Sulfur-containing thermosetting polymers and photopolymers and compositions thereof

Abstract

A composition includes the reaction products of sulfur monochloride with an allyl methacrylate. The compositions described herein provide photopolymers and. thermosetting polymers with attractive optical properties (RI, transparency) and thermomechanicals (high Tg).

Description

Atty. Dkt. No. 118537-0501 SULFUR-CONTAINING THERMOSETTING POLYMERS AND PHOTOPOLYMERS AND COMPOSITIONS THEREOF CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] The present application claims the benefit of and priority to U.S. Provisional Application No. 63 / 635,283, filed April 17, 2024, the contents of each of which are incorporated herein by reference in their entireties. GOVERNMENT SUPPORT

[0002] This invention was made with government support under Grant No. 2201155 awarded by the National Science Foundation. The government has certain rights in the invention. FIELD

[0003] The present invention relates to reacting sulfur monochloride with an allyl methacrylate to provide reaction products. Such reaction products are used to provide photopolymers and thermosetting polymers with attractive with attractive optical properties (high refractive index (RI), high transparency in the visible and near and short-wave infrared spectrum) and thermomechanicals (high glass transition (Tg) and high mechanical strength). BACKGROUND

[0004] The preparation of high refractive index polymers coupled with high optical transparency (also measured as optical transmittance = %T) is critical for numerous applications across the visible and infrared spectrum. The consumer eyewear global market as of 2018 was estimated to be around $120 billion with products spanning spectacles, plano sunglasses, metal based eye-wear and contact lenses across numerous distributions channels (From Statistica’s 2019 market study “Eyeware in the US”). For this application, high volume, low cost optical polymers are required with outstanding optical properties with respect to color, transparency and refractive index, along with excellent thermomechanical properties and environmental stability. These materials afford large advantages over metal oxide glasses in areas such as weight reduction andAtty. Dkt. No. 118537-0501fracture resistance. A number of optical figures of merit must be achieved for a polymerto be useful for specific optical application. For any plastic lens, the optical materials properties of interest are the summation of the refractive index (n), the chromatic dispersion as noted by the “Abbe number (VD)”, and the optical transmittance (%T) in the visible spectrum. The refractive index (RI, or n) of a material reports on the “bending” or “focusing power” of fabricated lenses at a certain spectral window, or wavelength of interest, where higher RI materials enable thinner, lighter lenses to be designed while maintaining suitable focal lengths for use as consumer spectacles and robust mechanical properties. Hence, the plastic optics industry has spent decades to raise the RI of polymeric materials by inclusion of a high content of polarizable atoms, such as, sulfur, or bromine to raise the molar refraction. The plastic eye-ware industry has recently pushed for lens materials with RI values exceeding n = 1.65 in the visible spectrum. In addition to high refractive index, plastic lenses for consumer eye-ware must also have a sufficiently high Abbe number, which reports on the refractive index, or chromatic dispersion of an optical material. A high Abbe number indicates that refractive index values of lenses are fairly constant over the visible spectrum and exhibit high optical transparency (as reported as a transmittance percentage (%T)), which indicates the absence of optical absorption and coloration in the material. The Abbe’s number (VD) as shown in Equation 1, where nD, nF, and nC are the refractive indices of the material at the wavelength of the sodium D (587.3 nm), hydrogen F (486.1 nm), and hydrogen C (656.3 nm) lines, respectively.

[0005] Current optical polymer technology revolves principally around well- established thermoplastic, or thermoset polymers, such as, poly(methyl methacrylate)(PMMA), or polyallylcarbonates (commercially, CR-39 from PPG), polycarbonates, poly(cyclic olefins)(e.g, TOPAS) and more recently from thermosetting resins based on episulfides, poly(thio)urethanes from companies such as Mitsui Chemical & Hoya. Very high Abbe number polymers (VD~ 59), such as, PMMA and CR-39 have low RI (n ~ 1.5). Highly aromatic plastics, such as polystyrene, polycarbonates and polyimides, possess higher refractive indices (n = 1.55-1.75), butAtty. Dkt. No. 118537-0501 have significantly lower Abbe numbers, where values below VD< 30 render these unusable for consumer eye-ware. In the vast majority of cases, high RI polymers above n = 1.60 typically possess lowered Abbe numbers and may be strongly colored, which has prompted significant investigated into new polymeric materials design to balance both higher RI and Abbe number values.

[0006] The preparation of both high RI (n > 1.60) and high Abbe number (VD> 30) plastic optics has primarily been achieved by the inclusion of a higher content of polarizable atoms and groups of high molar refraction, into either the backbone, or side chain groups of polymeric materials. The primary focus of these improvements has been the preparation of sulfur containing polymers, since regulations and toxicity concerns preclude the introduction of selenium, or transition metal units. Notable discoveries include the synthesis and polymerization of 2,5-bis(sulfanylmethyl)- 1,4-dithiane (BMMD) as initially reported and Okubo et al. Ueda et al. further explored BMMD chemistry via thiol-ene polymerizations, methacrylate free radical copolymerizations, or addition step-growth with diisocyanates to prepare high RI (n ~1.65) and high Abbe number (VD~ 40) polymers). Stiegman et al. reported on the copolymerization standard dithiols, or bis-thiophenolic monomers with either multi-vinylic Group IV monomers (i.e., organo Si, Ge, Sn), or trivinyl phosphine chalcogenide (S,Se) monomers to form high RI copolymer networks with Abbe number ranging from VD= 20-33. Examples of industrially commercialized high RI / / high Abbe number thermosets include Hoya’s EYAS 160 polythiourethanes (RI = 1.60, VD= 40) made from the BMMD dithiol, tetrathiols and diisocyanates, along with Hoya’s EYVIA 174 (RI = 1.74, VD= 30) made from bis-episulfides, dithiols and elemental sulfur.

[0007] Despite these advances, the major issue with larger scale production of high RI and high Abbe number consumer plastic lenses has been the high cost associated with di-, multi-thiol monomers. While thiol compounds are certainly commercially available, there remain a limited scope of di-, multi-thiol compounds available. Accordingly, the optics industry must conduct their own in house multi-step synthesis of specialty dithiane dithiol monomers, such as, BMMD, which ultimately results in small scale, low volume production of high RI plastic lenses. Hence, there remains a technological need for new polymerization chemistry to incorporate a high content of sulfur atoms using inexpensive sulfur containing monomers that are suitable for high volume optical plastics.Atty. Dkt. No. 118537-0501

[0008] The ability to photopolymerize optical polymeric materials holds significant advantages over classical thermal curing and casting methods for optical element- component-device fabrication as noted by the ability to arbitrary shape monomers and rapidly cure under irradiation. The current methods utilize UV-curing under ambient conditions using classical free radical polymerization of (meth)acrylate, vinylic, allylic, of thiol based monomers, or ionic polymerization of epoxide monomers (most notably SU8). While photopolymerization methods have gained significant attention, particularly for 3D printing photopolymerization methods (e.g., stereolithography, digital light processing), these methods have not been applied to optical component fabrication of bulk free form optics due to limitations in the monomer-resin chemistry and composition. Due to the need for making bulk free form lens, or windows for consumer eyeware, optical polymers should have the combination of high RI, high transparency- low birefringence-high Abbe number (to avoid haziness in thick optics), good thermomechnical properties, limited coloration-tinting and facile melt processabilty, while also being very low cost for high volume production. However, direct translation of these requirements into monomers that can be photopolymerized and afford desirable optical polymers for use in visible spectrum optics remain challenging.

[0009] Examples and limitations of existing photopolymers and photopolymer resins-monomers are listed below: 1) current photopolymer resins that afford high Tg polymers with good thermomechanicals typically have low refractive index (n ~ 1.49) 2) incorporation of aromatic groups into photopolymers resins raise refractive index, but also introduce birefringence which results in haziness for polymers when cast into thick windows, or lenses. Furthermore, aromatic groups optical absorb in the UV-spectrum which complicated UV-photopolymerization of bulk thick polymeric components. The commercial photoresist, “SU8” is an example of this issue, as the aromatic bisphenol A groups of this photopolymerizable epoxy affords higher RI values (n ~ 1.56), but is mainly limited to thin film photoresist product applications and not for bulk optical components. 3) high RI photopolymers have been produced by using thiol monomers with alkenes, or alkynes in thiol-ene, thiol-yne (“thiol-X”) photopolymerization.Atty. Dkt. No. 118537-0501 However, thiol monomers are manufactured from there reaction of hydrogen sulfide and aliphatic alcohols, which typically affords thiol monomers with aliphatic-flexible structural motifs, which affords mechanically softer photopolymers with lower Tg’s. Furthermore, thiol monomers are fairly narrow in scope, and tend to be more expensive than classical vinylic, or epoxy monomers. 4) many high RI monomers that afford high RI polymers contain sulfur or heteroatom atoms / groups in the monomer which confer yellow, or colored polymers rendering these unusable for visible spectrum optical products.

[0010] This disclosure addresses these needs by providing photopolymers and thermosetting polymers with attractive optical properties (high refractive index (RI), high transparency in the visible and near and short-wave infrared spectrum) and thermomechanicals (high glass transition (Tg) and high mechanical strength), in particular photopolymers with a high refractive index and low birefringence. In particular, such polymers are prepared from the reaction products that are obtained from reacting sulfur monochloride with an allyl methacrylate.

[0011] 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 present invention are apparent in the following detailed description and claims. SUMMARY

[0012] Sulfur monochloride (S2Cl2) is an inexpensive commodity petrochemical (~$5 per kg), but it is not widely used in chemical production. This disclosure describes the preparation of low cost di-, and multi-functional methacrylate monomers that are obtained by reacting sulfur monohalides (e.g., sulfur monochloride) with one or more methacrylate compounds (e.g., allyl methacrylate). The reaction of S2Cl2with allyl methacrylate affords a disulfide dimer bearing 2-methacrylate groups that can be used to prepare thermosetting polymers and photopolymers that have high glass transition (Tg >Atty. Dkt. No. 118537-0501 85 °C), high RI (n > 1.55) and provide transparent glassy materials. Terpolymerizations of S2Cl2with allyl comonomers (e.g., diallyl, or triallyl monomers) via sulfenyl chloride inverse vulcanization can be terminated by the addition of mono-allyl methacrylate agents (e.g., allyl methacrylate) to prepare macromonomer prepolymers which can be thermally, or photolytically cured to make glassy, crosslinked networks via free radical thermal, or photopolymerization. This disclosure has significant potential as a new commodity optical photopolymer resin for direct production for plastic optics, or as a photopolymer resin for 3D printing via photopolymerization stereolithography.

[0013] Provided in one aspect is a composition comprising the reaction products of sulfur monochloride with an allyl methacrylate.

[0014] In some embodiments, the reaction products are a mixture of anti- Markovnikov and Markovnikov addition products, wherein the anti-Markovnikov product is present in amount of greater than about 30 mol%, greater than about 40 mol%, greater than about 50 mol%, greater than about 60 mol%, greater than about 70 mol%, or greater than about 80 mol%.

[0015] In some embodiments, the reaction products further comprise one or more allylic olefins. In embodiments, the one or more allylic olefins comprise a diallyl or a triallyl compound. In some embodiments, the one or more allylic olefins comprise triallyltriazinetrione.

[0016] Provided in one aspect is a composition comprising a polymer that is a reaction product of one or more compositions comprising the reaction products of sulfur monochloride with an allyl methacrylate under thermal polymerization reaction conditions sufficient to produce the polymer.

[0017] In some embodiments, the thermal polymerization reaction conditions require a radical initiator. In some embodiments, the radical initiator comprises azobisisobutyronitrile (AIBN).

[0018] In some embodiments, the thermal polymerization reaction conditions require a low-temperature thermal initiator. In some embodiments, the low-temperature thermal initiator comprises 2,2’-azobis(4-methoxy-2,4-dimethylvalero-nitrile.Atty. Dkt. No. 118537-0501

[0019] Provided in one aspect is a composition comprising a polymer that is a reaction product of one or more compositions comprising the reaction products of sulfur monochloride with an allyl methacrylate under photo polymerization reaction conditions sufficient to produce the polymer.

[0020] In some embodiments, the photo polymerization reaction conditions require a photoinitiator. In some embodiments, the photoinitiator comprises diphenyl(2,4,6 trimethylbenzoyl)phosphine oxide.

[0021] In some embodiments for the compositions comprising the polymer, the reaction product further comprises one or more olefin compounds. In some embodiments, the one or more olefin compounds comprise methyl methacrylate.

[0022] Provided in another aspect for preparing composition comprising the reaction products of sulfur monochloride with an allyl methacrylate including contacting sulfur monochloride and allyl methacrylate in the presence of a tetraalkylammonium salt.

[0023] In some embodiments, the process further comprises heating at a temperature of about 50 °C. In some embodiments, the tetralkylammonium salt comprises tetrabutylammonium chloride. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] FIG. 1 illustrates the stackedNMR spectra of DSMR fractions after purification.

[0025] FIG. 2A illustrates the TGA of poly DSMR.

[0026] FIG. 2B illustrates the DSC thermogram of poly DSMR.

[0027] FIG. 2C illustrates refractive index measurement by ellipsometry and prism.

[0028] FIG. 2D illustrates UV-Vis transmittance measurements of DMSR windows coupling.Atty. Dkt. No. 118537-0501 DETAILED DESCRIPTION

[0029] 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).

[0030] 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.

[0031] 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.

[0032] 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.

[0033] This disclosure recognizes the use of sulfur monochloride (S2Cl2) for the preparation of low cost di-, and multi-functional methacrylate monomers for the preparation of thermosets and photopolymer networks. The high reactivity of sulfenylAtty. Dkt. No. 118537-0501 chloride to certain olefins via electrophilic addition reactions is exploited, namely selective electrophilic addition to allyl groups in the presence of methacrylate moeities, which are unreactive, to prepare methacrylate resins. The reaction of S2Cl2with allyl methacrylate affords a disulfide dimer bearing 2-methacrylate groups. The disulfide moeity raises the refractive index of the resulting thermoset or photopolymer without the need for introducing aromatic, or halogen groups. The resulting thermosets or photopolymers have high glass transition (Tg > 85 °C), high RI (n > 1.55) and highly transparent glassy materials. Terpolymerizations of S2Cl2with allyl comonomers (e.g., diallyl, or triallyl monomers) via sulfenyl chloride inverse vulcanization can be terminated by the addition of mono-allyl methacrylate agents (e.g., allyl methacrylate) to prepare macromonomer prepolymers which can be thermally, or photolytically cured to make glassy, crosslinked networks via free radical thermal, or photopolymerization. This disclosure recognizes that the preparation of low cost di-, and multi-functional methacrylate monomers from S2Cl2as described herein has significant potential as a new commodity optical photopolymer resin for direct production for plastic optics, or as a photopolymer resin for 3D printing via photopolymerization stereolithography.

[0034] A class of optical polymers, termed, ‘disulfide glass” was previously developed from the direct thermal curing of S2Cl2and 1,3,5-triallylisocyanurate, whichafforded, a high RI (n ~ 1.60) and very low birefringence ( n > 10-3) optical glassythermoset, which exhibited outstanding melt processing features, since these monomers are both liquid and can be cast-molded-cured in air with reasonable temperature windows (T ~ 25°C to 100°C). See, Kang, K.-S. et al., J. Am. Chem. Soc. 2022, 144, 50, 23044–23052. However, S2Cl2is moisture sensitive, and these disulfide glass materials were slightly yellow tinted, which required dye additives to offset this tinting when used for consumer eyeware. Furthermore, because of these limitations, S2Cl2, cannot be UV- photopolymerized efficiently due to the yellow color of S2Cl2, the moisture sensitivity- handling hazards from S-Cl hydrolysis, and cannot be 3D printed using photopolymerization methods. Hence, the one-step conversion of S2Cl2into a methacrylate resin by reaction with allyl methacylate as described herein addresses these limitations while retaining many desirable features of the S2Cl2-TIC disulfide glass in the final photopolymerized DSMR monomer as described herein.Atty. Dkt. No. 118537-0501

[0035] As discussed above, the present disclosure addresses the current limitations in developing high refractive index polymers for consumer eyeware and high refractive index photopolymers and photopolymer resins-monomers as discussed above. Specifically, the present disclosure shows that disulfide methacrylate resin (DSMR) prepared from the reaction with sulfur monochloride (S2Cl2) with an allyl methacrylate is a facile one-step synthesis from very low cost components. The resulting monomeric resin is intrinsically non-colored and can be used to afford low coloration / colorless optical polymers. As shown by the Examples, the disulfide methacrylate resins described herein may be thermally cured to afford a photopolymer disulfide glass withthermomechanical robust, reasonably high RI (n ~ 1.58-1.60) with low birefringence ( n> 10-3) with very low coloration. Also, the disulfide methacrylate resins described herein may be rapidly photopolymerized using classical UV-photoinitiators at from about 254nm to about 400 nm, including from about 365 nm-400 nm, to afford a photopolymer disulfide glass with thermomechanical robust, reasonably high RI (n ~ 1.58-1.60) withlow birefringence ( n > 10-3) with very low coloration. Finally, the low cost of thedisulfide methacrylate resins described herein, photopolymerizability, and resulting high RI and low birefringence of the resulting photopolymers make this a new commodity photopolymer resin as a neat monomer. Other higher RI resins exist, but require the addition of inorganic nanoparticles (e.g., TiO2-titania, zinc oxides-zirconia) which also raises birefringence-haziness and complicates photopolymerization.

[0036] Sulfenyl chlorides are a widely known but largely ignored class of sulfur compounds that are highly reactive toward nucleophiles and electrophilic unsaturated compounds. Sulfenyl chlorides are closely related to organosulfur thiol and mercaptan molecules where the R-S-H bond is replaced via chlorination reactions to form the R-S- Cl, which constitutes the sulfenyl chloride moiety. The S-Cl functional group is dipolar covalent in nature and can be considered a strong electrophile for attack by nucleophilic compounds such as, alcohols / alkoxides, Grignard reagents, organolithium reagents to form various organodisulfide compounds.

[0037] One particular illustrative example is an electrophilic addition of (organo)sulfenyl chlorides (e.g., sulfur monochloride) to unsaturated compounds, such as allyl methacrylate. These reactions proceed spontaneously in solution, in the bulk (i.e., neat) and can be done at very low temperatures (T ~ -78 °C).Atty. Dkt. No. 118537-0501

[0038] The formation of disulfidemethacrylate resin (DSMR) follows from the well- known addition of sulfenyl chlorides to olefins leading to the formation of the corresponding b-halo thioethers. However, this addition reaction to olefins has been shown to largely depend on the electron density in the double bond. The high difference in reactivity of sulfenyl chlorides to (meth)acrylate and allylic double bonds was exploited to form a reactive difunctional methacrylate (Scheme 1). Sulfenyl chloride addition to allylic monomer groups affords a mixture of Markovnikov and Anti- Markovnikov regioisomers formed by chloride anion addition to episulfonium intermediates. As shown in the Examples, the addition of tetraalkylammonium salts (e.g., tetrabutylammonium chloride at 1 mol%) results in nearly exclusive formation of the anti-Markovnikov addition product (e.g. 90 mol% versus 68 mol%).

[0039] Structural characterization of the DSMR resin described herein revealed that the DSMR resin is mixture of Anti-Markovnikov (90-mol%) and Markovnikov regioisomers, along with a mixture or disulfide (47-mol%), trisulfide (29-mol) and monosulfide (24-mol)% products. Hence, the descriptive nomenclature use of DSMR to describe this product mixture, which all uniformly polymerized to form a highly crosslinked, glassy network. Scheme 1: Equation of reaction showing the synthesis of poly(DSMR) from DSMR between allyl methacrylate and sulfur monochloride showing the formation the mono, di and tri variation of DSMR

[0040] Provided in one aspect is a composition comprising the reaction products of sulfur monochloride with an allyl methacrylate.Atty. Dkt. No. 118537-0501

[0041] In some embodiments, the reaction products are a mixture of anti- Markovnikov and Markovnikov addition products, wherein the anti-Markovnikov product is present in amount of from about 30 mol% to about 99 mol%, including about 30 mol%, about 40 mol%, about 50 mol%, about 60 mol%, about 70 mol%, about 80 mol%, about 85 mol%, about 90 mol%, about 95 mol%, about 96 mol%, about 97 mol%, about 98 mol%, and about 99 mol%. In some embodiments, the reaction products are a mixture of anti-Markovnikov and Markovnikov addition products, wherein the anti- Markovnikov product is present in amount of from about 80 mol% to about 99 mol%, including about 80 mol%, about 85 mol%, about 90 mol%, about 95 mol%, about 96 mol%, about 97 mol%, about 98 mol%, and about 99 mol%. In some embodiments, the reaction products are a mixture of anti-Markovnikov and Markovnikov addition products, wherein the anti-Markovnikov product is present in amount of greater than about 30 mol%, greater than about 40 mol%, greater than about 50 mol%, greater than about 60 mol%, greater than about 70 mol%, or greater than about 80 mol%. In some embodiments, the reaction products are a mixture of anti-Markovnikov and Markovnikov addition products, wherein the anti-Markovnikov product is present in amount of greater than about 80 mol%. In some embodiments, the anti-Markovnikov product is present in amount of greater than about 90 mol%. In some embodiments, the anti-Markovnikov product is present in amount of greater than about 95 mol%.

[0042] In some embodiments, the reaction products further comprise one or more allylic olefins. In embodiments, the one or more allylic olefins comprise a diallyl or a triallyl compound. In some embodiments, the one or more allylic olefins comprise triallyltriazinetrione.

[0043] Provided in one aspect is a composition comprising a polymer that is a reaction product of one or more compositions comprising the reaction products of sulfur monochloride with an allyl methacrylate under thermal polymerization reaction conditions sufficient to produce the polymer.

[0044] In some embodiments, the thermal polymerization reaction conditions require a radical initiator. In some embodiments, the radical initiator comprises azobisisobutyronitrile (AIBN).Atty. Dkt. No. 118537-0501

[0045] In some embodiments, the thermal polymerization reaction conditions require a low-temperature thermal initiator. In some embodiments, the low-temperature thermal initiator comprises 2,2’-azobis(4-methoxy-2,4-dimethylvalero-nitrile.

[0046] Provided in one aspect is a composition comprising a polymer that is a reaction product of one or more compositions comprising the reaction products of sulfur monochloride with an allyl methacrylate under photo polymerization reaction conditions sufficient to produce the polymer.

[0047] In some embodiments, the photo polymerization reaction conditions require a photoinitiator. In some embodiments, the photoinitiator comprises diphenyl(2,4,6 trimethylbenzoyl)phosphine oxide.

[0048] In some embodiments for the compositions comprising the polymer, the reaction product further comprises one or more olefin compounds. In some embodiments, the one or more olefin compounds comprise methyl methacrylate.

[0049] Still in further embodiments, the refractive index of the polymer described herein is greater than about 1.55. In some embodiments, the refractive index of the polymer described herein is from about 1.55 to about 1.75, including from about 1.55, about 1.56, about 1.57, about 1.58, about 1.59, about 1.60, about 1.61, about 1.62, about 1.63, about 1.65, about 1.66, about 1.67, about 1.68, about 1.69, about 1.70, about 1.71, about 1.72, about 1.73, about 1.74, and about 1.75. In some embodiments, the the refractive index of the polymer described herein is from about 1.57 to about 1.59. As used herein, the RI values are for those in visible spectrum, namely, in wavelength range from about 380 to about 750 nanometers. In some embodiments, the refractive index and Abbe numbers, see infra, refer to refractive indices at the wavelengths of the Fraunhofer C, D1, and F spectral lines (656.3 nm, 589.3 nm, and 486.1 nm respectively).

[0050] The polymers described herein are significantly less colored and have higher Abbe number (an optical metric for the wavelength dependence of the refractive index; higher Abbe number indicates low wavelength dependence of the refractive index and generally high transparency). In some embodiments, Abbe number of the polymers described herein (e.g., organochalcogenide polymers) is about 20 or higher, typically about 30 or higher, often 40 or higher, and most often about 50 or higher. In someAtty. Dkt. No. 118537-0501 embodiments, the polymer has an Abbe number of about 20 or higher. In some embodiments, the polymer has an Abbe number of about 30 or higher.

[0051] The polymers described herein (e.g., organochalcogen polymers) typically have RI of about 1.6 with high Abbe number. In some embodiments, the polymer has a refractive index of about 1.6 or higher in the visible spectrum, or near and / or short wave infrared spectral windows. In some embodiments, the polymer has a refractive index of from about 1.5 to about 1.75 in the visible spectrum, or near and / or short wave infrared spectral windows. As such, the polymers of the invention can be used in a wide variety of applications including, but not limited to, a new commodity optical photopolymer resin for direct production for plastic optics, or as a photopolymer resin for 3D printing via photopolymerization stereolithography.

[0052] The polymers described herein (e.g., organochalcogen polymers) typically have high glass transition values. In some embodiments, the polymers described herein have a glass transition value (Tg) of from about 80 °C to about 120 °C, including about about 80 °C, about 85 °C, about 90 °C, about 95 °C, about 100 °C, about 105 °C, about 110 °C, about 115 °C, and about 120 °C. In some embodiments, the polymers described herein have a glass transition value (Tg) of about 100 °C.

[0053] In some embodiments, polymers described herein have a purity of at least about 80%, typically at least about 85%, often at least about 90 %, and more often at least about 95%. In some embodiments, the polymer has a purity of at least about 90 %, including about 90%, about 91%, about 92%, about 93%, about 94%, about 95%, about 96%, about 97%, about 98%, and about 99%.

[0054] As shown in the Examples, DSMR resins described herein may be prepared by adding sulfur monochloride (0.5 equiv) to a mixture of allyl methacrylate (1 equiv) and a catalytic amount of a tetraalkylammonium salt (e.g., 0.01 equiv of tetrabutylammonium chloride). The reaction is then heated at 50 °C for an appropriate amount of time, such as 12 hours, to afford the crude product, which may be further purified by column chromatography.

[0055] The resulting product may then photochemically or thermally cured via classical free radical polymerizations. Photopolymerization may be conducted with anAtty. Dkt. No. 118537-0501 appropriate photoinitiator (e.g., Darocure-TPO or diphenyl(2,4,6 trimethylbenzoyl) phosphine oxide; 0.3 mol% at 385 nm). After photopolymerization, the photopolymerized product may then be subjected to post-thermal treatment (e.g., at about 100 °C or 140 °C). Thermal polymerization may be conducted with a radical intiator, such as azobisisobutyronitrile (AIBN) (at T = 60 °C) or using a low-temperature thermal initiator, such as V70 or 2,2’-azobis(4-methoxy-2,4-dimethylvalero-nitrile ( at T = 30 °C). In some embodiments, the thermal polymerization may be conducted at a temperature of from about 40 °C to about 80 °C. After thermal polymerization, the thermal polymerized product may then be subjected to post-thermal treatment (e.g., at about 100 °C).

[0056] Provided in another aspect for preparing composition comprising the reaction products of sulfur monochloride with an allyl methacrylate comprising: contacting sulfur monochloride and allyl methacrylate in the presence of a tetraalkylammonium salt.

[0057] In some embodiments, the process further comprises heating at a temperature of about 50 °C. In some embodiments, the tetralkylammonium salt comprises tetrabutylammonium chloride.

[0058] As shown in the Examples, TIC-AMA-S2Cl2(TAS)resins may also be prepared by adding triallyltriazinetrione (TIC, 1 equiv) to a mixture of sulfur monochloride (1.5 equiv) and allyl methacrylate (0.6 equiv). The reaction is then heated at about 45 °C for an appropriate amount of time until vitrification. The unreacted monomers may be removed by dissolving the crude product in chloroform and precipitating in methanol to afford the TAS resin. The TAS resin may then be photochemically or thermally cured via classical free radical polymerizations with the initiators described herein in the presence of allyl methacrylate or the DSMR resin. The resulting photo polymerized or thermal polymerized product may then be subjected to post-thermal treatment as described herein.

[0059] The polymers and resins described herein may be used in the fabrication of plastic optics by photo and thermal curing processes when co-formulated with addtitives for UV stability and coloring dyes. The polymers and resins described herein may alsoAtty. Dkt. No. 118537-0501 be used for the formulation for 3D vat photopolymerization printing via stereolithography or digital light processing methods or variations of these photopolymerized based additive manufacturing processes. In some embodiments, the polymer or resins are present at in an amount of about 20-mol% of the monomer formulation.

[0060] Also, the polymers and resins described herein are cured to provide DMSR photopolymer glass that are mechanically robust and optically clear to enable precision optics fabrication by diamond turn machining, grinding polishing methods in the form of plastic optics lenses, and prisms of other free form optical components. In some embodiments, the cured DSMR photopolymer glass can be molded into a precision plastic optical element via photopolymerization, or a combination of curing and post- machining methods.

[0061] 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

[0062] The following examples more specifically illustrate protocols for preparing compounds and devices according to various embodiments described above. These examples should in no way be construed as limiting the scope of the present technology. Example 1:

[0063] Synthesis of S2Cl2_AMA resin (DMSR resin)

[0064] As shown above, the reaction proceeds by the electrophilic addition of S-Cl sulfenyl chloride groups selectively to allyl groups forming a mixture of Markonikov and anti-Markovnikov addition products, which affords a mixture of primary and secondaryAtty. Dkt. No. 118537-0501 chlorides, along with some mono-sulfide and tri-sulfide products. The addition of tetra- alkylammonium salts adds in synthesizing the anti-Markonikov product in the DSMR This mixture can be purified to remove yellow coloration and afford colorless DSMR monomeric photopolymer resin as characterized by NMR spectroscopy, LC-MS and optical transmission UV-Vis spectroscopy. FIG. 1 shows the stacked1H NMR spectra of DSMR fractions after purification

[0065] The reaction proceeds by the electrophilic addition of S-Cl sulfenyl chloride groups selectively to allyl groups forming a mixture of Markonikov and anti- Markovnikov addition products, which affords a mixture of primary and secondary chlorides, along with some mono-sulfide and tri-sulfide products. The addition of tetra- alkylammonium salts adds in synthesizing the anti-Markonikov product in the DSRM. This mixture can be purified to remove yellow coloration and afford colorless DSMR monomeric photopolymer resin as characterized by NMR spectroscopy, LC-MS and optical transmission UV-Vis spectroscopy. The above figure shows the stacked 1H NMR spectra of DSMR fractions after purification.

[0066] To a 20 ml scintillation vial containing uninhibited allyl methacrylate (5 ml, 4.69 g, 37.18 mmol), sulfur monochloride (1.5 ml, 2.5 g, 18.59 mmol) was added. The mixture was allowed stir in an oil bath preset at 50 °C for 16 h. After the reaction, the unreacted allyl methacrylate was removed by column chromatography using a 95:5 mixture of hexane: ethyl acetate as eluent. The resulting liquid product was subjected to further separation into individual components by column chromatography using a 90:10 mixture of hexane: ethyl acetate.

[0067] Thermal polymerization of S2Cl2_AMA resin (DSMR resin)

[0068] The S2Cl2AMA (DSMR) resin after degassing readily undergoes thermal free radical polymerization using classical thermal initiators (e.g., AIBN, T = 60 °C) toAtty. Dkt. No. 118537-0501 afford high Tg, highly transparency glass optical thermosets. The DSC of these neat thermosets afforded featureless thermograms, but copolymerization of DSMR with aliphatic acrylates enabled correlation of comonomer feed with Tg which extrapolated to Tg > 90°C. Ellipsometry and prism coupling measurements of this material confirm the refractive index across the 400-600 nm wavelength is nearly n ~ 1.60, which already is one of the highest pure-neat photopolymer methacrylate resins free of thiols, bromines, or aromatic groups.

[0069] FIG. 2A shows the TGA of poly DSMR while FIG.2B shows the DSC thermogram of poly DSMR. FIG. 2C shows the refractive index measurement by ellipsometry and prism coupling, FIG. 2D shows the UV-Vis transmittance measurements of DMSR windows.

[0070] The Abbe number calculation of poly DSMR is shown below:

[0071] The birefringence measurement of poly DSMR is shown below.

[0072] DSMR resin (6.00 g, 15.54 mmol) was placed in a flame dried 20 ml scintillation vial. The vial was capped with a septum and the mixture was sparged with argon for 30 min. After sparging, 1 mol % azobisisobutyronitrile (AIBN) (25.52 mg, 0.155 mmol) was added to the crude mixture and then place in an oil bath preset at 70 .Atty. Dkt. No. 118537-0501 The polymerization was allowed to run until the mixture vitrified followed by an overnight curing in a 100 oven. A yellow transparent thermoset window was obtained.

[0073] DSMR resin (6.00 g, 15.54 mmol) was placed in a flame dried 20 ml scintillation vial. The vial was capped with a septum and the resin was degassed under vacuum for 30 min. After degassing, 0.3 mol % azobisisobutyronitrile (AIBN) (7.6 mg, 0.046 mmol) was added to the resin and the mixture was degassed for another 30 min then place in an oil bath preset at 50 ℃. The polymerization was allowed to run until the mixture vitrified followed by an overnight curing in a 100 ℃ oven. A clear transparent thermoset window was obtained.

[0074] Photo polymerization of DSMR resin

[0075] The DSMR resin after degassing exhibited rapid photopolymerization at ~ 365-390 nm a noted by NMR conversion measurements of DSMR conversion with time. Visual inspection of bulk photopolymerization under UV irradiation demonstrated rapid network glassification within minutes of exposure.

[0076] DSMR resin (1.505 g, 2.71 mmol), was placed in a flame dried 1 ml reaction vial. The vial was capped with a septum and the mixture was sparged with argon for 30 min. After sparging, 0.5 mol % diphenyl(2,4,6 trimethylbenzoyl)phosphine oxide (Darocur TPO) (25.52 mg, 0.155 mmol) was added to the crude mixture and the vial was placed under a 365 nm UV lamp. The polymerization reaction was let run for 48 h until vitrification was observed and then the crosslinked polymer was cured in a 100 oven overnight. A yellow transparent window was obtained.

[0077] DSMR resin (1.44 g, 3.73 mmol), was placed in a flame dried 1 ml reaction vial. The vial was capped with a septum and the resin was degassed for 30 min. After degassing, 0.3 mol % diphenyl(2,4,6 trimethylbenzoyl)phosphine oxide (Darocur TPO) (3.9 mg, 0.011 mmol) was added to the resin and the vial was further degassed for 30Atty. Dkt. No. 118537-0501 min, then placed under a 395 nm UV lamp. The polymerization reaction was let run for 5 s until vitrification was observed and then the crosslinked polymer was further UV cured for 30 min. A colorless transparent window was obtained.

[0078] Synthesis of TIC-AMA-S2Cl2 (TAS) Resin Mixtures

[0079] In a flame dried 20 ml scintillating vial, triallyltriazinetrione (1 eq. 3 ml, 3.45 g, 13.84 mmol), allyl methacrylate (0.6 eq 1.12 ml, 1.05 g, 8.30 mmol) and sulfur monochloride (1.5 eq, 1.66 ml, 2.89 g, 22.45 mmol) were added and the vial was placed in an oil bath preset at 45 . The reaction was run until vitrification and then unreacted monomers were removed by dissolving in chloroform and precipitating in methanol. The precipitate s then dried in a 60 oven overnight to afford a white powder Mn = 5370 g / mol, Mw = 22140, PD = 4.1).

[0080] Thermal polymerization of TAS Resin

[0081] In a flame dried 1 dram vial, TAS (0.70 g, 0.13 mmol), and AIBN (0.3 mol %, 11 mg, 67.0 μmol) were added to methyl methacrylate (MMA) (0.94 g, 9.4 mmol). The mixture was stirred at room temperature until dissolution then the vial was placed in an oil bath preset at 60 ℃. The reaction was let run for 16 h until vitrification and thenAtty. Dkt. No. 118537-0501 transferred to a 100 ℃ oven for curing overnight. A transparent colorless window was obtained.

[0082] Photo Polymerization of TAS Resin (in MMA)

[0083] In a flame dried 1 dram vial, TAS (0.70 g, 0.13 mmol), and diphenyl(2,4,6 trimethylbenzoyl)phosphine oxide (Darocur TPO) (1.0 mol %, 20 mg, 57.4 μmol), and degassed methyl methacrylate (MMA) (0.94 g, 9.4 mmol) were added. The mixture was stirred at room temperature until dissolution then the vial was placed under a 365 nm UV lamp. The reaction was let run until vitrification and then transferred to a 100 ℃ oven for curing overnight. A colorless window was obtained.

[0084] Photo Polymerization of TAS Resin (in DSMR)

[0085] In a flame dried 1 dram vial, TAS (0.20 g, 37.24 μmol), and diphenyl(2,4,6 trimethylbenzoyl)phosphine oxide (Darocur TPO) (1.0 mol % 9.16 mg, 0.026 mmol) were added to degassed DSMR resin (1.05 g, 2.71 mmol). The mixture was ultrasonicated at room temperature until dissolution then the vial was placed under a 365 nm UV lamp. The reaction was let run until vitrification and then transferred to a 100 ℃ oven for curing overnight. A transparent yellow window was obtained. Example 2

[0086] General Procedure for the Large Scale Synthesis of Disulfide Methacrylate Resin (DSMR)

[0087] Neat as received allyl methacrylate (100 mL) was filtered through a short basic aluminum oxide plug (glass column, diameter = 32mm, plugged with cotton, filled to height = 60 mm) to remove 4-methoxyphenol (MEHQ) inhibitor. The filtered allyl methacrylate (93.8 g, 743.56 mmol, 1 eq) was added to a 250 ml round bottom flask fitted with a 3-inch magnetic stir bar. Tetrabutylammonium chloride (2.066 g, 7.43 mmol, 0.01 eq) was added to the reaction vessel and the resulting mixture stirred at room temperature until completely dissolved. Distilled sulfur monochloride (50.09 g, 371.80 mmol, 0.5 eq) was at this point added via syringe into the reaction vessel, which was then placed into a 50 ℃ oil bath for 12 hours affording a yellow viscous fluid. The crude product was then dissolved in dichloromethane (DCM, 200 mL), washed consecutivelyAtty. Dkt. No. 118537-0501 with water and a saturated brine wash before being concentrated in vacuo on rotary evaporator. The resulting crude mixture was then purified by column chromatography employing a mixture of hexanes and ethyl acetate as eluents (starting with a 95:5 vol. ratio mixture and then 85:15 vol-ratio), which afforded a colorless, viscous fluid (yield, 115 g, 82 %).

[0088] Thermal Fabrication of Poly(DSMR) windows of varying thicknesses.

[0089] Thermal Free Radical Processing of Poly(DSMR) Window (D = 25 mm, Thickness = 6 mm): DSMR (7.000 g, 18.09 mmol) was placed in a 20 mL glass vial and freshly recrystallized AIBN (0.009 g, 0.05 mmol, 0.3 mol%) was added to the resin. The mixture was vortexed and ultrasonicated until AIBN was completely dissolved at which point the mixture was degassed in a vacuum oven at room temperature until no bubbles were observed. Thermal curing was initially conducted by placing the reaction vessel into a thermostatic oil (40 ℃) and the temperature was increased gradually over a 48 hour period from 40 ℃ to 80 ℃. After vitrification of the resin to form a solid after 2 days, the vial was taken out of the oil bath and immediately placed in a 100 ℃ oven to post-cure for 18 hours. After the final post-curing step, the crosslinked polymer was taken out of the vial by breaking the vial and then polished on both ends using a wet-dry sandpaper (150 / 220 / 400 / 1000 / 2000 / 3000 grit and a scratch remover polisher) to the required thickness and a smooth glassy flat surface was obtained.

[0090] Thermal Free Radical Processing of Poly(DSMR) Window (D = 25 mm, Thickness = 5 mm): DSMR (5.500 g, 14.21 mmol) was placed in a 20 mL glass vial and freshly recrystallized AIBN (0.007 g, 0.04 mmol, 0.3 mol%) was added to the resin. The mixture was vortexed and ultrasonicated until AIBN was completely dissolved at which point the mixture was degassed in a vacuum oven at room temperature until no bubbles were observed. Thermal curing was initially conducted by placing the reaction vessel into a thermostatic oil (40 ℃) and the temperature was increased gradually over a 48 hour period from 40 ℃ to 80 ℃. After vitrification of the resin to form a solid after 2 days, the vial was taken out of the oil bath and immediately placed in a 100 ℃ oven to post-cure for 18 hours. After the final post-curing step, the crosslinked polymer was taken out of the vial by breaking the vial and then polished on both ends using a wet-dry sandpaper (150 / 220 / 400 / 1000 / 2000 / 3000 grit and a scratch remover polisher) to the required thickness and a smooth glassy flat surface was obtained.Atty. Dkt. No. 118537-0501

[0091] Thermal Free Radical Processing of Poly(DSMR) Window (D = 25 mm, Thickness = 1.5 mm): DSMR (3.500 g, 9.04 mmol) was placed in a 20 mL glass vial and freshly recrystallized AIBN (0.004 g, 0.03 mmol, 0.3 mol%) was added to the resin. The mixture was vortexed and ultrasonicated until AIBN was completely dissolved at which point the mixture was degassed in a vacuum oven at room temperature until no bubbles were observed. Thermal curing was initially conducted by placing the reaction vessel into a thermostatic oil (40 ℃) and the temperature was increased gradually over a 48 hour period from 40 ℃ to 80 ℃. After vitrification of the resin to form a solid after 2 days, the vial was taken out of the oil bath and immediately placed in a 100 ℃ oven to post-cure for 18 hours. After the final post-curing step, the crosslinked polymer was taken out of the vial by breaking the vial and then polished on both ends using a wet-dry sandpaper (150 / 220 / 400 / 1000 / 2000 / 3000 grit and a scratch remover polisher) to the required thickness and a smooth glassy flat surface was obtained.

[0092] Room Temperature Free Radical Curing of Poly(DSMR) Window (D =25 mm, Thickness = 10 mm): DSMR (11.200 g, 29.94 mmol) was added into an 11-dram glass vial followed by a DCM solution (0.1 mL) of 2,2’-Azobis(4-methoxy-2,4- dimethylvaleronitrile) (V70) (0.027 g, 0.09 mmol). The mixture was thoroughly shaken to ensure efficient mixing and then attached to a Schlenk line to remove the solvent and air bubbles in the resin under vacuum. The resin was let stand under vacuum and polymerization was evident after 30 minutes. The vitrified resin was then allowed to sit on the bench overnight at room temperature followed by a thermal cure at 50 ℃ while slowly increasing the temperature over a 4 day period to 70 ℃ (50 ℃ for 24 hours, 60 for the next 24 hours and 70 ℃ for 48 hours). After the final post-curing step, the crosslinked polymer was taken out of the vial by breaking the vial and then polished on both ends using a wet-dry sandpaper (150 / 220 / 400 / 1000 / 2000 / 3000 grit and a scratch remover polisher) to the required thickness and a smooth glassy flat surface was obtained

[0093] Room Temperature Free Radical Curing of Poly(DSMR) Window (D =25 mm, Thickness = 18 mm): DSMR (17.800 g, 49.99 mmol) was added into an 11-dram glass vial followed by a DCM solution (0.1 mL) of 2,2’-Azobis(4-methoxy-2,4- dimethylvaleronitrile) (V70) (0.043 g, 0.14 mmol). The mixture was thoroughly shaken to ensure efficient mixing and then attached to a Schlenk line to remove the solvent and air bubbles in the resin under vacuum. The resin was left under vacuum andAtty. Dkt. No. 118537-0501 polymerization was evident after 30 minutes. The vitrified resin was then allowed to sit on the bench overnight at room temperature followed by a thermal cure at 50 ℃ while slowly increasing the temperature over a 4 day period to 70 ℃ (50 for 24 hours, 60 ℃ for the next 24 hours and 70 ℃ for 48 hours). After the final post-curing step, the crosslinked polymer was taken out of the vial by breaking the vial and then polished on both ends using a wet-dry sandpaper (150 / 220 / 400 / 1000 / 2000 / 3000 grit and a scratch remover polisher) to the required thickness and a smooth glassy flat surface was obtained.

[0094] Room Temperature Free Radical Curing of Poly(DSMR) Window (D =25 mm, Thickness = 35 mm): DSMR (24.000 g, 62.02 mmol) was added into an 11-dram glass vial followed by a DCM solution (0.1 mL) of 2,2’-Azobis(4-methoxy-2,4- dimethylvaleronitrile) (V70) (0.043 g, 0.19 mmol) predissolved in DCM (0.1 mL). The mixture was thoroughly shaken to ensure efficient mixing and then attached to a Schlenk line to remove the solvent and air bubbles in the resin under vacuum. The resin was left under vacuum and polymerization was evident after 30 minutes. The vitrified resin was then allowed to sit on the bench overnight at room temperature followed by a thermal cure at 50 ℃ while slowly increasing the temperature over a 4 day period to 70 ℃ (50 ℃ for 24 hours, 60 ℃ for the next 24 hours and 70 ℃ for 48 hours). After the final post- curing step, the crosslinked polymer was taken out of the vial by breaking the vial and then polished on both ends using a wet-dry sandpaper (150 / 220 / 400 / 1000 / 2000 / 3000 grit and a scratch remover polisher) to the required thickness and a smooth glassy flat surface was obtained.

[0095] Photofabrication of Poly(DSMR) windows of varying thicknesses (Diameter = 25 mm, Thickness = 1.4 - 30 mm)

[0096] Photofabrication of Poly(DSMR) window (Diameter = 25 mm, Thickness = 1.4 mm): DSMR (2.000 g, 5.17 mmol) was placed in a 20 mL glass vial and 2,4,6- trimethylbenzoyl-diphenyl phosphineoxide (DAROCUR TPO) photoinitiator (0.005 g, 0.02 mmol) was added. The mixture was vortexed and ultrasonicated until the photoinitiator completely dissolved followed by degassing in a vacuum oven at room temperature until no bubbles were observed. The reaction vial was placed adjacent to two 385-395 nm UV lamps (3.5 cm away from each lamp) in a dark chamber.Atty. Dkt. No. 118537-0501 Vitrification was completed under 3 minutes and was left under UV irradiation for 2 hours to improve the conversion followed by a thermal post cure at 100 ℃ for 6 hours. After the thermal curing step, the fully crosslinked polymer was taken out of the vial by breaking the vial and then polished on both ends using a wet-dry sandpaper (150 / 220 / 400 / 1000 / 2000 / 3000 grit and a scratch remover polisher) until the desired thickness was reached and a smooth glassy surface was obtained.

[0097] Photofabrication of Poly(DSMR) window (Diameter = 25 mm, Thickness = 3.3 mm): DSMR (4.050 g, 10.47 mmol) was placed in a 20 mL glass vial and 2,4,6- trimethylbenzoyl-diphenyl phosphineoxide (DAROCUR TPO) photoinitiator (0.010 g, 0.03 mmol) was added. The mixture was vortexed and ultrasonicated until the photoinitiator completely dissolved followed by degassing in a vacuum oven at room temperature until no bubbles were observed. The reaction vial was placed adjacent to two 385-395 nm UV lamps (3.5 cm away from each lamp) in a dark chamber. Vitrification was completed under 3 minutes and was left under UV irradiation for 2 hours to improve the conversion followed by a thermal post cure at 100 ℃ for 6 hours. After the thermal curing step, the fully crosslinked polymer was taken out of the vial by breaking the vial and then polished on both ends using a wet-dry sandpaper (150 / 220 / 400 / 1000 / 2000 / 3000 grit and a scratch remover polisher) until the desired thickness was reached and a smooth glassy surface was obtained.

[0098] Photofabrication of Poly(DSMR) window (Diameter = 25 mm, Thickness = 7.7 mm): DSMR (8.004 g, 20.68 mmol) was placed in a 20 mL glass vial and 2,4,6- trimethylbenzoyl-diphenyl phosphineoxide (DAROCUR TPO) photoinitiator (0.022 g, 0.06 mmol) was added. The mixture was vortexed and ultrasonicated until the photoinitiator completely dissolved followed by degassing in a vacuum oven at room temperature until no bubbles were observed. The reaction vial was placed adjacent to two 385-395 nm UV lamps (3.5 cm away from each lamp) in a dark chamber. Vitrification was completed under 3 minutes and was left under UV irradiation for 2 hours to improve the conversion followed by a thermal post cure at 100 ℃ for 6 hours. After the thermal curing step, the fully crosslinked polymer was taken out of the vial by breaking the vial and then polished on both ends using a wet-dry sandpaper (150 / 220 / 400 / 1000 / 2000 / 3000 grit and a scratch remover polisher) until the desired thickness was reached and a smooth glassy surface was obtained.Atty. Dkt. No. 118537-0501

[0099] Photofabrication of Poly(DSMR) window (Diameter = 25 mm, Thickness = 13 mm): DSMR (10.000 g, 25.82 mmol) was placed in a 20 mL glass vial and 2,4,6- trimethylbenzoyl-diphenyl phosphineoxide (DAROCUR TPO) photoinitiator (0.027 g, 0.08 mmol) was added. The mixture was vortexed and ultrasonicated until the photoinitiator completely dissolved followed by degassing in a vacuum oven at room temperature until no bubbles were observed. The reaction vial was placed adjacent to two 385-395 nm UV lamps (3.5 cm away from each lamp) in a dark chamber. Vitrification was completed under 3 minutes and was left under UV irradiation for 2 hours to improve the conversion followed by a thermal post cure at 100 ℃ for 6 hours. After the thermal curing step, the fully crosslinked polymer was taken out of the vial by breaking the vial and then polished on both ends using a wet-dry sandpaper (150 / 220 / 400 / 1000 / 2000 / 3000 grit and a scratch remover polisher) until the desired thickness was reached and a smooth glassy surface was obtained.

[0100] Photofabrication of Poly(DSMR) window (Diameter = 25 mm, Thickness = 18 mm): DSMR (15.000 g, 38.76 mmol) was placed in a 20 mL glass vial and 2,4,6- trimethylbenzoyl-diphenyl phosphineoxide (DAROCUR TPO) photoinitiator (0.041 g, 0.12 mmol) was added. The mixture was vortexed and ultrasonicated until the photoinitiator completely dissolved followed by degassing in a vacuum oven at room temperature until no bubbles were observed. The reaction vial was placed adjacent to two 385-395 nm UV lamps (3.5 cm away from each lamp) in a dark chamber. Vitrification was completed under 3 minutes and was left under UV irradiation for 2 hours to improve the conversion followed by a thermal post cure at 100 ℃ for 6 hours. After the thermal curing step, the fully crosslinked polymer was taken out of the vial by breaking the vial and then polished on both ends using a wet-dry sandpaper (150 / 220 / 400 / 1000 / 2000 / 3000 grit and a scratch remover polisher) until the desired thickness was reached and a smooth glassy surface was obtained.

[0101] Photofabrication of Poly(DSMR) window (Diameter = 25 mm, Thickness = 30 mm): DSMR (22.000 g, 56.85 mmol) was placed in a 20 mL glass vial and 2,4,6- trimethylbenzoyl-diphenyl phosphineoxide (DAROCUR TPO) photoinitiator (0.059 g, 0.17 mmol) was added. The mixture was vortexed and ultrasonicated until the photoinitiator completely dissolved followed by degassing in a vacuum oven at room temperature until no bubbles were observed. The reaction vial was placed adjacent toAtty. Dkt. No. 118537-0501 two 385-395 nm UV lamps (3.5 cm away from each lamp) in a dark chamber. Vitrification was completed under 3 minutes and was left under UV irradiation for 2 hours to improve the conversion followed by a thermal post cure at 100 ℃ for 6 hours. After the thermal curing step, the fully crosslinked polymer was taken out of the vial by breaking the vial and then polished on both ends using a wet-dry sandpaper (150 / 220 / 400 / 1000 / 2000 / 3000 grit and a scratch remover polisher) until the desired thickness was reached and a smooth glassy surface was obtained.

[0102] Post cure was done at 100 ℃ for 6 hours for window samples while samples used for mechanical analysis were post cured at 140 ℃ for variable times to improve crosslinking density.

[0103] The most quantitative physical measurement to validate transparency is reporting of the “optical absorption coefficient, alpha-values” which are typically measured in the most “flat” non-absorbing region of the UV-VIS-IR spectra which for VIS plastic optics is around 1310 nm and 1550 nm. For the DSMR photopolymer windows of different thicknesses (D = 25 mm, thickness = 1.4–30 mm) fabricated by photopolymerization and thermal-post bake as described above, the absorption coefficients for the DSMR photopolymer glass were determined from the opticaltransmission spectra and were found to be remarkably low at 1310 nm ( 1310 nm = 0.045cm−1) and 1550 nm ( 1550 nm = 0.128 cm−1) and notably lower than for poly(methylmethacrylate) (PMMA) ( 1310 nm = 0.075 cm−1; 1550 nm = 0.180 cm−1).

[0104] Polymer Applications and Fields of Use

[0105] The monomers and methods described herein provide an enabling polymer synthesis platform for the preparation of a broad class of engineering plastics, adhesives, elastomers and optical polymers. Exemplary fields of use include, but are not limited to: Consumer plastic optics: Optical polymers and plastic optics for consumer spectacle eyeware may be prepared. For this application, optical polymers ideally should have the following properties: (a) refractive index = 1.60-1.70, Abbe number > 25, 90%T or greater in the visible spectrum (b) no color, or limited pigmentation (c) Tg, Tm > 100 °C and tensile strength > 40 MPa.Atty. Dkt. No. 118537-0501 High photopolymer monomers resins: DSMR could be sold and used directly as a neat methacylate monomer for optical plastics, or sold as a high RI monomer / photopolymer resin. The table below illustrates representatbve examples of current ‘high RI” photopolymer monomers and resins. The big market would be for use in 3D printing photopoylmerizatio since the DSMR is low cost and can be made in large quantities vs most commercial high RI monomers which are sold in small quantities (see Nanoscribe IP-n 162).Atty. Dkt. No. 118537-0501

[0106] Para. 1. A composition comprising the reaction products of sulfur monochloride with an allyl methacrylate.

[0107] Para. 2. The composition of Para. 1, wherein the reaction products are a mixture of anti-Markovnikov and Markovnikov addition products, wherein the anti- Markovnikov product is present in amount of greater than about 80 mol%.

[0108] Para. 3. The composition of Paras. 1 or 2, the reaction products further comprise one or more allylic olefins.

[0109] Para. 4. The composition of Para. 3, wherein the one or more allylic olefins comprise a diallyl or a triallyl compound.

[0110] Para. 5. The composition of Para. 3, wherein the one or more allylic olefins comprise triallyltriazinetrione.

[0111] Para. 6. A composition comprising a polymer that is a reaction product of one or more compositions of any one of Paras. 1-5 under thermal polymerization reaction conditions sufficient to produce the polymer.

[0112] Para. 7. The composition of Para. 6, wherein the thermal polymerization reaction conditions require a radical initiator.

[0113] Para. 8. The composition of Para. 7, wherein the radical initiator comprises azobisisobutyronitrile (AIBN).

[0114] Para. 9. The composition of Para. 6, wherein the thermal polymerization reaction conditions require a low-temperature thermal initiator.Atty. Dkt. No. 118537-0501

[0115] Para. 10. The composition of Para. 9, wherein the low-temperature thermal initiator comprises 2,2’-azobis(4-methoxy-2,4-dimethylvalero-nitrile.

[0116] Para. 11. A composition comprising a polymer that is a reaction product of one or more compositions of any one of Paras. 1-5 under photo polymerization reaction conditions sufficient to produce the polymer.

[0117] Para. 12. The composition of Para. 11, wherein the photo polymerization reaction conditions require a photoinitiator.

[0118] Para. 13. The composition of Para. 12, wherein the photoinitiator comprises diphenyl(2,4,6 trimethylbenzoyl)phosphine oxide.

[0119] Para. 14. The composition of any one of Paras. 6-13, wherein the reaction product further comprises one or more olefin compounds.

[0120] Para. 15. The composition of Para. 14, wherein the one or more olefin compounds comprise methyl methacrylate.

[0121] Para.16. A process for preparing the composition of any one of Paras. 1-15 comprising: contacting sulfur monochloride and allyl methacrylate in the presence of a tetralkylammonium salt.

[0122] Para. 17. The process of Para.16, further comprising heating at a temperature of about 50 °C.

[0123] Para. 18. The process of Paras. 16 or 17, wherein the tetralkylammonium salt comprises tetrabutylammonium chloride. References 1. Kleine, T. S.; Lee, T.; Carothers, K. J.; Hamilton, M. O.; Anderson, L. E.; Ruiz Diaz, L.; Lyons, N. P.; Coasey, K. R.; Parker, W. O., Jr.; Borghi, L.; MacKay, M. E.; Char, K.; Glass, R. S.; Lichtenberger, D. L.; Norwood, R. A.; Pyun, J., Infrared Fingerprint Engineering: A Molecular-Design Approach to Long-Wave Infrared Transparency with Polymeric Materials. Angewandte Chemie, International Edition 2019, 58 (49), 17656-17660.Atty. Dkt. No. 118537-0501 Pavlopoulos, N. G.; Kang, K. S.; Holmen, L. N.; Lyons, N. P.; Akhoundi, F.; Carothers, K. J.; Jenkins, S. L.; Lee, T.; Kochenderfer, T. M.; Phan, A.; Phan, D.; Mackay, M. E.; Shim, I. B.; Char, K.; Peyghambarian, N.; LaComb, L. J.; Norwood, R. A.; Pyun, J., Polymer and magnetic nanoparticle composites with tunable magneto-optical activity: role of nanoparticle dispersion for high verdet constant materials. Journal of Materials Chemistry C 2020, 8 (16), 5417-5425. Carothers, K. J.; Lyons, N. P.; Pavlopoulos, N. G.; Kang, K.-S.; Kochenderfer, T. M.; Phan, A.; Holmen, L. N.; Jenkins, S. L.; Shim, I.-B.; Norwood, R. A.; Pyun, J., Polymer-Coated Magnetic Nanoparticles as Ultrahigh Verdet Constant Materials: Correlation of Nanoparticle Size with Magnetic and Magneto-Optical Properties. Chemistry of Materials 2021, 33 (13), 5010-5020. Dislich, H., Plastics as optical materials. Angewandte Chemie, International Edition 1979, 18, 49-59. Rubin, M. L., Spectacles: Past, Present and Future. Surv. Ophthalmol. 1986, 30, 321. A., C., High Refractive Index Plastic Optical Materials. VDM Verlag: 2009. Liu, J.-g.; Ueda, M., High refractive index polymers: fundamental research and practical applications. Journal of Materials Chemistry 2009, 19 (47), 8907-8919. Morishiri, H.; Kobayashi, S. Episulfide compound with high refractive index. Jpn Kokai Tokkyo Koho 3252742005. Morishiri, H.; Kobayashi, S. Polythiols, transparent polymer compositions containing them, their polymers, their manufactur their heat-resistant optical materials and lenses with high refractive index. Jpn Kokai Tokkyo Koho 131724 2006. Higashihara, T.; Ueda, M., Recent Progress in High Refractive Index Polymers. Macromolecules 2015, 48 (7), 1915-1929. Tsukada, H.; Kawaguchi, M. Process for producing episulfide compound for optical material, episulfide-containing composition, and polymerizableAtty. Dkt. No. 118537-0501 composition for optical material including the same composition. US Patent #10266636, 2019. 12. Okubo, T.; Kohmoto, S.; Yamamoto, M., Optical Polymer Having a High Refractive Index and High Abbe Number Prepared by Radical Polymerization Using 2,5-BiS(2-Thia-3-Butenyl)-1,4-Dithiane. Journal of Macromolecular Science, Part A 1998, 35 (11), 1819-1834. 13. Okutsu, R.; Ando, S.; Ueda, M., Sulfur-Containing Poly(meth)acrylates with High Refractive Indices and High Abbe’s Numbers. Chemistry of Materials 2008, 20 (12), 4017-4023. 14. Okutsu, R.; Suzuki, Y.; Ando, S.; Ueda, M., Poly(thioether sulfone) with High Refractive Index and High Abbe’s Number. Macromolecules 2008, 41 (16), 6165-6168. 15. Bhagat, S. D.; Chatterjee, J.; Chen, B.; Stiegman, A. E., High Refractive Index Polymers Based on Thiol–Ene Cross-Linking Using Polarizable Inorganic / Organic Monomers. Macromolecules 2012, 45 (3), 1174-1181. 16. Su, Y.; Filho, E. B. D. S.; Peek, N.; Chen, B.; Stiegman, A. E., High Refractive Index Polymers (n > 1.7), Based on Thiol–Ene Cross-Linking of Polarizable P═S and P═Se Organic / Inorganic Monomers. Macromolecules 2019, 52 (22), 9012- 9022. 17. Shigenori, K.; Mamoru, T.; Munehito, F.; Seiichi, K. Production method of polyepithiol-ethyl compound. Jpn Kokai Tokkyo Koho 4205329, 2009.

[0124] 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.

[0125] 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, theAtty. Dkt. No. 118537-0501 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.

[0126] 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.

[0127] 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.

[0128] 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 non-limiting example, each range discussed herein can be readily broken down into a lower third, middle third and upper third, etc. As will also be understood by one skilledAtty. Dkt. No. 118537-0501 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.

[0129] 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.

[0130] Other embodiments are set forth in the following claims.

Claims

Atty. Dkt. No. 118537-0501 WHAT IS CLAIMED IS:

1. A composition comprising the reaction products of sulfur monochloride with an allyl methacrylate.

2. The composition of claim 1, wherein the reaction products are a mixture of anti- Markovnikov and Markovnikov addition products, wherein the anti-Markovnikov product is present in amount of greater than about 80 mol%.

3. The composition of claim 1, the reaction products further comprise one or more allylic olefins.

4. The composition of claim 3, wherein the one or more allylic olefins comprise a diallyl or a triallyl compound.

5. The composition of claim 3, wherein the one or more allylic olefins comprise triallyltriazinetrione.

6. A composition comprising a polymer that is a reaction product of one or more compositions of any one of claims 1-5 under thermal polymerization reaction conditions sufficient to produce the polymer.

7. The composition of claim 6, wherein the thermal polymerization reaction conditions require a radical initiator.

8. The composition of claim 7, wherein the radical initiator comprises azobisisobutyronitrile (AIBN).

9. The composition of claim 6, wherein the thermal polymerization reaction conditions require a low-temperature thermal initiator.

10. The composition of claim 9, wherein the low-temperature thermal initiator comprises 2,2’-azobis(4-methoxy-2,4-dimethylvalero-nitrile.

11. A composition comprising a polymer that is a reaction product of one or more compositions of any one of claims 1-5 under photo polymerization reaction conditions sufficient to produce the polymer.Atty. Dkt. No. 118537-0501 12. The composition of claim 11, wherein the photo polymerization reaction conditions require a photoinitiator.

13. The composition of claim 12, wherein the photoinitiator comprises diphenyl(2,4,6 trimethylbenzoyl)phosphine oxide.

14. The composition of any one of claims 6-13, wherein the reaction product further comprises one or more olefin compounds.

15. The composition of claim 14, wherein the one or more olefin compounds comprise methyl methacrylate.

16. A process for preparing the composition of claim 1 comprising: contacting sulfur monochloride and allyl methacrylate in the presence of a tetralkylammonium salt.

17. The process of claim 16, further comprising heating at a temperature of about 50 °C.

18. The process of claim 16, wherein the tetralkylammonium salt comprises tetrabutylammonium chloride.

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