Chalcogenide hybrid inorganic organic polymers with medium and long wavelength infrared transparency

Abstract

A composition includes a polymer that is a reaction product of a co-monomer and one or more of elemental sulfur or a chalcogenide halide, wherein the co-monomer includes a vinyl monomer, isopropenyl monomer, acryl monomer, methacryl monomer, unsaturated hydrocarbon monomer, epoxide monomer, thiirane monomer, alkynyl monomer, diene monomer, butadiene monomer, isoprene monomer, norbornene monomer, amine monomer, thiol monomer, sulfide monomer, alkynyl unsaturated monomer, nitrone monomer, aldehyde monomer, ketone monomer, ethylenically unsaturated monomer, styrenic monomer, or a mixture of any two or more thereof; and the co-monomer comprises one or more deuterium atoms.

Description

CHALCOGENIDE HYBRID INORGANIC ORGANIC POLYMERS WITH MEDIUM AND LONG WAVELENGTH INFRARED TRANSPARENCYCROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority to U.S. Provisional Patent Application No. 63 / 514,043 filed July 17, 2023, which is incorporated herein by reference, in its entirety for any and all purposes.GOVERNMENT RIGHTS

[0002] This invention was made with government support under Grant Number 1940942, awarded by the National Science Foundation. The government has certain rights in the invention.FIELD

[0003] The present technology is directed to compositions including a polymer that is a reaction product of (a) one or more of elemental sulfur or a chalcogenide halide and (b) a co-monomer including one or more deuterium atoms.BACKGROUND

[0004] Optical technologies in the medium wavelength infrared (MWIR, 3-5 pm) and long wavelength infrared (LWIR spectrum, 7-14 pm) offer important advantages for high resolution thermal imaging in near, or complete darkness, which has been extensively utilized in the defence sector, but has significant potential in emerging consumer markets and transportation. Current transmissive materials used for IR imaging are based on inorganic materials, such as, germanium (Ge), or chalcogenide glasses (ChG’s). The use of polymeric transmissive materials would offer numerous cost and processing advantages, but historically have suffered from inferior optical properties and low transparency in the LWIR spectrum. A major challenge in the design of LWIR transparent organic materials is the fact that nearly all organic molecules absorb in this spectral window which lies within the “IR fingerprint region” (e.g., 600-1400 cm’1).

[0005] The synthesis of deuterated molecules and materials is an established field of chemistry with a resurgence of interest for a wide range of emerging uses in massspectroscopic labeling, pharmaceuticals and photonic devices.1'4The exchange of hydrogen with deuterium (H / D exchange) has long been studied as this simple chemical modification affords significant changes in the reactivity, chemical stability, optical absorbance windows, or pharmacological activity for certain organic (macro)molecules.5,6In a fundamental sense, physical organic chemistry has long exploited the use of deuterium labeled compounds for mechanistic studies using kinetic isotope effects (KIE)7For these types of KIE studies, compounds with selective deuterium labeling were required, which has spurred decades long activity in both synthetic methodology and catalyst development for H / D exchange.8Furthermore, the application of highly, or perdeuterated synthetic macromolecules has long been used to enhance contrast for both dilute solution and solid state morphological characterization of (co)polymeric materials using various neutron scattering techniques, most notably small angle neutron scattering (SANS).9,10Deuteration of polymers has also been conducted for use in telecommunication photonics to reduce the optical losses in polymer waveguide devices at 1310 nm.3However, wide scale deployment of deuterated chemical and material products remain fairly limited in scope, pointing to the potential for new systems to be developed that explicitly demonstrate the value of H / D exchange.

[0006] Described herein is new molecular design approach to prepare high refractive index polymers with enhanced medium wavelength infrared (MWIR) and / or long wavelength infrared (LWIR) transparency that are prepared from reacting with elemental sulfur with deuterated co-monomers. The polymers described herein are chalcogenide hybrid inorganic organic polymers (CHIPs) with enhanced MWIR and / or LWIR transparency and thermomechanical properties via the inverse vulcanization of elemental sulfur with new organic co-monomers.

[0007] Any feature or combination of features described herein are included within the scope of the present invention provided that the features included in any such combination are not mutually inconsistent as will be apparent from the context, this specification, and the knowledge of one of ordinary skill in the art. Additional advantages and aspects of the described embodiments are apparent in the following detailed description and claims.SUMMARY

[0008] Described herein is the first total synthesis of perdeuterated 1,3- diisopropenylbenzene (di4-DIB), co-polymerization with elemental sulfur via inverse vulcanization and IR optical characterization of these chalcogenide hybrid co-polymers comparing the effects of H / D exchange exactly at the C-H vibration resonance from 3.3-3.4 pm (-3000 cm’1). Deuterated diisopropenylbenzene (DIB) was chosen as the synthetic target for this study due to the importance of this monomer in the field of sulfur polymer chemistry and the prevalence of existing optical characterization of the sulfur co-polymer made from DIB and Ss, poly(sulfur-ra / ?tfom-(l,3-diisopropenylbenzene) (poly(S-r-DIB)). A total synthesis of t / w-DIB was devised beginning with abundant deuterated starting materials (t / s-toluene, t / e-acetone) to enable gram quantity synthesis of the deuterated monomer leading to production of the deuterated sulfur co-polymer in appreciable quantities to allow for bulk melt processing, fabrication of optical components and IR optical characterization. To demonstrate the benefits of deuteration for IR optics, both proteo- and t / ewtero-poly(S-r-DIB) co-polymers operating at 3.4 pm and optical diffraction gratings were prepared from both materials. This is the first demonstration of a functional IR optical element made from a CHIPs polymer that has been deuterated.

[0009] This disclosure provides a composition that includes a polymer that is a reaction product of (a) one or more of elemental sulfur or a chalcogenide halide and (b) a co-monomer, wherein the co-monomer is a vinyl monomer, isopropenyl monomer, acryl monomer, methacryl monomer, unsaturated hydrocarbon monomer, epoxide monomer, thiirane monomer, alkynyl monomer, diene monomer, butadiene monomer, isoprene monomer, norbornene monomer, amine monomer, thiol monomer, sulfide monomer, alkynyl unsaturated monomer, nitrone monomer, aldehyde monomer, ketone monomer, ethylenically unsaturated monomer, styrenic monomer, or a mixture of any two or more thereof; and the co-monomer includes one or more deuterium atoms.

[0010] In some embodiments, the polymer is the reaction product of the comonomer and the chalcogenide halide, and the chalcogenide halide is sulfur monochloride, sulfur dichloride, sulfur monobromide, selenium monochloride, selenium monobromide, selenium dichloride, selenium dibromide, selenium tetrachloride, selenium tetrabromide, or a combination of any two or more thereof. Still in other embodiments, the chalcogenidehalide is sulfur monochloride, sulfur dichloride, selenium monochloride, selenium dichloride, selenium tetrachloride, or a combination of any two or more thereof. In some embodiments, the polymer is the reaction product of the co-monomer and elemental sulfur and elemental sulfur is Ss. In some embodiments, the co-monomer has greater than about 90% deuterium incorporation. In some embodiments, the co-monomer has greater than about 95% deuterium incorporation. In some embodiments, the co-monomer has greater than about 99% deuterium incorporation.

[0011] In some embodiments, the co-monomer includes 1,3-diisopropenylbenzene. In some embodiments, the co-monomer includes di4-l,3-diisopropenylbenzene. In some embodiments, the di4-l,3-diisopropenylbenzene has about 99.2% deuterium incorporation.

[0012] In some embodiments, the composition has a refractive index of from about 1.70 to about 2.1.

[0013] In some embodiments, the composition is suitable for use in long wavelength infrared (LWIR) applications (e.g., the composition is transparent under LWIR applications). In some embodiments, the composition is suitable for use in medium wavelength infrared (MWIR) applications (e.g., the composition is transparent under MWIR applications). In some embodiments, the composition is suitable for use in medium wavelength infrared (MWIR) applications from about 3.3 to about 3.4 microns (e.g, the composition is transparent under MWIR applications from about 3.3 to about 3.4 microns). In some embodiments, the composition is suitable for use in medium wavelength infrared (MWIR) applications at about 3.3 microns or at about 3.4 microns (e.g, the composition is transparent under MWIR applications at about 3.3 microns or at about 3.4 microns).

[0014] In some embodiments, the composition is molded or solution processed into a fabricated optical element. In some embodiments, the fabricated optical element comprises a free standing film or nano or micropattemed polymer form. In some embodiments, wherein the composition improves the average IR transmission of the fabricated optical element over that of an element made from the undeuterated material, in a MWIR wavelength range (e.g, the composition increases the transparency of the fabricated optical element over that of an element made from the undeuterated material, in a MWIR wavelength range). In some embodiments, the MWIR wavelength is from about 3.0 microns wavelength to about 4.2 microns wavelength, from about 3.0 microns wavelength to about3.3 microns wavelength, or from about 3.3 microns wavelength to about 4.2 microns wavelength. In some embodiments, the composition is suitable for use in MWIR photonic devices (e.g., the composition is transparent under MWIR photonic devices). In some embodiments, the MWIR photonic devices are selected from waveguides, optical grating, and ring-resonators.

[0015] Provided in another aspect is an article of manufacture that may include any of the compositions described herein.

[0016] In some embodiments, the article of manufacture is an imaging device.

[0017] Provided in another aspect is a process for producing the compositions as described herein. Such processes include admixing a mixture of (a) one or more of elemental sulfur or a chalcogenide halide and (b) a co-monomer to form an admixture, and polymerizing the admixture. The co-monomer may include a vinyl monomer, isopropenyl monomer, acryl monomer, methacryl monomer, unsaturated hydrocarbon monomer, epoxide monomer, thiirane monomer, alkynyl monomer, diene monomer, butadiene monomer, isoprene monomer, norbornene monomer, amine monomer, thiol monomer, sulfide monomer, alkynyl unsaturated monomer, nitrone monomer, aldehyde monomer, ketone monomer, ethylenically unsaturated monomer, styrenic monomer, or a mixture of any two or more thereof, and the co-monomer may include one or more deuterium atoms.BRIEF DESCRIPTION OF THE DRAWINGS

[0018] FIG.1 shows suitably deuterium-enriched commercially available starting material candidates.

[0019] FIG. 2 shows the total synthesis of t / / v-DIB from ds- toluene (a-g) and inverse vulcanization (h) with Ss to prepare perdeuterated poly(S- / '-t / / vDIB).

[0020] FIGS. 3 A and 3B show the solution13C NMR spectra of t / / v-DIB (FIG. 3 A) and / ?roteo-DIB (FIG. 3B) taken in CDCh.

[0021] FIGS. 4A and 4B show the solution2H NMR spectra of t / / v-DIB (FIG. 4A) and1H NMR spectra of / -DIB (FIG. 4B) taken in benzene.

[0022] FIGS. 5A, 5B, 5C, and 5D show the stacked FTIR transmission spectra ofDIB (red) and dw-DIB (blue) from 2.5 to 20 m (FIG. 5 A), FTIR absorbance spectra DIB (red) and dw-DIB (blue) from 3.0 to 5.0 pm (FIG. 5B), stacked transmission spectra of poly(S-r-di4DIB) hot pressed films of varying thickness from 100-500 pm (FIG. 5C), and stacked FTIR spectra of 250 micron thick films of proteo C-H poly(S-r-DIB) vs deutero C- D poly(S-r-di4DIB) (FIG. 5D).DETAILED DESCRIPTION

[0023] Various embodiments are described hereinafter. It should be noted that the specific embodiments are not intended as an exhaustive description or as a limitation to the broader aspects discussed herein. One aspect described in conjunction with a particular embodiment is not necessarily limited to that embodiment and can be practiced with any other embodiment s).

[0024] As used herein, “about” will be understood by persons of ordinary skill in the art and will vary to some extent depending upon the context in which it is used. If there are uses of the term which are not clear to persons of ordinary skill in the art, given the context in which it is used, “about” will mean up to plus or minus 10% of the particular term.

[0025] The use of the terms “a” and “an” and “the” and similar referents in the context of describing the elements (especially in the context of the following claims) are to be constructed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., “such as”) provided herein, is intended merely to better illuminate the embodiments and does not pose a limitation on the scope of the claims unless otherwise stated. No language in the specification should be construed as indicating any non-claimed element as essential.

[0026] As used herein, the term “amine monomer” is a monomer having at least one amine functional group. The amine monomer may be polymerizable through its amine functional group. In one embodiment, aromatic amines and multi-functional amines may beused. Amine monomers include, but are not limited to, m-phenylenediamine, and p- phenylenediamine. The various types of phenylenediamines are inexpensive reagents due to their wide-spread use in the preparation of many conventional polymers, e.g., polyurethanes, polyamides. In the reaction of 1,3-phenylenediamine with Ss a surprising substitution of the aromatic ring with sulfur groups occurs in the co-polymerization. Furthermore, the resulting sulfur co-polymer carried reactive amine moieties that were further reacted with co-monomers, such as, isocyanates, acid chlorides, epoxides, carboxylic acids, esters, amides, alkyl halides, or acrylates to either modify the sulfur copolymer, or make new co-polymeric materials, such as, polyamides, polyurethanes, polyamides, and polyethers.

[0027] As used herein, the term “thiol monomer” is a monomer having at least one thiol functional group. The thiol monomer may be polymerizable through its thiol functional group. Thiol monomers include, but are not limited to, 4,4'-thiobisbenzenethiol and the like. The term “sulfide monomers” are those that have at least one sulfide functional group. The sulfide monomers may be polymerizable through its sulfide functional group.

[0028] As used herein, an alkynyl unsaturated monomer is a monomer having at least one alkynyl unsaturated functional group. The alkynyl unsaturated monomer may be polymerizable through its alkynyl unsaturation (i.e., its triple bond). The term “alkynyl unsaturated monomer” does not include compounds in which the alkynyl unsaturation is part of a long chain alkyl moiety (e.g., unsaturated fatty acids, or carboxylic salts, or esters such as oleates, and unsaturated plant oils). In one embodiment, aromatic alkynes, both internal and terminal alkynes, and multi-functional alkynes may be used. Examples of alkynyl unsaturated monomers include, but are not limited to, ethynylbenzene, 1- phenylpropyne, 1,2-diphenylethyne, 1,4-di ethynylbenzene, l,4-bis(phenylethynyl)benzene, and 1,4-diphenylbuta-l, 3-diyne.

[0029] As used herein, the term “nitrone monomer” is a monomer having at least one nitrone functional group. The nitrone monomer may be polymerizable through its nitrone functional group. In one embodiment, nitrones, dinitrones, and multi-nitrones may be used. Examples include, but are not limited to, N-benzylidene-2-methylpropan-2-amine oxide.

[0030] As used herein, the term “aldehyde monomer” is a monomer having at least one aldehyde functional group. The aldehyde monomer may be polymerizable through its aldehyde functional group. In one embodiment, aldehydes, dialdehydes, and multialdehydes may be used.

[0031] As used herein, a “ketone monomer” is a monomer with at least one ketone functional group. The ketone monomer may be polymerizable through its ketone functional group. In one embodiment, ketones, diketones, or multi-ketones may be used.

[0032] As used herein, the term “epoxide monomer” is a monomer having at least one epoxide functional group. The epoxide monomer may be polymerizable through its epoxide functional group. Non-limiting examples of such monomers include, generally, mono- or polyoxiranylbenzenes, mono- or polyglycidylbenzenes, mono- or polyglycidyloxybenzenes, mono- or polyoxiranyl(hetero)aromatic compounds, mono-or polyglycidyl(hetero)aromatic compounds, mono- or polyglycidyloxy(hetero)aromatic compounds, diglycidyl bisphenol A ethers, mono- or polyglycidyl(cyclo)alkyl ethers, mono- or polyepoxy(cyclo)alkane compounds and oxirane-terminated oligomers. In one preferred embodiment, the epoxide monomers may be benzyl glycidyl ether and tris(4- hydroxyphenyl)methane triglycidyl ether. In certain embodiments, the epoxide monomers may include a (hetero)aromatic moiety such as, for example, a phenyl, a pyridine, a triazine, a pyrene, a naphthalene, or a polycyclic (hetero)aromatic ring system, bearing one or more epoxide groups. For example, in certain embodiments, the one or more epoxide monomers are selected from epoxy(hetero)aromatic compounds, such as styrene oxide and stilbene oxide and (hetero)aromatic glycidyl compounds, such as glycidyl phenyl ethers (e.g., resorcinol diglycidyl ether, glycidyl 2-methylphenyl ether), glycidylbenzenes (e.g., (2,3- epoxypropyl)benzene) and glycidyl heteroaromatic compounds (e.g., N-(2,3- epoxypropyl)phthalimide). In certain desirable embodiments, an epoxide monomer will have a boiling point greater than 180 °C, greater than 200 °C, or even greater than 230 °C at the pressure at which polymerization is performed (e.g., at standard pressure, or at other pressures).

[0033] As used herein, the term “thiirane monomer” is a monomer having at least one thiirane functional group. The thiirane monomer may be polymerizable through its thiirane functional group. Non-limiting examples of thiirane monomers include, generally,mono- or polythiiranylbenzenes, mono- or polythiiranylmethylbenzenes, mono- or polythiiranyl(hetero)aromatic compounds, mono- or polythiiranylmethyl(hetero)aromatic compounds, dithiiranylmethyl bisphenol A ethers, mono- or polydithiiranyl (cyclo)alkyl ethers, mono- or polyepisulfide(cyclo)alkane compounds, and thiirane-terminated oligomers. In some embodiments, thiirane monomers may include a (hetero)aromatic moiety such as, for example, a phenyl, a pyridine, a triazine, a pyrene, a naphthalene, or a poly cyclic (hetero)aromatic ring system, bearing one or more thiirane groups. In certain desirable embodiments, a thiirane monomer will have a boiling point greater than 180 °C, greater than 200 °C, or even greater than 230 °C at the pressure at which polymerization is performed (e.g., at standard pressure).

[0034] As used herein, an ethylenically unsaturated monomer is a monomer having at least one ethylenically unsaturated functional group. The ethylenically unsaturated monomer may be polymerizable through its ethylenic unsaturation (i.e., its double bond). The term “ethylenically unsaturated monomer” does not include compounds in which the ethylenic unsaturation is part of a long chain alkyl moiety (e.g. unsaturated fatty acids such as oleates, and unsaturated plant oils).

[0035] In certain embodiments, the one or more ethylenically unsaturated monomers are vinyl monomers, (meth)acryl monomers, unsaturated hydrocarbon monomers, ethylenically-terminated oligomers, monocyclic and bicyclic olefins. In some embodiments, the ethylenically unsaturated monomers include hydroxyl groups or carboxylic acid groups. Examples of such monomers include, generally, mono- or polyvinylbenzenes, mono- or polyisopropenylbenzenes, mono- or polyvinyl(hetero)aromatic compounds, mono- or polyisopropenyl(hetero)aromatic compounds, alkylene di(meth)acrylates, bisphenol A di(meth)acrylates, benzyl (meth)acrylates, phenyl(meth)acrylates, heteroaryl (meth)acrylates, terpenes (e.g., squalene), or carotene. As molten sulfur is non-polar in character, in certain desirable embodiments the one or more ethylenically unsaturated monomers are non-polar. For example, in certain embodiments, the one or more ethylenically unsaturated monomers include a (hetero)aromatic moiety such as, for example, phenyl, pyridine, triazine, pyrene, naphthalene, or a polycyclic (hetero)aromatic ring system, bearing one or more vinylic, acrylic, or methacrylic substituents. Examples of such monomers include benzyl (meth)acrylates, phenyl (meth)acrylates, divinylbenzenes (e.g., 1,3-divinylbenzene, 1,4-divinylbenzene), isopropenylbenzene, styrenics (e.g., styrene, 4-methyl styrene, 4- chlorostyrene, 2,6-dichlorostyrene, 4-vinylbenzyl chloride), diisopropenylbenzenes (e.g., 1,3-diisopropenylbenzene), vinylpyridines (e.g., 2-vinylpyridine, 4-vinylpyridine), 2,4,6- tris((4-vinylbenzyl)thio)-l,3,5-triazine and divinylpyridines (e.g., 2,5-divinylpyridine). Examples of monocyclic olefins include, but are not limited to, cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, cycloundecene, cyclododecene and the like, Examples of bicyclic olefins, include but are not limited to bicyclo[2.2.1]heptene, norbomene, norbornadiene, cyclo[3.3.0]octene, octahydropentelene, decahydronaphthelene, bicyclo[2.2.2]octene, and the like and derivatives thereof. Compatible cyclic olefins also include strained olefins, dienes, trienes, and tetraenes. In certain embodiments, the one or more ethylenically unsaturated monomers (e.g., including an aromatic moiety) bears an amino (i.e., primary or secondary) group, a phosphine group or a thiol group. One example of such a monomer is vinyldiphenylphosphine. While not intending to be bound by theory, the inventors surmise that the amino or thiol group will undergo a ring-opening nucleophilic attack on an Ss ring, thus incorporating a short sulfide chain that promotes solubility in molten sulfur. Of course, a person of skill in the art will identify other ethylenically unsaturated monomers that can be used in forming the co-polymers described herein. In certain desirable embodiments, an ethylenically unsaturated monomer will have a boiling point greater than 180 °C, greater than 200 °C, or even greater than 230 °C at the pressure at which polymerization is performed (e.g., at standard pressure).

[0036] As used herein, the “X% of deuterium incorporation” is intended to refer to the extent to which all hydrogen content in the co-monomer is replaced by deuterium.

[0037] As used herein, the terms “those defined above” and “those defined herein” when referring to a variable incorporates by reference the broad definition of the variable as well as any narrow and / or preferred definitions, if any.

[0038] Described herein are compositions that includes a polymer that is a reaction product of (a) one or more of elemental sulfur or a chalcogenide halide and (b) a comonomer having one or more deuterium atoms. Such compositions have high refractive index polymers with enhanced medium long wavelength infrared (MWIR) and / or long wavelength infrared (LWIR) transparency.

[0039] At present time, the greatest interest and applications for industrial applications of deuterated products is in the area of small molecule drugs for pharmaceutical applications, which resulted in a major milestone in 2017 when the Food and Drug Administration (FDA) approved deutetrabenazine as a Huntington’s disease treatment. In all cases, deuterated pharmaceutical targets like deutetrabenazine are minimally deuterated at strategic positions. Total syntheses of fully deuterated complex targets are rare and uniquely challenging for several reasons.2,4,5Firstly, deuterated starting materials need not only to be affordable, but they should ideally be 99%+ enriched in deuterium for the final product to reach high enrichment levels. Secondly, it is critical that no unwanted deuterium-proton exchanges happen during any of the synthetic steps including work-up and purification.

[0040] Synthetic methods to prepare (per)deuterated molecules classically have employed either heavy water (D2O), or molecular deuterium (D2) as the deuterium source, although more recently deuterated solvents have also been utilized.4,5,11These H / D exchange reactions have been conducted in the presence of acid, base, and metal complexes for both homogeneous, or heterogeneous processes.1,2,4,5Platinum catalysts in conjunction with D2O, have been extensively reported for deuteration of aromatic compounds.12,13Well-defined iridium based transition metal catalysts have been widely used for deuteration of activated aromatic13vinylic C-H bonds11,15or non-activated aliphatic C-H bonds with heterogeneous metal oxide catalysts5have also been reported. Deuteration via D2 in conjunction with solid supported rhodium16or platinum-rhenium alloyed supported catalysts17'21have been employed for hydrogenated polyolefins and polydienes. More recent efforts on H / D exchange catalysis have focused on selective isotopic labelling of bioactive molecules which prior to these recent reports were largely unexplored due to the challenging nature of these reactions. Photoredox catalysts for H / D exchange was developed by McMillan et al. using iridium based complexes with isotopically labeled water for selective deuteration of commercially available drug molecules.22Chirik et al. reported on the use of homogeneous iron catalysts for H / D exchange in conjunction with D2 gas for selective isotopic labelling of a wide range of aromatic substrates and various commercially available pharmaceuticals including, varenicline, loratadine, cinacalcet and flumenzil.23Beller et al. reported on the development of a heterogeneous Fe(0) / FeC catalysts in conjunction with heavy water deuterium sources, where the catalyst was derived via the pyrolysis of iron nitrate complexes with cellulose.24

[0041] The synthesis of partially, or perdeuterated monomers for preparing deuterated co-polymers has also been conducted via multi-step methods using deuterated, reagents, or solvents. Fetters notably developed a total synthesis of perdeuterated a-methyl styrene beginning with hexadeuterobenzene.25Beers developed an elegant synthesis of wholly, or partially deuterated polyethylene(s)26that can be thought of as “isotopic copolymers,” by exploiting the polyhomologation methods of Shea27using a deuterated sulfoxide ylide monomer that was prepared from NMR grade deuterated solvents (de- DMSO, 99.9% D). To date the primary use of making and studying deuterated polymers has been for analytical solution characterization of macromolecule dimensions, or interrogation of the solid-state morphology of co-polymers, or polymer blends using SANs. Hence, there remain technological opportunities to exploit deuterated polymeric materials beyond these current uses as contrast agents for fundamental scattering and reflectivity characterization tools.6

[0042] The application of H / D exchange holds intriguing possibilities for infrared (IR) optical polymeric materials, particular for the midwave IR (MWIR) spectral window from 3-5 pm (or 3300 cm to 2200 cm’1), where replacement of C-H for C-D bonds shifts the vibration resonances from -3.3 pm (-3000 cm’1) to 4.2 pm (-2200 cm’1). Synthetic polymers have not been used for MWIR optical applications, such as for MWIR thermal imaging, or waveguiding photonic devices due to the comparatively low refractive index of plastic optics (n - 1.4 to 1.8) vs inorganic optical components using germanium, or chalcogenide glasses (n = 2-4), coupled with the very low optical transmittance of MWIR radiation through organic based materials due to C-H bond vibrations.28While H / D exchange does not completely remove MWIR absorbances from the 3-5 pm wavelength region, shifting of the vibrational resonance away from the 3.3-3.4 pm wavelength by replacing C-H with C-D bonds has significant utility given the importance of this narrow spectral wavelength for chemical sensing (methane, etc.) and other emerging on chip- miniaturized IR photonic devices.29Also, the application of H / D exchange may also be applied towards the long wavelength IR (LWIR) spectral window from 7-14 pm.

[0043] A recent breakthrough in polymer chemistry and optical sciences has been the development of the inverse vulcanization process via the co-polymerization of elemental sulfur (Ss) with organic co-monomers.30,31High sulfur content co-polymers prepared from this process afford organic / inorganic hybrid materials of high RI (n -1.70-2.1) andenhanced IR transparency. These hybrid polymers are analogous to wholly inorganic chalcogenide glasses, but essentially replace inorganic covalent atoms (e.g. Ge, As) with organic moieties, and hence have been referred to as Chalcogenide Hybrid Inorganic / Organic Polymers (CHIPs) when used in optical or photonic applications.32,33The optical properties of these materials have garnered significant interest for use in the MWIR spectrum for photonic devices, or IR thermal imaging since the high sulfur content in these polymers allows for a dramatic reduction in the volume fraction of C-H bonds which has been shown to be essential for improved MWIR transparency between 3 and 5 pm.28This has been further explored in the LWIR via “IR fingerprint engineering” by computational design of new organic co-monomers and sulfur co-polymers with improved IR transparency.34However, the development of new proton-free organic monomers for the inverse vulcanization process has not yet been explored due to the synthetic complexities of this compositional requirement and is a new technological area of interest for deuteration chemistry and materials. Deuteration has been explored in optical polymers for waveguide photonic devices as means to reduce optical losses and absorption at telecommunication wavelengths (1310 nm) due to the shifting of overtone absorption bands of C-H vs C-D bonds.3However, to date, other uses of deuteration for optical polymeric materials and photonic devices has not been explored, or demonstrated. This may be attributed to deuteration impairing the performance at 1550 nm due to the shift of the 1400 nm vibrational band to the red.

[0044] Keeping these parameters in check is particularly crucial for the total synthesis efforts described herein as reduced deuterium enrichment for the target compound (t / / v-DIB) will negatively affect the MWIR transparency of the final optical sulfur copolymer. Further complications include the 1,3-relationship (meta) of the target isopropenyl aryl substituent, which is well established to be the most challenging of the possible di -substituted aryl substitution patterns for synthesis. Following careful analysis of commercially available deuterated starting material candidates factoring in both price and deuterium enrichment levels (99%+), only a handful of aromatic precursors were identified as suitable along with reagents, such deuterium oxide and acetone-t / e, that fit the criteria (FIG. 1). This short list of suitable starting material candidates is a testament to the constraints placed on the t / / v-DIB total synthesis quest and its challenge.

[0045] Described herein is a composition that includes a polymer that is a reaction product of (a) one or more of elemental sulfur or a chalcogenide halide and (b) a comonomer, wherein the co-monomer is a vinyl monomer, isopropenyl monomer, acryl monomer, methacryl monomer, unsaturated hydrocarbon monomer, epoxide monomer, thiirane monomer, alkynyl monomer, diene monomer, butadiene monomer, isoprene monomer, norbornene monomer, amine monomer, thiol monomer, sulfide monomer, alkynyl unsaturated monomer, nitrone monomer, aldehyde monomer, ketone monomer, ethylenically unsaturated monomer, styrenic monomer, or a mixture of any two or more thereof, and the co-monomer includes one or more deuterium atoms.Chalcogenide Halides

[0046] Examples of suitable chalcogenide halides include, but are not limited to, sulfur monohalide, a sulfur dihalide, a selenium monohalide, a selenium dihalide, a selenium tetrahalide, or a combination of any two or more thereof. In some embodiments, the chalcogenide halide is sulfur monochloride, sulfur dichloride, sulfur monobromide, selenium monochloride, selenium monobromide, selenium dichloride, selenium dibromide, selenium tetrachloride, selenium tetrabromide, or a combination of any two or more thereof. Still in other embodiments, the chalcogenide halide is sulfur monochloride, sulfur dichloride, selenium monochloride, selenium dichloride, selenium tetrachloride, or a combination of any two or more thereof.Elemental Sulfur

[0047] Co-polymerizing elemental sulfur with organic co-monomers via a process termed, inverse vulcanization, affords hybrid polymers of chalcogenide and organic comonomer units. These hybrid polymers are subsequently termed, chalcogenide hybrid inorganic / organic polymers (CHIPs). These materials are intriguing for IR optics, since the S-S bonds in the co-polymer are largely IR inactive in the MWIR and LWIR regime enabling a dramatic reduction in organic C-H, C-C, C-X bond content to below 50-wt% of the material, which results in a dramatic reduction of MWIR and LWIR absorbance of these chalcogenide hybrid polymers vs classical synthetic plastics, while also imparting high refractive index to the macromolecule, which provides for thinner optics. While CHIPs have significantly improved IR transparency relative to state of the art optical polymers, the residual organic content in these materials arising from the organic co-monomers limits theoverall IR transparency relative to inorganic transmissive materials, hindering direct application of CHIPs for IR plastic optics.

[0048] In the embodiments described herein, the elemental sulfur is Ss. The reaction product of elemental sulfur and any of the co-monomers described herein is a sulfur co-polymer. The sulfur can be provided as elemental sulfur, for example, in powdered form. Under ambient conditions, elemental sulfur primarily exists in an eightmembered ring form (Ss) which melts at temperatures in the range of 120-124 °C and undergoes an equilibrium ring-opening polymerization (ROP) of the Ss monomer into a linear polysulfane with diradical chain ends.

[0049] As the person of skill in the art will appreciate, while Ss is generally the most stable, most accessible and lowest cost feedstock, many other allotropes of sulfur can be used (such as other cyclic allotropes, derivable by melt-thermal processing of Ss). Any sulfur species that yield diradical or anionic polymerizing species when heated as described herein can be used in practicing the present invention.

[0050] The sulfur polymers / co-polymers described herein may be prepared by providing elemental sulfur, heating the elemental sulfur to a suitable temperature (e.g., from about 120 to about 230° C) to form molten sulfur, and polymerizing one or more comonomers with the molten sulfur to form the sulfur co-polymer. In some embodiments, the technique of polymerizing is free radical polymerization, controlled radical polymerization, ring-opening polymerization, ring-opening metathesis polymerization, step-growth polymerization, or chain-growth polymerization.

[0051] The sulfur content of the reaction product (e.g., the sulfur co-polymer) may be from about 1% to about 99 wt%, including from about 1% to about 95 wt% and from about 5% to about 95 wt%. In some embodiments, the sulfur content of the reaction product (e.g., the sulfur co-polymer) may be from about 50% to about 99 wt%.Co-monomers

[0052] The co-monomers described herein are those that polymerize with the molten sulfur to form the sulfur co-polymer and include one or more deuterium atoms. Illustrative co-monomers include one or more of vinyl monomers, isopropenyl monomers, acryl monomers, methacryl monomers, unsaturated hydrocarbon monomers, epoxide monomers,thiirane monomers, alkynyl monomers, diene monomers, butadiene monomers, isoprene monomers, norbomene monomers, amine monomers, thiol monomers, sulfide monomers, alkynylly unsaturated monomers, nitrone monomers, aldehyde monomers, ketone monomers, ethylenically unsaturated monomers, or styrenic monomers. In some embodiments, the co-monomer is or includes a norbornene dimer. In some embodiments, the co-monomer is or includes 1,3-diisopropenylbenzene. In some embodiments, the comonomer includes di4-l,3-diisopropenylbenzene.

[0053] The co-monomers including one or more deuterium atoms are those that polymerize with the molten sulfur to form the sulfur co-polymer. Illustrative co-monomers include, but are not limited to, vinyl monomers, isopropenyl monomers, acryl monomers, methacryl monomers, unsaturated hydrocarbon monomers, epoxide monomers, thiirane monomers, alkynyl monomers, diene monomers, butadiene monomers, isoprene monomers, norbomene monomers, amine monomers, thiol monomers, sulfide monomers, alkynylly unsaturated monomers, nitrone monomers, aldehyde monomers, ketone monomers, ethylenically unsaturated monomers, or styrenic monomers. In some embodiments, the comonomer is or includes a norbornene dimer. In some embodiments, the co-monomer is or includes 1,3-diisopropenylbenzene. In some embodiments, the co-monomer includes di4- 1,3-diisopropenylbenzene.

[0054] In some embodiments, the co-monomer has greater than about 90% deuterium incorporation. In some embodiments, the co-monomer has greater than about 95% deuterium incorporation. In some embodiments, the co-monomer has greater than about 99% deuterium incorporation. In some embodiments, the di4-l ,3- diisopropenylbenzene has about 99.2% deuterium incorporation.

[0055] In some embodiments, the reaction product (e.g., sulfur polymer or copolymer) may further include one or more termonomers selected vinyl monomers, isopropenyl monomers, acryl monomers, methacryl monomers, unsaturated hydrocarbon monomers, epoxide monomers, thiirane monomers, alkynyl monomers, diene monomers, butadiene monomers, isoprene monomers, norbomene monomers, amine monomers, thiol monomers, sulfide monomers, alkynylly unsaturated monomers, nitrone monomers, aldehyde monomers, ketone monomers, ethylenically unsaturated monomers, or styrenicmonomers. These one or more termonomers may also include one or more deuterium atoms.

[0056] In other embodiments, the reaction product (e.g., sulfur polymer or copolymer) may further include one or more polyfunctional co-monomers such as polyvinyl co-monomers, polyisopropenyl co-monomers, polyacryl co-monomers, polymethacryl comonomers, polyunsaturated hydrocarbon co-monomers, polyepoxide co-monomers, polythiirane co-monomers, polyalkynyl co-monomers, polydiene co-monomers, polybutadiene co-monomers, polyisoprene co-monomers, polynorbornene co-monomers, polyamine co-monomers, polythiol co-monomers, polysulfide co-monomers, polyalkynylly unsaturated co-monomers, polynitrone co-monomers, polyaldehyde co-monomers, polyketone co-monomers, and polyethylenically unsaturated co-monomers. The polyfunctional co-monomers may be present in an amount ranging from about 0.5 wt% to 1 wt%, or about 1 wt% to 5 wt%, or about 5 wt% to 15 wt%, or about 15 wt% to 25 wt%, or about 25 wt% to 35 wt%, or about 35 wt% to 45 wt%, or about 45 wt% to 50 wt%.

[0057] In certain embodiments, it can be desirable to use a nucleophilic viscosity modifier in liquefying the elemental sulfur when preparing the sulfur monomers, for example, before adding the co-monomers. The nucleophilic viscosity modifier can be, for example, a phosphorus nucleophile (e.g., a phosphine), a sulfur nucleophile (e.g., a thiol), or an amine nucleophile (e.g., a primary or secondary amine). When elemental sulfur is heated in the absence of a nucleophilic viscosity modifier, the elemental sulfur rings can open to form sulfur radicals that can combine to form linear polysulfide chains, which can provide a relatively high overall viscosity to the molten material. Nucleophilic viscosity modifiers can break these linear chains into shorter lengths, thereby making shorter polysulfides that lower the overall viscosity of the molten material, making the sulfur monomers easier to mix with other species, and easier to stir for efficient processing. Some of the nucleophilic viscosity modifier will react to be retained as a covalently bound part of the co-polymer, and some will react to form separate molecular species, with the relative amounts depending on nucleophile identity and reaction conditions. While some of the nucleophilic viscosity modifier may end up as a separate molecular species from the polymer chain, as used herein, nucleophilic viscosity modifiers may become part of the co-polymer. Non-limiting examples of nucleophilic viscosity modifiers include triphenylphosphine, aniline, benzenethiol, and N,N-dimethylaminopyridine. Nucleophilic viscosity modifiers can beused, for example, in an amount up to about 5 wt%, or even up to about 10 wt% of the sulfur co-polymer. When a nucleophilic viscosity modifier is used, in certain embodiments it can be used in the range of about 1 wt% to about 10 wt% of the sulfur co-polymer.

[0058] The co-polymerization of the one or more monomers of amine monomers, thiol monomers, sulfide monomers, alkynylly unsaturated monomers, nitrone monomers, aldehyde monomers, and ketone monomers in liquid as used herein produces the advantageous sulfur co-polymer compositions. For example, the amine monomer, such as those on aromatic compounds, results in direct C — S bond formation and co-polymerization with sulfur concurrently. Thiol monomers from a wide range of co-monomer precursors widely used in the preparation of condensation polymers can be dissolved and copolymerized with liquid sulfur to afford high sulfur content co-polymers. Unexpectedly, the thiol derived co-polymer was solution processable despite the high content of sulfur and rigid aromatic moieties. Sulfide monomers can co-polymerize with sulfur via either ionic or free radical processes. Unexpectedly, the sulfide monomer was able to afford both low glass transition polymers or higher glass transition polymers. As another example, the alkynylly unsaturated monomer is expected to react via known thiol-yne processes, however, unexpectedly, the alkynylly unsaturated monomer was able to afford polythiophene and other heterocycles. The nitrone monomer is expected to react via free radical polymerizations with sulfur radicals. Unexpectedly, the nitrone monomer was designed to afford polymeric materials when co-polymerized with elemental sulfur. Aldehyde based monomers are not expected to react with sulfur radicals, however, the formation of polymers was observed when the appropriate di-, or multifunctional aldehydes are co-polymerized with sulfur. Ketone based monomers are not expected to react with sulfur radicals, however, the formation of polymers was observed when the appropriate di-, or multifunctional ketones are co-polymerized with sulfur.

[0059] The co-monomer content of the reaction product (e.g., the sulfur co-polymer) may be from about 1% to about 99 wt%, including from about 1% to about 50 wt% and from about 1% to about 30 wt%. In some embodiments, the co-monomer content of the reaction product (e.g., the sulfur co-polymer) may be from about 1% to about 40 wt%.

[0060] The sulfur polymers (e.g., reaction products) described herein have a refractive index of from about 1.5 to about 2.6, including from about 1.5, about 1.6, about1.7, about 1.75, about 1.8, about 1.9, about 2.0, about 2.1, about 2.2, about 2.3, about 2.4, about 2.5, and about 2.6. In some embodiments, the sulfur polymer (e.g., reaction product) described herein has a refractive index of from about 1.70 to about 2.1.

[0061] The sulfur polymers (e.g., reaction products) described herein have a glass transition temperature of from about 75 °C to about 100 °C, including about 75 °C, about 80 °C, about 85 °C, about 90 °C, about 95 °C, and about 100 °C. In some embodiments, the sulfur polymer (e.g., reaction product) described herein has a glass transition temperature of about 100°C.

[0062] Provided in another aspect is a process for producing any of the compositions described herein. The processes include admixing a monomeric mixture of (a) one or more of elemental sulfur or chalcogenide halide and (b) a co-monomer to form an admixture and polymerizing the admixture. In the process, the co-monomer may include a vinyl monomer, isopropenyl monomer, acryl monomer, methacryl monomer, unsaturated hydrocarbon monomer, epoxide monomer, thiirane monomer, alkynyl monomer, diene monomer, butadiene monomer, isoprene monomer, norbornene monomer, amine monomer, thiol monomer, sulfide monomer, alkynyl unsaturated monomer, nitrone monomer, aldehyde monomer, ketone monomer, ethylenically unsaturated monomer, styrenic monomer, or a mixture of any two or more thereof. Additionally, the co-monomer may include one or more deuterium atoms.

[0063] In some embodiments, the composition is suitable for use in long wavelength infrared (LWIR) applications (e.g., the composition is transparent under LWIR applications). In some embodiments, the composition is suitable for use in mediume wavelength infrared (MWIR) applications (e.g., the composition is transparent under MWIR applications). In some embodiments, the composition is suitable for use in medium wavelength infrared (MWIR) applications from about 3.3 to about 3.4 microns (e.g., the composition is transparent under MWIR applications from about 3.3 to about 3.4 microns). In some embodiments, the composition is suitable for use in medium wavelength infrared (MWIR) applications at about 3.3 microns or at about 3.4 microns (e.g., the composition is transparent under MWIR applications at about 3.3 microns or at about 3.4 microns).

[0064] In some embodiments, the composition is molded or solution processed into a fabricated optical element. Such fabricated optical elements may include free standingfilms or nano or micropatterned polymer forms. In some embodiments, the composition improves the average IR transmission of the fabricated optical element over that of an element made from the undeuterated material, in a MWIR wavelength range (e.g., the composition increases the transparency of the fabricated optical element over that of an element made from the undeuterated material, in a MWIR wavelength range). In some embodiments, the MWIR wavelength range of about 3.0 microns wavelength to about 4.2 microns wavelength, from about 3.0 microns wavelength to about 3.3 microns wavelength, or from about 3.3 microns wavelength to about 4.2 microns wavelength. In some embodiments, the composition is suitable for use in MWIR photonic devices. Suitable MWIR photonic devices include waveguides, optical grating, and ring-resonators.

[0065] Provided in another aspect is an article of manufacture that may include any of the compositions described herein.

[0066] In some embodiments, the article of manufacture is an imaging device.

[0067] The present invention, thus generally described, will be understood more readily by reference to the following examples, which are provided by way of illustration and are not intended to be limiting of the present invention.EXAMPLES

[0068] The following examples illustrate various protocols for preparing compounds and devices according to the embodiments described above. The examples should in no way be construed as limiting the scope of the present technology.

[0069] While certain embodiments have been illustrated and described, it should be understood that changes and modifications can be made therein in accordance with ordinary skill in the art without departing from the technology in its broader aspects as defined in the following claims.Example 1

[0070] Synthesis of d -DIB. Our first approaches focused on synthesizing ch- 1 ,3- dibromo benzene, which is the deuterated variant of the intermediate from the a \-proteo synthesis of DIB. In the first route, t / s-toluene was oxidized and meta-brominated and then a photochemically-mediated decarb oxy lative bromo installation was evaluated,35whichunfortunately suffered from low yields, unwanted over-bromination, proto-incorporation and product separation issues. A complementary route from t / j-nitrobenzene involved meta-bromination and nitro-group reduction to set the stage for bromo-incorporation via diazotization also failed as the intermediate aniline36readily exchanged deuterium, which proved difficult to suppress. The problem with this route became more apparent when we evaluated installation of the ewtero-propenyl groups via Suzuki and Stille couplings respectively. Synthesis of the Suzuki reagent involved significant challenges, such as unattractive volatile intermediates GA-2-bromopropene) and use of expensive and atom uneconomical tris-triisopropyl sulfonyl hydrazide and t / e-acetone as the solvent along with other hydrazines for this umpolung approach resulting in unacceptable levels of proton incorporation33In contrast, the Stille reagent was readily synthesized by using the anion of tributyl stannane to attack t / e-acetone followed by dehydration.38Disappointingly, Stille cross-couplings were not-successful, although we were able to realize such a coupling with deuterated 3 -bromomethyl benzoate. Transmetallations of t / v-dibromobenzene and trapping with t / e-acetone were also evaluated but with no success. These synthesis attempts, and others we assessed, illustrated the challenges of synthesizing fully deuterated target structures with high enrichment levels of deuterium.

[0071] After several rounds of unsuccessful t / / v-DIB total synthesis attempts, we used those lessons and insights while factoring in the few viable low-cost deuterium rich starting materials to design a total synthesis of t / / v-DIB that negated the use of transition metals and employed steps with low chance of unwanted hydrogen atom incorporation. Deuterated toluene (tfe-toluene) emerged quickly as promising starting material, and strategies involving careful addition and elimination steps proved most reliable in ensuring and maintaining high deuterium incorporation throughout the total synthesis (FIG. 2). Toward that end, after oxidation39and bromination of t / s-toluene40the resulting meta-bromo carboxylic acid (1) was esterified and subjected to CDsMgl addition to afford 2 following deuteration with CH3OD. Dehydration was accomplished with deuterated para- toluenesulfonic acid ( / ?-TsOD), yielding propene 3. Transmetallation of the bromide and trapping of the resulting aryl lithium nucleophile with t / e-acetone delivered alcohol 4. The final step in the total synthesis was an alcohol dehydration with / ?-TsOD, which interestingly proceeded not only faster but at lower temperatures than the earlier dehydration step. We were able to realize the first total synthesis of t / / v-DIB with 99.2%deuterium incorporation, as evident from spectral (FIGS. 3A-3B and 4A-4B) and high- resolution mass spectrometry.

[0072] Structural characterization of t / zv-DIB was confirmed using a combination of solution13C,2H NMR spectroscopy along with mass spectrometry. Solution13C NMR spectroscopy of t / 14-DIB (99.2% Z>) vs proteo DIB as shown in FIG. 3 revealed striking differences in both chemical shift and splitting of resonances, where C-H decoupling affords singlet peaks in the13C NMR spectra. However, since C-D peaks were not decoupled in these experiments, multiplet peaks were observed for C-D nuclei in the13C NMR spectra since deuterium is a nuclear magnetic spin type / = 1 as seen in for sp2hybridized carbon atoms bonded to deuterium atoms from the isopropenyl moieties (Cb-D2, 6 = 112.19, multiplet) and from the aromatic ring (Cc-D, Cd-D, Ce-D, 6 = 127.79, 124.13, 121.80, triplets) (FIG. 3 A). These13C resonances afforded multiplets and triplets due to C- D splitting (FIG. 3 A), without any traces of C-H resonances observed in these spectra, as noted by direct comparison the C-H decoupled singlet peaks observed in the13C NMR spectra of / -DIB (FIG. 3B). The chemical shifts of C-D peaks of tZ / v-DIB were also shifted by varying ppm values ranging from 6 = 0.99 to 0.24 relative to the analogous proteo C-H peaks of DIB. Solution2H deuterium NMR spectroscopy of t / 14-DIB (99.2% D) taken in proteo benzene also provided clear evidence for the synthesis of perdeuterated DIB monomers as noted by the expected five single peaks presented in FIG. 4A, which are contrasted with the proton-NMR spectrum of proteo- DIB (FIG. 4B) in benzene.

[0073] Synthesis of perdeuterated sulfur co-polymers via inverse vulcanization.With t / i4-DIB in hand, the inverse vulcanization with S8 was conducted with both 50:50 wt% feed ratio to prepare deuterated poly(S- / '-t / i4DIB). t / zv-DIB was observed to be miscible in liquid sulfur at elevated temperatures (T = 175 °C) and produced orange amorphous glassy co-polymers comparable to the proteo sulfur co-polymers. Elemental analysis of the neat co-polymer confirmed the target composition was present. Thermal analysis using differential scanning calorimetry (DSC) confirmed a slight difference of a few degrees Celsius in the Tgvalues for the deuterated co-polymers in comparison to proteo poly(S-r-DIB) 50 / 50 composition (Tg Proteo = 29.7 °C, Tgdeutero = 23.6 °C). The effect of deuteration was not found to significantly effect the Tgof poly(S-r-DIB) vs poly(S-r- tZ / vDIB) since the fairly high content of sulfur in the co-polymer smeared out any observable effects that would be more pronounced for deutero vs proteo homopolymers(full DSC profiles can be found in the SI).5,22TGA profiles also indicated identical decomposition profiles (decomposition at -250 °C) for both proteo and deutero poly(S-r- DIB), which was not surprising given how decomposition of S-S bonds mechanistically drives the weight loss irrespective of H / D exchange on the organic co-monomer.

[0074] IR spectroscopic characterization of du-DIB and poly S-r-d DIB). IR spectroscopy of t / / v-DIB vs proteo DIB was initially conducted with neat liquids between NaCl plates to interrogate the effects of deuteration on key vibrational C-H bonds in the MWIR from 3.3-3.4 pm (-3000-2900 cm’1). The spectral features in the MWIR region of proteo DIB for sp3and sp2hybridized C-H bonds resulted in a series of complex vibrational bands in aromatic CH stretching region (-3030 cm '), alkenyl (-3100-3050 cm’1), and in the alkyl stretching region (3000-2850 cm '). In contrast the MWIR spectrum of t / 14-DIB (99.2% D) was nearly featureless in the CH aromatic, alkenyl and alkyl spectral windows from 3.2-3.5 pm (3100-2850 cm’1) along with the observation of series of new vibrations resonances from (-2400-2000 cm’1) which were attributed to both fundamental and overtone bands from aromatic and methyl C-D bonds, as previously reported for related deuterated toluene compounds (FIGS. 5A and 5B).37IR spectroscopic features of the proteo and deutero DIB in the LWIR region of the spectra from 6-20 pm exhibited numerous fundamental vibrations and combination bands as expected for aromatic and organic compounds. The IR spectroscopy features of poly(S-r-di4DIB) (50 / 50, wt / wt) were taken of free-standing melt processed films of varying thickness from (-100-500 pm) and were found largely similar to those of the t / u-DIB monomer except for observed broadening of C-D fundamental vibrations from 2400-2000 cm’1. A notable difference in IR spectra of poly(S-r-t / i4DIB) co-polymer films vs t / / v-DIB was two peaks around 2900 cm-1 / 3.4 pm and 3250 cm-1 / 3.1 pm (FIG. 5C). After extensive comparisons with ds-toluene of comparable deuteration levels (99%) we concluded that these peaks from around 2900 cm’1were due to C-H fundamental vibrations arising from trace C-H impurities carried from the deuterated NMR solvents (ds-toluene, e-acetone) used as the starting materials in the synthesis of di4- DIB. The peak observed around 3250 cm’1was attributed to C-D overtone vibrations, that were shifted into the MWIR, since no other vibrational bands are observed for the proteo toluene, or acetone analogues. Despite the low levels of C-H present in the t / / v-DIB and poly(S-r-d7vDIB), these absorbances are more pronounced in thicker melt pressed samples, which we start to observe at film thicknesses above 100-200 um. These trace C-H peaks are faintly observable in the MWIR region from 3100-2900 cm-1 in the baseline of the t / / v-DIBspectra, where the sample prep was done as a thin fill of the neat monomer between NaCl plates, which we estimate is on the order of tens of microns and much thinner than the spectra shown for the deuterated sulfur co-polymer. The observation of these trace C-H vibration and overtone peaks from the IR spectra poly(S-r-di4DIB) films was initially surprising given the high level of deuteration achieved in the synthesis of t / / v-DIB (99+%, Z>), however, the model solution IR spectra of t / s-toleune (99+%, D) of similar purity and comparable pathlengths (0.1-0.5 mm), confirmed similar levels of transmission arising from these proteo impurities; this is a natural result of Beer's law of transmission, which is exponentially dependent on the sample thickness. This further explains why inorganic semiconductors, such as, germanium require ultra-high levels of purity (>99.999%) to enable use for fabrication of free-standing lenses and windows exceeding 1 mm in thickness.

[0075] Nevertheless, in comparison to proteo poly(S-r-DIB) co-polymer films prepared as control films at identification thicknesses, the 3.3-3.4 micron region of the MWIR spectrum was completely saturated from C-H vibrational absorbances, which points to the benefits of deuteration to significantly improve MWIR transparency at the technologically important wavelength around 3.3 microns.

[0076] Embodiments

[0077] Embodiment 1. A composition comprising a polymer that is a reaction product of a co-monomer and one or more of elemental sulfur and a chalcogenide halide, wherein the co-monomer is a vinyl monomer, isopropenyl monomer, acryl monomer, methacryl monomer, unsaturated hydrocarbon monomer, epoxide monomer, thiirane monomer, alkynyl monomer, diene monomer, butadiene monomer, isoprene monomer, norbomene monomer, amine monomer, thiol monomer, sulfide monomer, alkynyl unsaturated monomer, nitrone monomer, aldehyde monomer, ketone monomer, ethylenically unsaturated monomer, styrenic monomer, or a mixture of any two or more thereof; and the co-monomer comprises one or more deuterium atoms.

[0078] Embodiment 2. The composition of Embodiment 1, wherein the polymer is the reaction product of the co-monomer and elemental sulfur, and the elemental sulfur is Ss.

[0079] Embodiment 3. The composition of Embodiments 1 or 2, wherein the comonomer has greater than about 90% deuterium incorporation.

[0080] Embodiment 4. The composition of Embodiments 1 or 2, wherein the comonomer has greater than about 95% deuterium incorporation.

[0081] Embodiment 5. The composition of Embodiments 1 or 2, wherein the comonomer has greater than about 99% deuterium incorporation.

[0082] Embodiment 6. The composition of any one of Embodiments 1-5, wherein the co-monomer comprises 1,3-diisopropenylbenzene.

[0083] Embodiment 7. The composition of Embodiment 6, wherein the comonomer comprises di4-l,3-diisopropenylbenzene.

[0084] Embodiment 8. The composition of Embodiment 7, wherein the di4- 1,3- diisopropenylbenzene has about 99.2% deuterium incorporation.

[0085] Embodiment 9. The composition of any one of Embodiments 1-8, wherein the composition has a refractive index of from about 1.70 to about 2.1.

[0086] Embodiment 10. The composition of any one of Embodiments 1-9, wherein the composition is transparent under long wavelength infrared (LWIR) applications.

[0087] Embodiment 11. The composition of any one of Embodiments 1-9, wherein the composition is transparent under medium wavelength infrared (MWIR) applications.

[0088] Embodiment 12. The composition of Embodiment 11, wherein the composition is transparent under medium wavelength infrared (MWIR) applications from about 3.3 to about 3.4 microns.

[0089] Embodiment 13. The composition of Embodiment 11, wherein the composition is transparent under medium wavelength infrared (MWIR) applications at about 3.3 microns or at about 3.4 microns.

[0090] Embodiment 14. The composition of any one of Embodiments 1-9, wherein the composition is molded or solution processed into a fabricated optical element.

[0091] Embodiment 15. The composition of any one of Embodiments 1-9, wherein the composition increases the transparency of the fabricated optical element over that of an element made from the undeuterated material, in a MWIR wavelength range, and optionally, wherein the MWIR wavelength is from about 3.0 microns wavelength to about 4.2 microns wavelength, from about 3.0 microns wavelength to about 3.3 microns wavelength, or from about 3.3 microns wavelength to about 4.2 microns wavelength.

[0092] Embodiment 16. The composition of any one of Embodiments 1-9, wherein the composition is transparent under MWIR photonic devices, and optionally, wherein the MWIR photonic devices are selected from waveguides, optical grating, and ring-resonators.

[0093] Embodiment 17. An article of manufacture comprising the composition of any one of Embodiments 1-16.

[0094] Embodiment 18. The article of Embodiment 17 which is an imaging device.

[0095] Embodiment 19. A process for producing a composition that includes any of Embodiments 1-16, the process comprising: admixing a mixture comprising (a) one or more of elemental sulfur or a chalcogenide halide and (b) a co-monomer to form an admixture; polymerizing the admixture; wherein: the co-monomer comprises a vinyl monomer, isopropenyl monomer, acryl monomer, methacryl monomer, unsaturated hydrocarbon monomer, epoxide monomer, thiirane monomer, alkynyl monomer, diene monomer, butadiene monomer, isoprene monomer, norbornene monomer, amine monomer, thiol monomer, sulfide monomer, alkynyl unsaturated monomer, nitrone monomer, aldehyde monomer, ketone monomer, ethylenically unsaturated monomer, styrenic monomer, or a mixture of any two or more thereof; and the co-monomer comprises one or more deuterium atoms.

[0096] The embodiments, illustratively described herein may suitably be practiced in the absence of any element or elements, limitation, or limitations, not specifically disclosed herein. Thus, for example, the terms “comprising,” “including,” “containing,”etc. shall be read expansively and without limitation. Additionally, the terms and expressions employed herein have been used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding 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 claimed technology.Additionally, the phrase “consisting essentially of’ will be understood to include those elements specifically recited and those additional elements that do not materially affect the basic and novel characteristics of the claimed technology. The phrase “consisting of’ excludes any element not specified.

[0097] The present disclosure is not to be limited in terms of the particular embodiments described in this application. Many modifications and variations can be made without departing from its spirit and scope, as will be apparent to those skilled in the art. Functionally equivalent methods and compositions within the scope of the disclosure, in addition to those enumerated herein, will be apparent to those skilled in the art from the foregoing descriptions. Such modifications and variations are intended to fall within the scope of the appended claims. The present disclosure is to be limited only by the terms of the appended claims, along with the full scope of equivalents to which such claims are entitled. It is to be understood that this disclosure is not limited to particular methods, reagents, compounds, compositions, or biological systems, which can of course vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting.

[0098] In addition, where features or aspects of the disclosure are described in terms of Markush groups, those skilled in the art will recognize that the disclosure is also thereby described in terms of any individual member or subgroup of members of the Markush group.

[0099] As will be understood by one skilled in the art, for any and all purposes, particularly in terms of providing a written description, all ranges disclosed herein also encompass any and all possible subranges and combinations of subranges thereof. Any listed range can be easily recognized as sufficiently describing and enabling the same range being broken down into at least equal halves, thirds, quarters, fifths, tenths, etc. As a nonlimiting example, each range discussed herein can be readily broken down into a lowerthird, middle third and upper third, etc. As will also be understood by one skilled in the art all language such as “up to,” “at least,” “greater than,” “less than,” and the like, include the number recited and refer to ranges which can be subsequently broken down into subranges as discussed above. Finally, as will be understood by one skilled in the art, a range includes each individual member.

[0100] All publications, patent applications, issued patents, and other documents referred to in this specification are herein incorporated by reference as if each individual publication, patent application, issued patent, or other document was specifically and individually indicated to be incorporated by reference in its entirety. Definitions that are contained in text incorporated by reference are excluded to the extent that they contradict definitions in this disclosure.

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Claims

WHAT IS CLAIMED IS:

1. A composition comprising: a polymer that is a reaction product of a co-monomer and one or more of elemental sulfur and a chalcogenide halide; wherein: the co-monomer is a vinyl monomer, isopropenyl monomer, acryl monomer, methacryl monomer, unsaturated hydrocarbon monomer, epoxide monomer, thiirane monomer, alkynyl monomer, diene monomer, butadiene monomer, isoprene monomer, norbornene monomer, amine monomer, thiol monomer, sulfide monomer, alkynyl unsaturated monomer, nitrone monomer, aldehyde monomer, ketone monomer, ethylenically unsaturated monomer, styrenic monomer, or a mixture of any two or more thereof; and the co-monomer comprises one or more deuterium atoms.

2. The composition of claim 1, wherein the polymer is the reaction product of the comonomer and elemental sulfur, and the elemental sulfur is Ss.

3. The composition of claim 1, wherein the co-monomer has greater than about 90% deuterium incorporation.

4. The composition of claim 1, wherein the co-monomer has greater than about 95% deuterium incorporation.

5. The composition of claim 1, wherein the co-monomer has greater than about 99% deuterium incorporation.

6. The composition of claim 1, wherein the co-monomer comprises 1,3- diisopropenylbenzene.

7. The composition of claim 6, wherein the co-monomer comprises di4- 1 ,3- diisopropenylbenzene.

8. The composition of claim 7, wherein the di4-l,3-diisopropenylbenzene has about 99.2% deuterium incorporation.

9. The composition of claim 1, wherein the composition has a refractive index of from about 1.70 to about 2.1.

10. The composition of claim 1, wherein the composition is transparent under long wavelength infrared applications.

11. The composition of claim 1, wherein the composition is transparent under medium wavelength infrared applications.

12. The composition of claim 11, wherein the composition is transparent under medium wavelength infrared applications from about 3.3 to about 3.4 microns.

13. The composition of claim 11, wherein the composition is transparent under medium wavelength infrared applications at about 3.3 microns or at about 3.4 microns.

14. The composition of claim 1, wherein the composition is molded or solution processed into a fabricated optical element.

15. The composition of claim 1, wherein the composition increases the transparency of the fabricated optical element over that of an element made from the undeuterated material, in a MWIR wavelength range, and optionally, wherein the MWIR wavelength range is from about 3.0 microns wavelength to about 4.2 microns wavelength, from about 3.0 microns wavelength to about 3.3 microns wavelength, or from about 3.3 microns wavelength to about 4.2 microns wavelength.

16. The composition of claim 1, wherein the composition is transparent under MWIR photonic devices, and optionally, wherein the photonic devices are selected from waveguides, optical grating, and ring-resonators.

17. An article of manufacture comprising the composition of claim 1.

18. The article of claim 17 which is an imaging device.

19. A process for producing a composition of claim 1, the process comprising: admixing a mixture comprising (a) one or more of elemental sulfur and a chalcogenide halide, and (b) a co-monomer to form an admixture; and polymerizing the admixture;wherein: the co-monomer comprises a vinyl monomer, isopropenyl monomer, acryl monomer, methacryl monomer, unsaturated hydrocarbon monomer, epoxide monomer, thiirane monomer, alkynyl monomer, diene monomer, butadiene monomer, isoprene monomer, norbornene monomer, amine monomer, thiol monomer, sulfide monomer, alkynyl unsaturated monomer, nitrone monomer, aldehyde monomer, ketone monomer, ethylenically unsaturated monomer, styrenic monomer, or a mixture of any two or more thereof; and the co-monomer comprises one or more deuterium atoms.

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