refers to a temperature between about 15°C and 28°C.

[0041] As used herein, the term "standard temperature and pressure" refers to 20°C and 101 kPa.

[0042] Monomers for holographic recording Compounds of formula (I) or those described herein can be prepared according to the general schemes described herein using synthetic methods known to those skilled in the art. The following examples illustrate non-limiting embodiments of the compounds described herein and their preparation.

[0043] In certain embodiments, the composition for a monomer suitable for holographic recording comprises: at least one polymer; a polymeric binder containing a plurality of allyl groups; and Formula (I): At least one monomer of TIFF0007823896000003.tif14128 and formula (II): At least one monomer of TIFF0007823896000004.tif14128 Including, During the ceremony X, in each occurrence, is independently H, optionally substituted C 1~12 Hydrocarbyl or optionally substituted C 6~14 is aryl; each Y is independently -S-, -CH2-, -CH2CH2-, -CH(CH3)CH2-, -CH2CH(CH3)-, -CH(SH)-, -CH[O-CH2-CH=CH2]-, or -CH[O-CH2-C≡CH]-; Each Y T are independently H, -SH, -CHSH, -CH=CH, -C≡CH, or optionally substituted C 6~14 is aryl; each Z is independently -S-, -CH2, -CH2CH2-, -CH(CH3)CH2-, -CH2CH(CH3)-, or -CH(SH)-; each Z T are independently H, -SH, or -CHSH; m is an integer ranging from 0 to 100; and n is an integer ranging from 0 to 100.

[0044] In the monomer of formula (I), (Y) m-Y T is the terminal Y T (Y)-Y T is YYY T where each Y and Y T are independently selected as described herein. Similarly, in the monomer of formula (II), (Z)-Z T ZZZ T where each Z T are independently selected as described herein. In the monomers of formula (I) and formula (II), the terminal Y T or Z T The groups are selected to form chemically stable compounds. In various embodiments, the terminal Y T The group may be optionally substituted C 6~14 In various embodiments, the terminal Z T The group is -SH or -CH2SH.

[0045] In one embodiment, the polymer is a linear polyurethane. Other suitable polymers may include those useful as holographic recording media described herein and known in the art. In some embodiments, the polymer may be a block copolymer. Suitable block copolymers include polycaprolactone-block-polytetrahydrofuran-block-polycaprolactone (M), as described herein. n Approximately 2000).

[0046] In one embodiment, the polymer binder contains from about 0 to about 80 mol % allyl groups. The polymer contains 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, or about 100 mol% allyl groups. In one embodiment, the polymer comprises polycaprolactone-block-polytetrahydrofuran-block-polycaprolactone. The mol% allyl groups is based on the total number of moles of allyl-containing monomer / binder and block copolymer in various embodiments.

[0047] In various embodiments, the ratio of the monomer of Formula (I) to the monomer of Formula (II) is about 9:1 to about 1:9. The ratio of Formula (I):Formula (II) can be any value between 9:1 and 1:9, and in various embodiments, the ratio of Formula (I):Formula (II) can be about 9:1, 8.5:1.5, 8:2, 7.5:2.5, 7:3, 6.5:3.5, 6:4, 5.5:4.5, 1:1, 4.5:5.5, 4:6, 3.5:6, 3:7, 2.5:7.5, 2:8, 1.5:8.5, or about 1:9. In various embodiments, the ratio of the monomer of Formula (I) to the monomer of Formula (II) is a stoichiometric ratio between the thiol group in Formula (II) and the ene or yne group in Formula (I).

[0048] In various embodiments, (Z) n contains at least one -SH moiety. In various embodiments, (Z) n contains at least two -SH moieties. In various embodiments, (Z) ncontains at least three -SH moieties. In various embodiments, the monomer of formula (II) is TIFF0007823896000005.tif31128.

[0049] In various embodiments, X is C 6~10 In some embodiments, X is phenyl. In various embodiments, (Y) m is linear. In one embodiment, (Y) m can be at least one -CH(O-CH-CH=CH)- or -CH(O-CH-C≡CH)- moiety. m can be at least two moieties independently selected from -CH(O-CH2-CH=CH2)- and CH(O-CH2-C≡CH)-.

[0050] In certain embodiments, the monomer of formula (I) is TIFF0007823896000006.tif95152.

[0051] In one embodiment, the total of the monomers of formula (I) and formula (II) can be about 1 to 80% (w / w) of the composition. In some embodiments, the monomers can be about 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 1 , 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, or about 80% (w / w).

[0052] In one embodiment, the compositions described herein are polymerized. In some embodiments, the polymerized compositions may be polymerized using light, such as laser light, a photoinitiator, a radical initiator, a transition metal complex, or the like.

[0053] In various embodiments, holograms produced by the claimed methods have a refractive index modulation depth (Δn) of about 0.01 to about 0.06. In one embodiment, the holograms described herein have a refractive index modulation depth (Δn) of about 0.01, 0.015, 0.02, 0.025, 0.03, 0.035, 0.04, 0.045, 0.05, 0.055, or about 0.06. In some embodiments, the monomers of Formula (I) and Formula (II) are combined with a polymer binder to form a solution.

[0054] In one embodiment, the polymerized composition contains multiple allyl groups crosslinked with the monomer. The crosslinks can be, for example, between the allyl groups of the polymer binder and one or more thiol, allyl, or propargyl groups in the monomer. In some embodiments, the unpolymerized compositions described herein can be formed into a film.

[0055] The refractive index of network polymers can be further increased compared to that of conventional high-refractive-index polymer systems through the formation of thioether bonds. Toward this goal, a series of high-refractive-index writing monomers containing thiol, ene, and yne functional groups have been designed and synthesized as described herein. Each monomer contains a flexible, high-refractive-index core containing aryl and / or thioether groups. Taking advantage of the advantages of step-growth thiol-ene and thiol-yne "click" reactions, such as negligible oxygen sensitivity and low shrinkage, excellent control over material properties, such as refractive index, dispersibility, viscosity, and glass transition temperature, can be achieved.

[0056] In some embodiments, the monomers described herein exhibited high refractive indices in the range of 1.59 to 1.67. Photopolymerization of neat thiol-ene and thiol-yne resins with TPO photoinitiators resulted in n values ​​in the range of 1.6 to 1.7. D An exemplary set of RI values ​​for the synthesized monomers and photopolymers, measured at a wavelength of 589 nm, is shown in Table 1 below.

[0057] Table 1. Refractive index measured at 25°C and 589 nm wavelength for synthesized liquid writing monomers and their photopolymer blends after curing. TIFF0007823896000007.tif74153

[0058] Here, high dynamic range (Δn) holographic media based on thiol-ene click chemistry were conceived and fabricated as shown in Figures 1A-1D. 1,3-bis(2-mercaptoethylthio)-2-mercaptopropane (BMEMP, a trithiol, Figure 1A) and 1,2-ethanedithiol-based diallyl ether (EDTDAE, a diene, Figure 1B) were selected as writing monomers based on their ability to form high refractive index polymers (Table 2) from readily available precursors via a simple synthetic route.

[0059] (Table 2) Refractive index of writing monomers TIFF0007823896000008.tif46128 a) Abbe number = (n d -1) / (n f -n c )

[0060] In an approach similar to the traditional two-step method for producing holographic cross-linked binders, we synthesized a linear polyurethane binder by step-growth polymerization of a diol (trimethylolpropane allyl ether (TMPAE) and a polyol with a Mw of approximately 2000) and a diisocyanate (hexamethylene diisocyanate), which could then be dissolved in a volatile organic solvent along with the writing monomer and photoinitiator. Because the traditional two-step strategy requires orthogonal matrix formation and writing chemistry, using a thiol-X reaction as the writing chemistry in combination with a conventionally polymerized and cross-linked urethane matrix is ​​challenging due to the potential for cross-reaction between the thiol from the writing monomer and the isocyanate from the binder.

[0061] Because having the binder as a linear polymer allows the two processes to be decoupled, we unexpectedly discovered that low-refractive-index urethane-based binders can be formed in the absence of thiol-writing monomers. These polymers were formed with varying levels of TMPAE to facilitate varying levels of thiol-ene writing monomer binding and matrix crosslinking. After blade coating and thermal annealing, films with controllable thicknesses ranging from 3 to 30 microns were prepared and used for holographic recording. Transmission holograms were recorded by exposing the sample to two interfering 405 nm laser beams (Figure 11). Simultaneously, the diffraction efficiency of the hologram was monitored in real time using a 633 nm probe beam, to which the medium is insensitive. A relatively low-intensity exposure of less than 10 seconds is required to achieve the highest diffraction efficiency (DE) (Figure 4), during which the thiol and ene monomers react with each other and with the pendant ene functional groups of the linear polymer to form a crosslinked matrix only within the exposed regions of the film. After exposure, angular reconstruction was performed using the same 633 nm probe beam, and the diffraction efficiency was monitored as a function of angular detuning.

[0062] Figure 2B shows the highest achievable holographic index modulation depths achieved with various loadings of the write monomer (for a transmission hologram with a fringe spacing of Λ = 0.5 μm). As expected, higher write monomer loadings generally resulted in higher index modulation depths, in some cases as high as 0.04. The one exception is the control formulation, in which the binder does not contain allyl side groups. Here, the index modulation depth drops sharply as the write monomer loading increases to as high as 40 wt%. At this high loading, we speculate that the write monomer phase separates from the binder upon polymerization, resulting in a decrease in optical clarity and, correspondingly, diffraction efficiency. However, when allyl reactive sites are present on a linear polymer binder, the binder and write polymer react to form a single crosslinked network in the exposed regions, preventing phase separation and enabling the use of high monomer loadings. To elucidate the effect of allyl side chains, we replot the same data with allyl loading as the independent variable (Figures 7A-7B). Generally, there is an optimum allyl content; low allyl content results in poor anchoring, while excess allyl can interfere with thiol-ene photopolymerization.

[0063] Next, we evaluated the effect of diffuse blurring in the presence of allyl reactive sites on the binder. To this end, holographic performance at two different spatial frequencies is compared (corresponding to a pitch Λ = 0.5 μm vs. 1 μm, as shown in Figures 7A-7B). In the absence of allyl reactive sites, the index modulation depth drops significantly at higher spatial frequencies due to diffuse blurring. In the presence of allyl reactive sites, the index modulation depth remains almost unchanged as a function of spatial frequency, as seen in Figure 2C. Through the reaction, the writing polymer is effectively anchored and immobilized to the binder reactive sites, significantly reducing diffuse blurring. Figures 9A-9B show the performance of all formulations except the control, demonstrating the excellent tunability of thiol-ene-based holograms in terms of dynamic range.

[0064] In Figure 2D, atomic force microscopy (AFM) observation of small surface relief variations allows direct visualization of the recorded fringes. The measured fringe spacing matches the nominal value, and fringe uniformity is good for all formulations (Figures 13A-13B). The surface relief features in Figures 13A-13B are on the order of 10 nm, making their contribution to optical diffraction negligible compared to the variation in volume index within the film. This finding is confirmed by applying an index-matching fluid and a coverslip during holographic reconstruction, achieving the same results.

[0065] Finally, to further demonstrate the performance of this thiol-ene-based recording medium at higher spatial frequencies, reflection holograms were recorded. Generally, index modulation depth often drops sharply at these smaller pitches due to diffuse blur. However, improved reflection hologram performance was expected for this system due to the introduction of covalent chemical bonds between the polymer binder and the writing monomer. Recording was performed at a pitch of Λ = 140 nm with a nominal reflection notch near 405 nm using a single-beam Denisiuk configuration. In one embodiment, the formulation from the previous transmission experiment was used here (30 mol% allyl and 43 wt% thiol-ene writing monomer). Repeated blade coating yielded thicker films of approximately 25 μm, resulting in acceptable surface profiles (Figure 6). Figure 4B shows a typical hologram transmission spectrum (after a 10-second exposure). For comparison, the prediction of the Kogelnik coupled-wave model is also shown (note that the index modulation depth and film thickness were manually selected, rather than the previous least-squares fitting parameters). This behavior is consistent with a 5 × 10 -3 This suggests an index modulation depth exceeding 4×10 for larger pitch transmissions. -2 ), but is still sufficient to achieve diffraction efficiencies better than 90% in these relatively thin films. The spectrally broadened central notch is characteristic of Kogelnik overmodulation and indicates good grating uniformity throughout the sample thickness.

[0066] In summary, thiol-ene click chemistry combined with a linear functionalized polymer binder was implemented to fabricate holographic materials capable of achieving a high dynamic range. By selecting a linear, low-RI polyurethane matrix, holographic films were prepared using a roll-to-roll blade coating method. By incorporating optimal reactive allyl side chains into the linear polyurethane polymer binder, a high dynamic range exceeding 0.04 was obtained, which addressed the issue of diffuse blur occurring at high spatial frequencies. Significant overmodulated reflection holograms were demonstrated, demonstrating the excellent performance of the films at extremely high spatial frequencies and reduced diffuse blur.

[0067] How to record a hologram In one embodiment, a method for recording a hologram is provided. The method includes providing a composition containing a polymeric binder described herein, a monomer of Formula (I), and a monomer of Formula (II), and exposing the composition to laser radiation to form a hologram. The laser radiation can include using two laser beams from a suitable source, such as that shown in FIG. 11. Holograms can also be recorded using other art-recognized methods. Holograms produced by the claimed methods can be used in applications such as head-up displays in vehicles and aircraft, holographic data storage, and holographic optical elements.

[0068] In some embodiments, the preparing step can include coating an inert substrate with the film. Suitable inert substrates can include glass, plastic, metal, semiconductor material, ceramic, rubber, and combinations of these materials. In one embodiment, the exposing step can include crosslinking a polymer binder with the monomers of Formula (I) and Formula (II).

[0069] High refractive index photopolymer In various embodiments, the compounds of formula (IA) and formula (II) can be crosslinked to form photopolymers with high refractive indexes. High refractive index polymers (HRIPs) are recognized as interesting alternatives to silicon and glass for various optoelectronic applications due to their light weight, ease of processing, low cost, and versatile control over material properties. While significant progress has been made in the development of intrinsic HRIPs, most of these strategies rely on thermally driven polymerization techniques, which suffer from a lack of optical transparency, spatial, and temporal control.

[0070] Increasing the refractive index and crosslink density of network polymers without modifying the monomer molecular weight or core structure is challenging. While there have been several recent reports on thiophosphate-based photopolymers, there has been far less research and application directed toward the scalable synthesis of high-refractive-index monomers and photopolymers. Based on a general synthetic protocol developed for high-refractive-index thiol-yne photopolymers, we report here a series of high-refractive-index, low-viscosity propargyl ethers that form miscible resins with multifunctional thiols. Photopolymerization of these resin mixtures under mild conditions yields optically transparent films with refractive index values ​​(nD) ranging from 1.60 to 1.75 in various embodiments.

[0071] In various aspects, compositions are provided. In certain aspects, the compositions are Formula (IA): At least one monomer of TIFF0007823896000009.tif16128 and formula (II): At least one monomer of TIFF0007823896000010.tif14128 Including, During the ceremony X in each occurrence is independently H or optionally substituted C 6~14 is aryl; Y and Y in each occurrence are independently -S-, -CH-, -CHCH-, -CH(CH)CH-, -CHCH(CH)-, -CH(SH)-, -CH[O-CH-CH=CH]-, or -CH[O-CH-C≡CH]-; Y T1 and Y T2 is independently in each occurrence H, -SH, -CH=CH2, -C≡CH, or an optionally substituted C 6~14 is aryl; each Z is independently -S-, -CH2, -CH2CH2-, -CH(CH3)CH2-, -CH2CH(CH3)-, or -CH(SH)-; each Z T are independently H, -SH, or -CHSH; each m1 and m2 is independently an integer ranging from 0 to 100; and n is an integer ranging from 0 to 100.

[0072] Compositions containing at least one monomer of Formula (IA) and Formula (II) can be polymerized using any of the conditions described herein. Polymerization can be photopolymerization, achieved by exposing the monomer composition to UV and / or visible light.

[0073] In various embodiments, the polymeric composition has a refractive index of about 1.63 to about 1.69. In various embodiments, the refractive index of the polymeric composition is at, equal to, or greater than at least about 1.60, 1.61, 1.62, 1.63, 1.64, 1.65, 1.66, 1.67, 1.68, 1.69, 1.70, 1.71, 1.72, 1.73, 1.74, or about 1.75.

[0074] In various embodiments, (Z) n -Z T contains at least one -SH moiety. In various embodiments, (Z) n -Z T contains at least two -SH moieties.

[0075] In various embodiments, the monomer of formula (II) is TIFF0007823896000011.tif31128.

[0076] In various embodiments, m1 is 1, Y1 is -S-, and YT1 is phenyl.

[0077] In various embodiments, (Y1) m1 and (Y2) m2 At least one of them is linear.

[0078] In various embodiments, (Y1) m1 and (Y2) m2 At least one of the groups contains at least one of -CH(O-CH2-CH=CH2)- or -CH(O-CH2-C≡CH)-.

[0079] In various embodiments, (Y1) m1 and (Y2) m2 At least one of Y comprises at least two moieties independently selected from -CH(O-CH-CH=CH)- and -CH(O-CH-C≡CH)-. T1 and Y T2 is -C≡CH.

[0080] In various embodiments, the monomer of formula (IA) is TIFF0007823896000012.tif63152.

[0081] Judicious use of various thiol-X click reactions in monomer synthesis not only allows for the incorporation of numerous sulfide groups but also results in high-yield reactions with minimal by-products. The monomers discussed here were synthesized starting from inexpensive and widely available raw materials and efficiently utilize thiol-epoxide and thiol-halide click reactions (Scheme 1).

[0082] TIFF0007823896000013.tif171159 Scheme 1. Basic synthetic routes for the high refractive index polyfunctional thiols (a), alkyne thioethers (b), and alkyne ethers (c) used in this study, along with their measured viscosity and refractive index (nD / 20°C) values.

[0083] The basic strategy developed here also offers a high degree of freedom in the selection of the backbone and the polymerizable pendant groups. As can be seen from Scheme 2, the structures of each monomer differ in their core structure and the nature and location of the reactive functional groups. For example, the simplest aryl monomer 2a, with only one alkynal group, forms polymers with low crosslink density, but has a lower viscosity (32 cP) and a higher n (1.611) compared to the remaining aryl-containing monomers 2c and 2d.

[0084] The diyne monomer 2b has only sulfur in its backbone and no aryl groups. Although it has a low refractive index (1.591), monomer 2b is the least sterically hindered and has primary thiopropargyl functionality. Similarly, as we progress from 1a to 1c in the thiol monomers, the number of secondary thiol groups increases, correspondingly increasing the refractive index. While maintaining backbone flexibility for improved solubility, the T g Specific material properties such as modulus, elasticity, and hydrophobicity are easily tuned. For example, flexible sulfide linkages throughout the monomer design facilitate increasing the refractive index without substantially increasing the initial resin viscosity or sacrificing the solubility or other optically desirable properties of a given monomer / resin.

[0085] TIFF0007823896000014.tif112152 Scheme 2. Structures of high refractive index polyfunctional thiols (A) and alkynes (B) used in this study and their measured viscosity and refractive index (nD / 20°C) values.

[0086] Because the minimum number of thiol functionalities required to form linear polymers via the thiol-yne click reaction is two, commercially available 2,2'-thiodiethanethiol (1a), with a refractive index (nD / 20 °C) of 1.596, was used as the simplest dithiol. Trithiol (1b) and tetrathiol (1c) were obtained according to a conventional procedure starting from the ring-opening reaction of epichlorohydrin with 2-mercaptoethanol under mild reaction conditions. Thus, the reaction of one equivalent of 2-mercaptoethanol with epichlorohydrin in the presence of a catalytic amount of borax quantitatively and selectively afforded the monosubstituted product, 1-chloro-3-(phenylthio)-2-propanol (CPTP), which was further reacted with half an equivalent of ethanedithiol to afford the corresponding tetrahydroxy intermediate (TetraOH). Similarly, the trihydroxy intermediate (TriOH) was obtained by the reaction of two equivalents of 2-mercaptoethanol with epichlorohydrin in the presence of NaOH as a base. Reaction of TriOH and TetraOH with thiourea, followed by hydrolysis of the corresponding thiouronium salts using 50% NaOH solution, afforded the corresponding TriSH and TetraSH in 74% and 66% overall yields, respectively. Both monomers were isolated as colorless liquids with viscosities of 43 and 189 cP and refractive index values ​​(nD / 20 °C) of 1.636 and 1.647, respectively. Because each alkyne functional group is bifunctional (i.e., capable of reacting twice), the simplest alkyne monomer 2a used in this study was prepared in two high-yield steps, starting with the reaction of epichlorohydrin with thiophenol. In the second step, deprotonation of the 2° alcohol BPTP, followed by alkylation with propargyl bromide, afforded the low-viscosity (32 cP) 2a with a refractive index (nD / 20 °C) of 1.611 in 91% yield. In contrast, monomer 2d, with a viscosity of 14 cP and a refractive index value (nD / 20°C) of 1.591, was in turn prepared in one step in 85% yield via alkylation of dithiol 1a with propargyl chloride in the presence of KOH as a base.

[0087] The first step in the synthesis of diyne monomers 2c and 2d involves the borax-catalyzed selective thiol-epoxide ring-opening reaction of epichlorohydrin with thiophenol. Reaction of epichlorohydrin with one equivalent of thiophenol afforded the chloro intermediate 1-chloro-3-(phenylthio)-2-proponal (CPTP) as a colorless liquid in excellent yield (>90%). Further reaction of the chloro intermediate CPTP with high refractive index dithiol "cores" such as 1,2-ethanedithiol (EDT) and 4,4'-thiobisbenzenethiol (TBT) in the presence of NaOH as a base afforded the corresponding alcohols EDTOH and TBTOH as clear viscous liquids in over 90% yield, respectively. Following this strategy, any high refractive index multifunctional thiol previously reported in the literature can be used to tailor the final material properties depending on the requirements of the application being investigated. Finally, deprotonation of the diol with sodium hydride, followed by alkylation with two equivalents of propargyl bromide, afforded the dipropargyl ethers 2c and 2d in high overall yields of 66% and 76%, respectively. Both 2c and 2d monomers were obtained as liquids with viscosities of 171 cP and 732 cP, respectively, in addition to refractive index values ​​(nD / 20°C) of 1.603 and 1.668, respectively. Overall, the synthesis of these intermediates for both multifunctional thiol and diyne monomers is easily scaled up and stored for several months without special precautions. [Example]

[0088] Various aspects of the present application can be better understood by reference to the following examples, which are provided by way of illustration, and the scope of the present application is not limited to the examples provided herein.

[0089] Basic information regarding chemical synthesis: Commercially available reagents were used without further purification. Thiophenol, epichlorohydrin, 2-mercaptoethanol, and ethanedithiol were purchased from Alfa Aesar. 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) was purchased from Chem-Impex International. Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO) photoinitiator was purchased from TCI America. Thiourea was purchased from Sigma-Aldrich. Reagent-grade sodium hydroxide (NaOH) was purchased from Fisher Scientific. Absolute ethanol (200 proof) was purchased from Decon Labs Inc. 1 H and 13 C-NMR spectra were obtained on a Bruker 400 MHz spectrometer using CDCl3 (internal standard: 7.26 ppm, 1 H: 77.0 ppm, 13 C).

[0090] Example 1: Preparation of 1,3-bis(2-mercaptoethylthio)-2-mercaptopropane (BMEMP, 1b) 1,3-Bis(2-mercaptoethylthio)-2-mercaptopropane (BMEMP) : To a dry 500 g round-bottom flask equipped with a magnetic stir bar, 17.8 g of 2-mercaptoethanol (228 mmol, 2.08 equiv.) was added, diluted with 69 mL (1.58 M) of absolute ethanol, and homogenized. To this solution was added 9.13 g (228 mmol, 2.09 equiv.) of sodium hydroxide. After stirring at room temperature for 10 minutes, 10.1 g (109 mmol, 1 equiv.) of epichlorohydrin was slowly added to the reaction mixture under a N2 atmosphere. The mixture was heated to 50 °C and stirred for 1 hour. After this period, the reaction mixture was cooled to room temperature, and 13.5 g of 36% hydrochloric acid (133 mmol, 1.22 equiv.) was added, resulting in the formation of a precipitate.

[0091] The precipitate was filtered and concentrated under reduced pressure to give 22.05 g (95%) of 1,3-bis(2-hydroxyethylthio)-2-propanol (BHETP) as a slightly yellow viscous liquid, which was used directly in the next step without further purification. In the second step, 22 g of BHETP (104 mmol, 1 equiv.) and 28.9 g (379 mmol, 3.66 equiv.) of thiourea were added to a dry 500 g round-bottom flask equipped with a reflux condenser and a magnetic stir bar, and the mixture was dissolved in 63.3 g (1.58 M) of 36% aqueous hydrochloric acid and homogenized. The solution was heated to 110 °C and stirred for 1 h. After this period, the reaction was cooled to room temperature, and 61.5 g (762 mmol, 7.35 equiv.) of 50% aqueous NaOH was added under a N2 atmosphere. The suspension was stirred at room temperature for 24 h. After this period, 200 mL of toluene was added, and the mixture was suction filtered and then transferred to a separatory funnel. The organic layer was washed with 1 M hydrochloric acid solution, water, and brine, and then dried over sodium sulfate. The solution was filtered and concentrated under reduced pressure to give 25.2 g (93%) of the title compound as a colorless liquid, which was used directly without further purification. TIFF0007823896000015.tif27159

[0092] Example 1a: Alternative preparation of 1,3-bis(2-mercaptoethylthio)-2-mercaptopropane (BMEMP, 1b) TIFF0007823896000016.tif171281-Chloro-3-(hydroxyethylthio)-2-propanol (CHTEP) 2A 500 mL round-bottom flask equipped with a magnetic stir bar was charged with 21.2 mL (25.0 g, 0.27 mol, 1 equiv.) of epichlorohydrin and 10.3 g (0.027 mol, 0.1 equiv.) of borax and diluted with 135 mL of deionized water. To this suspension, 19 mL (21.1 g, 0.27 mol, 1 equiv.) of 2-mercaptoethanol was added dropwise over 1 hour using an addition funnel. The reaction was stirred at room temperature for 4 hours. After this period, the mixture was extracted with CHCl (3 × 100 mL). The combined organics were washed with water (approx. 100 mL, 2X), brine (approx. 50 mL, 1X), dried over NaSO, filtered, and evaporated under reduced pressure to afford 43.0 g (93%) of the title compound CHTEP as a colorless viscous liquid, which was used directly in the next step without further purification. TIFF0007823896000017.tif18158TIFF0007823896000018.tif17128

[0093] 1,3-Bis-(hydroxyethylthio)-2-propanol (BHETP): BHETP was synthesized by adapting procedures reported in the patent literature. 2 To a 1 L round-bottom flask equipped with a magnetic stir bar was added 33.6 mL (37.2 g, 0.48 mol, 2.1 equiv.) of 2-mercaptoethanol and diluted with 318 mL of reagent-grade ethanol. To this solution was added 19.0 g (0.48 mmol, 2.1 equiv.) of NaOH. After stirring at room temperature for 10 min, 21.0 g (0.23 mol, 1.0 equiv.) of epichlorohydrin was added slowly under a N2 atmosphere. The resulting suspension was stirred at room temperature for 16 h. After this period, 27.5 g (0.27 mol, 1.2 equiv.) of 36% hydrochloric acid was added. The precipitate was filtered and concentrated under reduced pressure to give 46.7 g (97%) of the title compound BHETP as a colorless viscous liquid, which was used directly in the next step without further purification. TIFF0007823896000019.tif11143TIFF0007823896000020.tif16128

[0094] 1,3-Bis(2-mercaptoethylthio)-2-mercaptopropane (1b): To a 1 L round-bottom flask equipped with a reflux condenser and stir bar, 46.7 g (0.22 mol, 1 equiv.) of BHETP was dissolved in 133.7 g (1.32 mol, 6 equiv.) of 36% aqueous hydrochloric acid. To this solution, 75.3 g (0.99 mol) of thiourea was added and heated to 110 °C for 1 h. After this period, the flask was cooled to room temperature, and 132.0 g (1.65 mol, 7.5 equiv.) of 50% aqueous NaOH was added under a N2 atmosphere. The suspension was then stirred at room temperature for 24 h. After this period, 200 mL of toluene was added and the mixture was transferred to a separatory funnel and washed with 1 M hydrochloric acid solution (150 mL, 1X), water (approximately 100 mL, 1X), brine (50 mL, 1X), dried over Na2SO4, filtered, and evaporated under reduced pressure to afford the title compound 1b as a colorless viscous liquid, which was used without further purification. TIFF0007823896000021.tif17163

[0095] Example 1b: Preparation of TetraOH TetraOH: To a 500 mL round-bottom flask equipped with a magnetic stir bar was added 4.46 mL (5.00 g, 0.053 mol, 1 equiv.) of 1,2-ethanedithiol and diluted with 106 mL of ethanol. To this solution was added 4.24 g (0.106 mol, 2 equiv.) of NaOH. After stirring for 10 minutes at room temperature, 18.1 g (0.106 mol, 2 equiv.) of CHTEP was slowly added under a N2 atmosphere. The resulting suspension was stirred at room temperature for 16 hours. After this period, 12.9 g (0.127 mol, 2.4 equiv.) of 36% hydrochloric acid was added, and the precipitated solid was filtered off. The filtrate was evaporated under reduced pressure to give 18.1 g (94%) of the title compound as a colorless viscous liquid, which was used directly in the next step without further purification. TIFF0007823896000022.tif19155TIFF0007823896000023.tif17165

[0096] Example 1c: Preparation of Monomer 1c 1c: In a 500 mL round-bottom flask equipped with a reflux condenser and a stir bar, 18 g (0.049 mol, 1 eq.) of TetraOH was dissolved in 40.2 g (0.397 mol, 8 eq.) of 36% aqueous hydrochloric acid. To this solution, 18.1 g (0.238 mol, 4.8 eq.) of thiourea was added and heated to 110 °C for 1 h. After this period, the flask was cooled to room temperature, and 19.9 g (0.496 mol, 10 eq.) of 50% aqueous NaOH was added under a N2 atmosphere. The suspension was then stirred at room temperature for 24 h. After this period, 500 mL of toluene was added and the mixture was transferred to a separatory funnel and washed with 1 M hydrochloric acid solution (250 mL, 1X), water (ca. 150 mL, 1X), brine (100 mL, 1X), dried over Na2SO4, filtered, and evaporated under reduced pressure to afford 16.2 g (76%) of the title compound 1c as a colorless viscous liquid, which was used without further purification. TIFF0007823896000024.tif26155

[0097] Example 1d: Preparation of 1,3-bis-(phenylthio)-2-propanol (BPTP) TIFF0007823896000025.tif171281,3-Bis-(phenylthio)-2-propanol (BPTP): To a 250 mL round-bottom flask equipped with a magnetic stir bar, 16 mL (157 mmol, 2.2 equiv.) of thiophenol was added, then diluted with 230 mL of toluene (0.3 M, w / epichlorohydrin). To this solution, 23 mL of DBU (154 mmol, 2.2 equiv.) was added under a N2 atmosphere and stirred at room temperature for 10 minutes. After this period, 5.5 mL of epichlorohydrin (70.3 mmol, 1.0 equiv.) was added dropwise, and the reaction vessel was stirred at room temperature for 16 hours. After this period, the volatiles were removed under reduced pressure. The residue was diluted with 500 mL of DCM, washed with 1 M HCl (100 mL), water (100 mL), brine (50 mL), dried over anhydrous NaSO, filtered, and concentrated under reduced pressure to give the crude product as a pale yellow liquid. Purification by silica gel column chromatography using 50% EtOAc in hexane as the eluent gave BPTP (17.1 g, 88% yield) as a colorless viscous liquid. TIFF0007823896000026.tif27159

[0098] Example 1e: Preparation of 1-chloro-3-(phenylthio)-2-propanol (CPTP) TIFF0007823896000027.tif17128 1-Chloro-3-(phenylthio)-2-propanol (CPTP): To a 500 mL round-bottom flask equipped with a magnetic stir bar was added 50.0 mL (0.64 mol, 1 equiv.) of epichlorohydrin and 24.4 g (0.064 mol, 0.1 equiv.) of borax, diluted with 320 mL of deionized water. To this suspension, 65 mL (0.64 mol, 1 equiv.) of thiophenol was added dropwise over 1 h using an addition funnel. The reaction was stirred at room temperature for 4 h. After this period, the mixture was extracted with CHCl (3 × 100 mL). The combined organic extracts were washed with water (approx. 100 mL, 2X), brine (approx. 50 mL, 1X), dried over Na2SO4, filtered, and evaporated under reduced pressure to give 99.3 g (96%) of the title compound CPTP as a colorless liquid, which was used directly in the next step without further purification. TIFF0007823896000028.tif20151

[0099] Example 1f: Alternative Preparation of 1,2-Ethanedithiol-Based Intermediate Diol (EDTOH) TIFF0007823896000029.tif19128 1,2-Ethanedithiol-Based Intermediate Diol (EDTOH): 4.46 mL (5.00 g, 53.08 mmol, 1 equiv.) of 1,2-ethanedithiol was added to a 500 mL round-bottom flask equipped with a magnetic stir bar and diluted with 106 mL of ethanol. To this solution was added 4.25 g (106.16 mmol, 2 equiv.) of NaOH. After stirring at room temperature for 10 min, 21.5 g (106.16 mmol, 2 equiv.) of CPTP was added slowly under a N2 atmosphere. The resulting suspension was stirred at room temperature for 24 h. After this period, the ethanol was removed under reduced pressure to give a crude residue that was diluted with EtOAc (approximately 500 mL) and washed with 1N HCl (approximately 150 mL, 2×), water (approximately 150 mL, 1×), and brine (approximately 150 mL, 1×). The combined organics were dried over Na2SO4, filtered, and concentrated under reduced pressure to give a yellow viscous liquid that was subjected to silica gel column chromatography using 60% EtOAc / Hex as the eluent. Fractions containing the desired material were evaporated to give 22.1 g (97%) of the title compound EDTOH as a colorless viscous liquid. TIFF0007823896000030.tif27155

[0100] Example 1g: Preparation of 4,4'-thiobisbenzenethiol intermediate diol (TBTOH) TIFF0007823896000031.tif26146 4,4'-Thiobisbenzenethiol-based intermediate diol (TBTOH): 5.00 g (19.97 mmol) of 4,4'-thiobenzenethiol was added to a 500 mL round-bottom flask equipped with a magnetic stir bar and diluted with 200 mL of toluene. To this suspension was added 6.08 g (39.93 mmol, 2 equiv.) of DBU (1,8-diazabicyclo[5.4.0]undec-7-ene). After stirring at room temperature for 10 min, 8.09 g (39.93 mmol, 2 equiv.) of CPTP was added slowly under a N2 atmosphere. The resulting suspension was heated to 90 °C for 16 h. After this period, the reaction was cooled to room temperature and the toluene was removed under reduced pressure to give a crude residue which was diluted with EtOAc (approximately 250 mL) and washed with 1N HCl (approximately 100 mL, 2×), water (approximately 100 mL, 1×), and brine (approximately 50 mL, 1×). The combined organics were dried over Na2SO4, filtered, and concentrated under reduced pressure to give a yellow viscous liquid which was subjected to silica gel column chromatography using 60% EtOAc / Hex as the eluent. Evaporation of fractions containing the desired material gave 10.6 g (91%) of the title compound TBTOH as a light yellow viscous liquid. TIFF0007823896000032.tif27158

[0101] Example 1h: Preparation of 1,3-bis-(n-propylthio)-2-propanol (BPrTP) TIFF0007823896000033.tif181281,3-Bis-(n-propylthio)-2-propanol (BPrTP): 7.8 mL (8.6 g, 113.5 mmol, 2.1 equiv.) of n-propylthio was added to a 250 mL round-bottom flask equipped with a magnetic stir bar and diluted with 75 mL of reagent-grade ethanol. To this solution was added 4.54 g (113.5 mmol, 2.1 equiv.) of NaOH. After stirring at room temperature for 10 min, 5.0 g (54.0 mmol, 1.0 equiv.) of epichlorohydrin was added slowly under a N2 atmosphere. The resulting suspension was heated to 50 °C for 1 h. After this period, the flask was cooled to room temperature and 6.4 g (64.8 mmol, 1.2 equiv.) of 36% hydrochloric acid was added. The precipitate was filtered and concentrated under reduced pressure to give 10.2 g (91%) of the title compound as a colorless liquid, which was used directly in the next step without further purification. TIFF0007823896000034.tif26157

[0102] Example 1i: Preparation of 1,3-bis-(n-propylthio)-2-propanethiol (3a) TIFF0007823896000035.tif321281,3-Bis-(n-propylthio)-2-propanethiol (3a): In a 250 mL round-bottom flask equipped with a reflux condenser and a stir bar, 10.2 g (48.95 mmol, 1 equiv.) of BPrTP was dissolved in 9.9 g (97.9 mmol, 2 equiv.) of 36% aqueous hydrochloric acid. To this solution, 5.6 g (73.42 mmol, 1.5 equiv.) of thiourea was added and heated to 110 °C for 1 h. After this period, the flask was cooled to room temperature, and 9.8 g (122.4 mmol, 2.5 equiv.) of 50% aqueous NaOH was added under a N atmosphere. The suspension was then stirred at room temperature for 24 h. After this period, 200 mL of toluene was added and the mixture was transferred to a separatory funnel and washed with 1 M hydrochloric acid solution (150 mL, 1X), water (ca. 100 mL, 1X), brine (50 mL, 1X), dried over Na2SO4, filtered and evaporated under reduced pressure to give the crude product which was purified by silica gel column chromatography using 10% EtOAc / hexanes as the eluent to give 8.4 g (77%) of the title compound 3a as a colorless liquid. TIFF0007823896000036.tif27155

[0103] Example 2: Preparation of 1,2-ethanedithiol-based diallyl ether (EDTDAE) 1,2-Ethanedithiol-Based Diallyl Ether (EDTDAE): EDTDAE was prepared according to a previously reported procedure. Briefly, 50 mL (640 mmol, 1 equiv.) of epichlorohydrin and 24.4 g (64 mmol, 0.1 equiv.) of borax were added to a dry 500 g round-bottom flask equipped with a magnetic stir bar and 320 mL (2 M) of deionized water. Using an addition funnel, 65 mL (635 mmol, 1 equiv.) of thiophenol was added dropwise to the stirred solution over 1 h. The reaction was carried out at room temperature for 4 h. The mixture was then extracted with CHCl (3 × 100 mL) and then washed with water (200 mL) and brine (50 mL). The combined extracts were dried over NaSO and concentrated in vacuo to give 99.3 g of 1-chloro-3-(phenylthio)-2-propanol (CPTP) (96% yield). The compound was used as is without further purification. In the second step, 4.46 mL (5.00 g, 53.08 mmol, 1 equiv.) of 1,2-ethanedithiol was added to a 500 mL round-bottom flask equipped with a magnetic stir bar and diluted with 106 mL of ethanol. To this solution, 4.25 g (106.16 mmol, 2 equiv.) of NaOH was added. After stirring at room temperature for 10 minutes, 21.5 g (106.16 mmol, 2 equiv.) of CPTP was slowly added under a N2 atmosphere.

[0104] The resulting suspension was stirred at room temperature for 24 hours. After this period, the ethanol was removed under reduced pressure to give a crude residue, which was diluted with EtOAc (approximately 500 mL) and washed with 1N HCl (approximately 150 mL, 2X), water (approximately 150 mL, 1X), and brine (approximately 150 mL, 1X). The combined organics were dried over Na2SO4, filtered, and concentrated under reduced pressure to give a yellow viscous liquid, which was subjected to silica gel column chromatography using 60% EtOAc / hexanes as the eluent. Fractions containing the desired material were evaporated to give 22.1 g (97%) of 1,2-ethanedithiol-based diol (EDT-OH) as a colorless viscous liquid. In the final step, 10.0 g (23.44 mmol, 1 equiv.) of EDT-OH was added to a 500 mL round-bottom flask equipped with a magnetic stir bar and diluted with 117 mL of anhydrous THF. The flask was cooled to 0 °C, and 1.69 g (70.31 mmol, 3 equiv.) of NaH was added portionwise. After stirring at room temperature for 30 minutes, 8.50 g (70.31 mmol, 3 equiv.) of allyl bromide was added, followed by 0.39 g (2.34 mmol, 0.1 equiv.) of potassium iodide. The resulting solution was stirred at room temperature for 16 hours. After this period, the reaction mixture was diluted with EtOAc (approx. 300 mL) and washed with 1 N HCl (approx. 100 mL, 2X), water (approx. 100 mL, 1X), and brine (approx. 50 mL, 1X). The combined organics were dried over Na2SO4, filtered, and concentrated under reduced pressure to give the crude material as a pale yellow liquid, which was purified by silica gel column chromatography eluting with (30% EtOAc / hexanes). The product-containing fractions were evaporated under reduced pressure to give 8.3 g (71%) of the title compound (EDTDAE) as a pale yellow viscous liquid. TIFF0007823896000037.tif78156

[0105] Example 3: Hologram recording film Preparation of holographic recording film: Polycaprolactone-block-polytetrahydrofuran-block-polycaprolactone (M nApproximately 2000), 1,6-diisocyanatohexane, and 2-(allyloxymethyl)-2-ethyl-1,3-propanediol were mixed in a vial according to Table 3 to obtain linear polyurethanes with various allyl side chain contents.

[0106] (Table 3) Linear matrix composition table TIFF0007823896000038.tif38151 a) Allyl content = moles TMPAE / (moles TMPAE + moles Polyol 2000). HDI = 1,6-hexane diisocyanate.

[0107] The vials were then placed in a 70°C oven overnight for polymerization. Afterwards, a polymer solution with a controlled concentration of 20% w / w (determined by the mass of polymer binder relative to the total of polymer and solvent) was prepared using acetone as the solvent, while a thiol-ene writing monomer was also dissolved in the solution using the stoichiometric ratio that can be found in Table 4.

[0108] Table 4: Composition of writing monomers a TIFF0007823896000039.tif75128 a) Thiol-ene content = mass of thiol-ene monomer / (mass of polymer matrix + mass of thiol-ene) Each film was blade-coated with 100 μL of solution onto one glass slide (Fisherbrand, 2.54 cm × 7.62 cm) using a ZAA 2300 Automatic Film Applicator while the temperature was maintained at 45° C. Finally, the film was held on a platform at 45° C. for 2 minutes.

[0109] The refractive indices of linear matrices with various allyl contents according to various embodiments are summarized in Table 5.

[0110] Table 5. Refractive index of linear matrices with varying amounts of allyl content TIFF0007823896000040.tif75165 a) All refractive indices are the average of three samples. b) Abbe number = (n d -1) / (n f -n c )

[0111] The molecular weights of linear polymer matrices according to some embodiments are listed in Table 6.

[0112] Table 6. Molecular weight of linear polymer matrix a TIFF0007823896000041.tif61165 a) The molecular weight was measured twice and the average of the two tests was used. The PDI was calculated using the average molecular weight.

[0113] Example 4: Properties of recorded holograms Holographic recording and dynamic range (Δn) determination: Transmission holograms were recorded in a two-beam interference setup as shown in Figure 11. A spatially filtered, wavelength-stabilized 405 nm laser diode (Ondax, 40 mW) was used to obtain a total intensity of approximately 16 mW / cm. 2 An optically modulated recording beam of 0.5 μm and 1 μm was generated. In the experiments, two grating periods, 0.5 μm and 1 μm, were used, achieved by recording at external recording half angles of 23.9° and 11.2°, respectively. Hologram generation during the recording process was simultaneously investigated via a 633 nm He-Ne laser (Thorlabs) aligned approximately to the Bragg reconstruction angle. After writing, the sample was rotated from -15° to 15° at a rate of 0.2° / s to determine the angular selectivity of the recorded hologram; during this rotation, the diffraction efficiency (DE), defined as the quotient of the diffracted light to the total light (transmitted and diffracted), was recorded versus time. A 15-second exposure was used for the 33 wt% and 43 wt% monomer loading groups, while the 20 wt% group was exposed for 45 seconds; thus, the best diffraction efficiency was achieved for all samples. Finally, the Kogelnik coupled-wave theory was applied to fit the angular selectivity to determine the refractive index modulation depth (Δn) and film thickness.

[0114] Determination of film profile: Measurements of the surface roughness and thickness of the films were performed using an XT model stylus profilometer from Dektak. The thickness was obtained by scanning from a blank area of ​​the glass substrate to the area covered with the polymer film. The roughness of the film was analyzed by scanning within the film area.

[0115] Shelf-life evaluation of the writing monomer: Trithiol and diene monomers were mixed in a vial in a stoichiometric ratio; 3 wt% photoinitiator diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO) was added according to the mass of the monomers and homogenized using a vortex mixer. The mixture was then cast onto a clean glass slide (Fisher Scientific) and sandwiched between the same slides using binder clips with a 250 μm-thick polyethylene terephthalate spacer. The area of ​​the double bond peak (approximately 6113 cm) was measured using a Thermo Scientific Nicolet iS50 FT-IR spectrometer in the near-IR range. -1 ) and the area of ​​all peaks (5570 cm -1 ~6180cm -1 The remaining double bonds were monitored over time by calculating the ratio of the double bonds remaining after different times to the initial ratio.

[0116] Stability Evaluation of Holograms and Unrecorded Film: Three stability evaluations were performed in this experiment. The stability of empty film (EF) was determined using the ratio of the dynamic range of a hologram recorded at a specific time after film preparation to the dynamic range of a hologram recorded immediately after film preparation. The dynamic range obtained from reading the same hologram at various times was compared to the initial dynamic range to determine the stability of hologram-recorded film (HF) and flood-cured hologram film (FCHF). Flood curing was performed by exposing the samples to a 27W 405nm LED lamp for 3 minutes.

[0117] Haze measurement for holograms and films: Transmitted haze percentage is measured over an 18mm measurement area. 2 The haze was measured using a haze meter named Haze-gard i from BYK. Three samples were prepared for each formulation, while three measurements were taken at different points on each sample. Thus, the average with standard deviation was obtained and plotted in the figures.

[0118] Microscopic characterization of the gratings in the holograms: A Digital Instruments Dimensional 3100 Atomic Force Microscope (AFM) was applied to determine the height profile within the holograms with a scan size of 10 μm at a scan rate of 0.5003 Hz. The holograms were analyzed with a Hitachi SU3500 scanning electron microscope (SEM).

[0119] Refractive index (RI) measurements: An Anton Paar refractometer was used to determine the refractive index at the wavelengths of the Fraunhofer C, D, and F spectral lines (656.3 nm, 589.3 nm, and 486.1 nm, respectively). The Abbe number could then be calculated according to the definition. The refractive index of the writing monomer and the linear polymer matrix was measured directly. The thiol-ene writing monomer was mixed stoichiometrically with 3% w / w% TPO and exposed to a 405 nm LED lamp for 3 minutes to form a polymer. The RI of the polymer was then measured, showing the RI of the writing polymer formed in bright fringes during recording.

[0120] Reflection hologram recording: The films used for reflection holography were prepared using multiple blade coatings to obtain thick films around 25 μm thick. Reflection holograms were recorded using a 405 nm LED at 131 mW / cm at a 10° angle of incidence following a 3-minute flood cure. 2 The signal was recorded in a single-beam Denisyuk configuration with a laser intensity of 1000 Hz (Figure 4A); then, the transmission spectrum was measured at the same recording position by a high-resolution spectrometer (Avantes AvaSpec-ULS4096CL-EVO).

[0121] The terms and expressions used in this specification are used as terms of description and not of limitation, and the use of such terms and expressions is not intended to exclude any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the embodiments of this specification. Thus, although this specification describes specific embodiments and optional features, it should be understood that modifications and variations of the compositions, methods, and concepts disclosed herein may be made by those skilled in the art, and that such modifications and variations are considered to be within the scope of the embodiments of this specification.

[0122] Example 5: Photopolymerization of thiol-yne monomers and real-time FTIR kinetics Without being bound by theory, the generally accepted mechanism for thiol-yne photopolymerization is shown in Scheme 2. Mechanistically, the radical-mediated thiol-yne reaction is similar to that of the radical-mediated thiol-ene reaction, except that here each alkyne group reacts twice with a thiyl radical. An additional step involves the reaction of the vinyl sulfide intermediate formed in the first step with a second thiyl radical, followed by chain transfer to a thiol, resulting in the formation of another sulfide bond. In kinetic analysis, each terminal alkyne group is considered bifunctional; therefore, to generate a network polymer, both the thiol and alkyne monomers must have at least two functional groups. TIFF0007823896000042.tif108139 Scheme 2: Mechanism of the radical-mediated thiol-yne click reaction showing sequential addition and hydrogen abstraction steps.

[0123] Table 7. Physical and optical properties of thiol-yne based photopolymer networks. TIFF0007823896000043.tif124151 Thiol-yne resins were prepared by mixing thiol and alkyne monomers with a 2:1 molar ratio of thiol:yne functional groups with approximately 1 wt% of 2,4,6-trimethylbenzoyldiphenylphosphine oxide (TPO) and irradiating them with 405 nm LED light at 30 mW / cm. 2 The mixture was irradiated and photopolymerized. a Determined by rotational rheometry, b The refractive index is expressed by the Fraunhofer D line (589 nm). c Determined by DSC.

[0124] To investigate the photopolymerization kinetics, resin mixtures with stoichiometric amounts of thiol and alkyne (Yne:SH = 1:2) groups were generated from the synthesized thiol and yne monomers (Table 7). All formulations formed miscible resin mixtures with low viscosity (>473 cP), and the conversion was monitored using real-time Fourier transform infrared (FTIR) spectroscopy. At 30 mW / cm 2 When irradiated at 405 nm with an intensity of 1000 kJ / s, the corresponding thiol (2570 cm -1 ) and alkynes (2120cm -1 Both the thiol and alkyne groups reacted rapidly, as indicated by the disappearance of the α-thiol peak. However, we found that the reactivity of thiols and alkynes varied significantly depending on the steric and electronic properties of the monomers, as well as the viscosity of the resin, dramatically affecting the polymerization kinetics. For example, in formulations A1–A4, monomer 1a, which contains only a 1° thiol, showed differential reactivity among alkyne monomers 2a–2d, indicating viscosity and steric effects.

[0125] Interestingly, the thiol and alkyne conversions for the highly flexible diyne monomer 2b and monoyne 2a reached a maximum of 80% in 5 min, compared with only approximately 70% for the remaining diyne monomers 2c and 2d (Figure 16A). This large difference in polymerization kinetics for 2b is speculated to be due to its less sterically hindered backbone and its ability to form low-viscosity resin mixtures. However, the influence of secondary interactions such as π-π stacking in the aryl-containing diyne monomers 2a, 2c, and 2d cannot be excluded. All formulations containing 2b showed high thiol and yne conversions (approximately 80%), whereas all remaining formulations containing aryl-containing yne monomers showed significantly lower conversions. Without being bound by theory, this large difference in conversions indicates the influence of steric hindrance and resin viscosity, which restrict mobility and inhibit the accessibility of thiols to react with alkynes during network formation (Figures 16A-16C).

[0126] Furthermore, formulations containing 1a, A3 and A4, which have higher vinyl sulfide concentrations than A1 and A2, clearly demonstrate the inability of thiols to react even with vinyl sulfides, which are often several times more reactive than the corresponding alkynes (Figure 21A). This inactivity of vinyl sulfides in the system may be due to steric hindrance induced after the reaction of a single thiol. The reactivity of multifunctional thiols is significantly influenced by the nature (i.e., 1° or 2°) and relative position of the thiol. As expected, for formulations of 2b with monomers 1b and 1c containing the 2° thiol, the conversion rate decreased to <80%. As seen in the kinetic rate plots, the conversion rates achieved with other monomers 2a, 2c, and 2d, which have bulky core structures, were below 60% in all cases (Figures 16B-16C). This discrepancy was inferred to be due to the limited mobility and potentially lower reactivity of the shorter 2° thiol group, which becomes difficult to access when reacting with the primary thiol of the same monomer. As previously pointed out, the large steric hindrance of the 2° thiol increases the activation energy of the chain transfer step, resulting in a significant decrease in the reaction rate. Similar trends in the reactivity of 1°, 2°, and 3° thiols were observed in thiol-ene photopolymer systems due to steric factors, albeit under lower initiation conditions. 14 To better understand the reactivity of 2°-thiols toward alkynes, model 2°-thiols were synthesized according to the basic synthetic protocol described herein (Figure 22). The difference in reactivity of alkynes toward 1°- and 2°-thiols was analyzed using hexanethiol (HT) and 3a as model 1°- and 2°-thiols, respectively. Real-time FT-IR kinetics for formulations M1 and M2 (i.e., SH:Yne = 2:1) containing stoichiometric amounts of 3a and HT along with 2a clearly demonstrates that the reaction rate of the 2°-thiol is slower than that of the 1°-thiol (Figures 23A-23B). Because the 2°-thiol shares most structural similarities with 1b and 1c, the lower conversion rate of the model 2°-thiol clearly demonstrates that steric bulk and position have a significant impact on the reactivity of thiol-ynes.

[0127] We also found that in some cases, the functional group conversion rate at a given time point was slightly higher for alkynes than for thiols. This behavior reflects the reaction of vinyl sulfides formed by the initial thiol-yne reaction and is consistent with previous findings that the addition of thiols to alkynes leads to the formation of vinyl sulfides, which is significantly slower than the reaction between thiols and vinyl sulfides. This difference may also be due to the consumption of alkyne or vinyl sulfide functional groups by chain-growth addition mechanisms, i.e., homopolymerization or copolymerization. Photopolymerizations were also performed at a high temperature of 60 °C and under nonstoichiometric conditions (Yne:SH = 1:3). While a slight increase in yne conversion was observed under nonstoichiometric conditions, no significant change in conversion was observed at higher temperatures, indicating that resin viscosity has little effect on conversion and confirming the inability of 2° thiols to participate in efficient reactions, even at high temperatures.

[0128] Example 6: Thermomechanical properties of high n thiol-yne photopolymers One key feature of the thiol-yne reaction compared to the analogous thiol-ene click reaction is that one alkyne reacts with two thiol moieties, resulting in polymers with higher crosslink density than the corresponding thiol-ene formulations. As previously mentioned, all formulations formed fully miscible resin mixtures with low viscosity (>473 cP) and a crosslink density of 30 mW / cm. 2 Irradiation at 405 nm at 1000 rpm resulted in the formation of optically transparent films between glass slides. Although conversions were particularly low for resin formulations containing diynes 2c and 2d along with multithiols 1b and 1c, all of these far exceeded gel point conversions and formed mechanically robust films. Furthermore, as previously noted, stoichiometrically balanced step-growth polymerization systems in which the initial addition rate is slower than the subsequent addition rates (i.e., kP,2 / kP,1 > 1) exhibit lower gel point conversions than Flory-Stockmeyer predicted. One important feature of step-growth thiol-ene and thiol-yne networks is their relatively narrow glass transition region, which results from uniform network formation.

[0129] A similar trend was observed for the thiol-yne networks formed here, indicating relatively uniform network formation. However, the tan δ curves obtained for networks formed from dithiol and diyne formulations were found to be somewhat broader compared to previously reported dithiol-diyne networks (Figures 17A-17C). The reason for this discrepancy is believed to be heterogeneous network formation due to the presence of two different thiol functional groups with different chemical environments. All glass transition temperatures for the network polymers were measured by DMA, except for formulations A1, B1, and C1, which were measured by DSC analysis due to the difficulty of large-scale sample preparation. The glass transition temperatures obtained for the various thiol-yne formulations are listed in Table 7. As expected, the photopolymers obtained from formulations A2, B2, and C2 exhibited higher T values ​​between 0°C and 19°C, consistent with higher conversion rates. g On the other hand, formulations A1, B1 and C1 showed T values ​​below -30°C due to the formation of nearly linear polymers by these formulations. g showed.

[0130] However, for all remaining formulations containing diynes 2c and 2d, T g As expected, polymers A4, B4, and C4 with rigid thiobenzenethiol (TBT) cores exhibited T values ​​in the range of −18 to −6 °C. g A3, B3, and C3 with an ethanedithiol (EDT) core have higher T values g Although the thiol and alkyne conversions in these formulations far exceeded the gel point, the low overall conversions resulted in the expected crosslink density and T g Therefore, the T formed from diynes and polyfunctional thiols g A wide range of thermomechanical properties was obtained for each of these photopolymer systems, with T values ​​ranging from -18 to 19 °C. gThe low modulus makes the material suitable for applications in optics and ophthalmic implants. Furthermore, each sample exhibits a similar transition from a glassy region with an elastic modulus above 1 GPa to a rubbery region with a significantly lower modulus.

[0131] Example 7: Refractive index of thiol-yne photopolymers: As a result of their high intrinsic atomic refraction, sulfur-containing polymers are expected to exhibit high refractive indices. Therefore, the increase in refractive index of photopolymers formed from thiol-x polymerization is a direct result of the incorporation of sulfide moieties within the network. One important feature of thiol-yne photopolymerization is the ability to introduce more sulfide bonds compared to the corresponding thiol-ene formulations. This feature of the thiol-yne reaction results from the ability of one alkyne to react with two thiol groups, which is not possible with thiol-ene systems, resulting in an increase in the number of sulfur atoms in the system. Using this approach, photopolymers with large changes in refractive index were easily achieved by simply switching the monomer functionality from vinyl to the corresponding alkyne reactive group.

[0132] As can be seen from Table 7, each combination of thiol and yne monomers synthesized had a refractive index n D (20 °C) yielded photopolymers with a RI ranging from approximately 1.65 to 1.69 (0.04). These RI values ​​at low conversion (approximately 60%) are already higher than those previously reported for similar thiol-ene systems. The high refractive index values ​​exhibited by these network polymers are a direct result of the monomer core design, which incorporates high molar refractive index substituents. Thus, the aromatic dithiol core in 2d increases the refractive index by as much as 0.03 compared to its alkyl counterpart, 2c. Using an excess of thiol, i.e., a nonstoichiometric amount, in the resin formulation may improve the polymer refractive index and conversion of the limiting reagent (i.e., the yne monomer) by reducing diffusional constraints. However, attempts to improve the polymer refractive index by a nonstoichiometric combination of 1b and 1c with 2d (thiol-yne, 3:1) had the negative effect of decreasing the refractive index by 0.02.

[0133] A plausible explanation for this discrepancy is that the free thiol contributes less to the refractive index enhancement compared to the thioether moiety resulting from the thiol-yne click reaction. This behavior is evident from the dramatic change in refractive index (0.08) observed for formulation B2 (dithiol 1b and yne monomer 2b) upon polymerization. 2 Upon exposure to 405 nm light at an intensity of 1.60, the refractive index of the resin changed from 1.60 to 1.68 in 5 minutes, indicating the formation of numerous thioether bonds with high conversion. Because no aryl groups are present in this resin system, the concentration of sulfide bonds provides a direct measure of the polymer refractive index. Interestingly, the measured polymer refractive index showed a linear relationship with thiol conversion, as shown in Figure 18.

[0134] Example 8: Use of high RI thiol-yne monomers in a two-step photopolymer system The ability of photopolymer systems to achieve high refractive index contrast between the matrix and the writing monomer upon exposure is one of the key specifications for developing novel holographic materials. However, achieving such high refractive index contrast is often difficult due to the limited availability of suitable high-RI monomers with low viscosity. To this end, thiol-ene writing chemistry has recently been devised and implemented for high-fidelity hologram recording via a linear polyurethane binder approach. Following a similar approach, these synthetic high-RI alkyne monomers were used to record relatively high Δn holograms in thin films. As can be seen in Figure 18, peak diffraction efficiencies of 80% were achieved at high spatial frequencies when using 2d and commercial trimethylolpropane tris(3-mercaptopropionate) (TMPTMP) as writing monomers. The angular reconstruction spectra of the recorded holograms were in good agreement with the coupled-wave theory fit. The dynamic range (Δn) and thickness of holograms using other alkyne writing monomers, 2a and 2c, are also summarized in Figures 19A–19B. The hologram recorded with 2d exhibits the highest Δn of 0.018, likely due to the higher refractive index of this writing monomer formulation compared to 2a and 2c. However, the diffuse blur caused by the incomplete conversion of these writing monomers reduces the overall refractive index contrast and remains a limitation in achieving high index modulation depth. Interestingly, the measured haze values ​​for all these holograms were found to be lower than 1.5%. The slightly higher haze observed for monomer 2d is attributed to the poor miscibility of this rigid-core monomer with the urethane binder introduced here.

[0135] Another application of high-refractive-index photocurable thiol-yne resins is demonstrated by recording two-dimensional, micrometer-scale, high-fidelity refractive index structures on a poly(urethane-thiourethane) stage 1 matrix. The model system demonstrated here consisted of a poly(urethane-thiourethane) matrix incorporating high-refractive-index B2 resin. The first-stage poly(urethane-thiourethane) matrix was cured at ambient temperature and cast as a 250 μm-thick film of this material between two glass slides. In the second stage, the film was irradiated with a 405 nm LED source through a photomask to record a two-dimensional array (100 μm square) of refractive index structures, as shown by the optical microscope image in Figure 20.

[0136] Numbering method The following exemplary aspects are provided, the numbering of which is not to be construed as indicating order of importance.

[0137] Aspect 1 provides the following: at least one polymer; a polymeric binder containing a plurality of allyl groups; and Formula (I): At least one monomer of TIFF0007823896000044.tif14128 and formula (II): At least one monomer of TIFF0007823896000045.tif14128 A composition comprising: During the ceremony X in each occurrence is independently H or optionally substituted C 6~14 is aryl; each Y is independently -S-, -CH2-, -CH2CH2-, -CH(CH3)CH2-, -CH2CH(CH3)-, -CH(SH)-, -CH[O-CH2-CH=CH2]-, or -CH[O-CH2-C≡CH]-; Each Y T are independently H, -SH, -CH=CH2, -C≡CH, or optionally substituted C 6~14 is aryl; each Z is independently -S-, -CH2, -CH2CH2-, -CH(CH3)CH2-, -CH2CH(CH3)-, or -CH(SH)-; each Z T are independently H, -SH, or -CHSH; m is an integer ranging from 0 to 100; and n is an integer ranging from 0 to 100.

[0138] Aspect 2 provides the following: 2. The composition of embodiment 1, wherein the polymer is a linear polyurethane.

[0139] Aspect 3 provides the following: Aspect 3. The composition of any one of aspects 1-2, wherein the polymer binder comprises about 0-80 mol % allyl groups.

[0140] Aspect 4 provides the following: Aspect 4. The composition of any one of aspects 1-3, wherein the polymer comprises polycaprolactone-block-polytetrahydrofuran-block-polycaprolactone.

[0141] Aspect 5 provides the following: Aspect 5. The composition of any one of aspects 1 to 4, wherein the ratio of the monomer of formula (I) to the monomer of formula (II) is from about 9:1 to about 1:9.

[0142] Aspect 6 provides the following: (Z) n -Z T 6. The composition of any one of embodiments 1-5, wherein

[0143] Aspect 7 provides the following: (Z) n -Z T 7. The composition of any one of embodiments 1-6, wherein comprises at least two —SH moieties.

[0144] Aspect 8 provides the following: The monomer of formula (II) 8. The composition of any one of embodiments 1 to 7, selected from the group consisting of: TIFF0007823896000046.tif31128.

[0145] Aspect 9 provides the following: Aspect 9. The composition of any one of aspects 1 to 8, wherein X is phenyl.

[0146] Aspect 10 provides the following: (Y) m Aspect 10. The composition of any one of aspects 1 to 9, wherein is linear.

[0147] Aspect 11 provides the following: (Y) m 11. The composition of any one of aspects 1-10, wherein comprises at least one of —CH(O—CH 2 —CH═CH 2 )— or —CH(O—CH 2 —C≡CH)—.

[0148] Aspect 12 provides the following: (Y) m comprises at least two moieties independently selected from —CH(O—CH 2 —CH═CH 2 )— and —CH(O—CH 2 —C≡CH)—.

[0149] Aspect 13 provides the following: The monomer of formula (I) 13. The composition of any one of embodiments 1 to 12, selected from the group consisting of: TIFF0007823896000047.tif95152.

[0150] Aspect 14 provides the following: Aspect 14. The composition of any one of aspects 1 to 13, wherein the monomer of formula (I) and the monomer of formula (II) together comprise about 1 to 80% (w / w) of the composition.

[0151] Aspect 15 provides the following: A composition according to any one of embodiments 1 to 14, which is polymerized.

[0152] Aspect 16 provides the following: A polymeric composition according to any one of aspects 1 to 15, wherein a plurality of allyl groups are crosslinked with the monomers of formula (I) and formula (II).

[0153] Aspect 17 provides the following: A film comprising the composition of any one of embodiments 1 to 14.

[0154] Aspect 18 provides the following: providing a composition according to any one of aspects 1 to 14; and exposing the composition to laser radiation to form a hologram. A method for recording a hologram, including:

[0155] Aspect 19 provides the following: 20. The method of embodiment 18, wherein the providing step comprises coating an inert substrate with a film.

[0156] Aspect 20 provides the following: Aspect 20. The method of any one of aspects 18-19, wherein the exposing step comprises crosslinking the polymer binder with the monomers of Formula (I) and Formula (II).

[0157] Aspect 21 provides the following: 21. The method of any one of embodiments 18 to 20, wherein the hologram has an index modulation depth (Δn) of about 0.01 to about 0.06.

[0158] Aspect 22 provides the following: Formula (IA): At least one monomer of TIFF0007823896000048.tif16128 and formula (II): At least one monomer of TIFF0007823896000049.tif14128 A composition comprising: During the ceremony X in each occurrence is independently H or optionally substituted C6~14 is aryl; Y and Y in each occurrence are independently -S-, -CH-, -CHCH-, -CH(CH)CH-, -CHCH(CH)-, -CH(SH)-, -CH[O-CH-CH=CH]-, or -CH[O-CH-C≡CH]-; Y T1 and Y T2 is independently in each occurrence H, -SH, -CH=CH2, -C≡CH, or an optionally substituted C 6~14 is aryl; each Z is independently -S-, -CH2, -CH2CH2-, -CH(CH3)CH2-, -CH2CH(CH3)-, or -CH(SH)-; each Z T are independently H, -SH, or -CHSH; each m1 and m2 is independently an integer ranging from 0 to 100; and n is an integer ranging from 0 to 100.

[0159] Aspect 23 provides the following: 23. The composition of embodiment 22, polymerized.

[0160] Aspect 24 provides the following: 24. The polymeric composition of embodiment 23, having a refractive index of about 1.63 to about 1.69.

[0161] Embodiment 25 provides the following: (Z) n -Z T 25. The composition of any one of embodiments 22-24, wherein comprises at least one —SH moiety.

[0162] Embodiment 26 provides the following: (Z) n -Z T 26. The composition of any one of embodiments 22-25, wherein comprises at least two —SH moieties.

[0163] Aspect 27 provides the following: The monomer of formula (II) 27. The composition of any one of embodiments 22 to 26, selected from the group consisting of: TIFF0007823896000050.tif31128.

[0164] Embodiment 28 provides the following: Aspect 28. The composition of any one of aspects 22-27, wherein m1 is 1, Y1 is -S-, and YT1 is phenyl.

[0165] Aspect 29 provides the following: (Y1) m1 and (Y2) m2 The composition of any one of aspects 22 to 28, wherein at least one of the following is linear:

[0166] Aspect 30 provides the following: (Y1) m1 and (Y2) m2 29. The composition of any one of embodiments 28, wherein at least one of comprises at least one of —CH(O—CH 2 —CH═CH 2 )— or —CH(O—CH 2 —C≡CH)—.

[0167] Aspect 31 provides the following: (Y1) m1 and (Y2) m2 31. The composition of any one of embodiments 30, wherein at least one of comprises at least two moieties independently selected from —CH(O—CH 2 —CH═CH 2 )— and —CH(O—CH 2 —C≡CH)—.

[0168] Aspect 32 provides the following: Y T1 and Y T2 32. The composition of any one of aspects 22-31, wherein is —C≡CH.

[0169] Aspect 33 provides the following: The monomer of formula (IA) 33. The composition of any one of embodiments 22 to 32, selected from the group consisting of: TIFF0007823896000051.tif63152.

Claims

1. A linear polyurethane polymer binder containing at least 10 mol % allyl side chains; and Formula (I): At least one monomer of and formula (II): At least one monomer of A composition comprising: During the ceremony X in each occurrence is optionally substituted phenyl; Y is independently -S-, -CH 2 -, -CH 2 CH 2 -, -CH(CH 3 )CH 2 -, -CH 2 CH(CH 3 )-, -CH(SH)-, -CH[O-CH 2 -CH=CH 2 ]-, or -CH[O-CH 2 -C≡CH]- and at least one Y is -CH(O-CH2-CH=CH2)- or -CH(O-CH2-C≡CH)-; Y T are independently -SH, -CH=CH in each occurrence. 2 , -C≡CH, or optionally substituted C 6～14 is aryl; Z is independently -S-, -CH 2 -, -CH 2 CH 2 -, -CH(CH 3 )CH 2 -, -CH 2 CH(CH 3 )-, or -CH(SH)-; Z T is independently -SH or -CH in each occurrence 2 SH; m is an integer ranging from 2 to 100; and n is an integer ranging from 1 to 100.

2. A linear polyurethane polymer binder containing at least 10 mol % allyl side chains; and Formula (I) selected from the group consisting of: At least one monomer of and formula (II): At least one monomer of A composition comprising: During the ceremony Z in each occurrence is independently -S-, -CH2-, or -CH(SH)-; ZT in each occurrence is independently -SH or -CH2SH; and n is an integer ranging from 2 to 100.

3. 3. The composition of claim 1 or 2, wherein the linear polyurethane polymer binder comprises polycaprolactone-block-polytetrahydrofuran-block-polycaprolactone.

4. 3. The composition of claim 1, wherein the ratio of the monomer of formula (I) to the monomer of formula (II) is from about 9:1 to about 1:

9.

5. (Z) n -Z T 3. The composition of claim 1 or 2, wherein said at least one -SH moiety is present.

6. The monomer of formula (II) 3. The composition of claim 1 or 2, selected from the group consisting of:

7. (Y) m The composition of claim 1, wherein is linear.

8. (Y) m -CH(O-CH 2 -CH=CH 2 )- and -CH(O-CH 2 10. The composition of claim 1, comprising at least two moieties independently selected from -C≡CH)-.

9. The monomer of formula (I) 2. The composition of claim 1, selected from the group consisting of:

10. 3. The composition of claim 1 or 2, wherein the monomer of formula (I) and the monomer of formula (II) together comprise about 1 to 80% (w / w) of the composition.

11. 3. The composition of claim 1 or 2 which has been polymerized.

12. The polymeric composition of claim 11, wherein the allyl groups of the linear polyurethane polymer binder are crosslinked with the monomers of formula (I) and formula (II).

13. A film comprising the composition of claim 1 or 2.

14. Providing a composition according to claim 1 or 2; and exposing the composition to laser radiation to form a hologram. A method for recording a hologram, comprising:

15. 15. The method of claim 14, wherein the providing step comprises coating an inert substrate with a film.

16. 15. The method of claim 14, wherein the exposing step comprises crosslinking the linear polyurethane polymer binder with the monomers of formula (I) and formula (II).

17. 15. The method of claim 14, wherein the hologram has an index modulation depth (Δn) of about 0.01 to about 0.06.

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