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Abstract Multiple relaxation times are used to capture the numerous stress relaxation modes found in bulk polymer melts. Herein, inverse vulcanization is used to synthesize high sulfur content (≥50 wt%) polymers that only need a single relaxation time to describe their stress relaxation. The S-S bonds in these organopolysulfides undergo dissociative bond exchange when exposed to elevated temperatures, making the bond exchange dominate the stress relaxation. Through the introduction of a dimeric norbornadiene crosslinker that improves thermomechanical properties, we show that it is possible for the Maxwell model of viscoelasticity to describe both dissociative covalent adaptable networks and living polymers, which is one of the few experimental realizations of a Maxwellian material. Rheological master curves utilizing time-temperature superposition were constructed using relaxation times as nonarbitrary horizontal shift factors. Despite advances in inverse vulcanization, this is the first complete characterization of the rheological properties of this class of unique polymeric material. 

The production of elemental sulfur from petroleum refining has created a technological opportunity to increase the valorization of elemental sulfur by the synthesis of high-performance sulfur-based plastics with improved optical, electrochemical, and mechanical properties aimed at applications in thermal imaging, energy storage, self-healable materials, and separation science. In this Perspective, we discuss efforts in the past decade that have revived this area of organosulfur and polymer chemistry to afford a new class of high-sulfur-content polymers prepared from the polymerization of liquid sulfur with unsaturated monomers, termed inverse vulcanization. 

Abstract In this study, the first fabrication of phase‐shifted Bragg gratings utilizing chalcogenide hybrid inorganic/organic polymers (CHIPs) is presented based on poly(sulfur‐random‐(1,3‐isopropenylbenzene) to measure the thermo‐optic coefficient (TOC) of this new class of optical polymers. The unique properties ofCHIPs, such as high index contrast and low optical losses, are leveraged to fabricate Bragg gratings that enable precise determination of the TOC and glass transition temperature (T_g) of these polymers. The optical measurement introduces a novel technique to measure the TOC and T_gof optical polymers which can be difficult to determine using traditional methods such as differential scanning calorimetry (DSC) after fabrication into photonic device constructs. The findings demonstrate thatCHIPs exhibit low thermo‐optic (TO) effects, making them exceptionally well‐suited for the development of thermally stable photonic integrated circuits. 

Abstract The development of infrared (IR) plastic optics for infrared thermal imaging, particularly, in the long‐wave IR (LWIR) spectrum (7–14 µm) is an area of growing technological interest due to the potential advantages associated with plastic optics (e.g., moldability and low cost). The development of a new class of optical polymers, chalcogenide‐based inorganic/organic hybrid polymers (CHIPs) derived from the inverse vulcanization of elemental sulfur, has enabled significant improvements in IR transparency due to reduction of IR absorbing organic comonomer units. The vast majority of effort has focused on new chalcogenide hybrid polymer synthesis and optical property improvements (e.g., refractive index, Abbe number, and LWIR transmission); however, fabrication and IR imaging methodology to prepare optical components has not been demonstrated, which remains critical to develop viable IR plastic optics. A new methodology is reported to fabricate optical components and evaluate LWIR imaging performance of this emerging class of optical polymers. New diffractive flat optics with a Fresnel lens design for these materials have been developed, along with a basic LWIR imaging system to evaluate CHIPs for LWIR imaging. This system‐based approach enables correspondence of copolymer structure‐property correlations with LWIR imaging performance, along with demonstration of room temperature LWIR imaging. 

Abstract Optical polymer‐based integrated photonic devices are gaining interest for applications in optical packaging, biosensing, and augmented/virtual reality (AR/VR). The low refractive index of conventional organic polymers has been a barrier to realizing dense, low footprint photonic devices. The fabrication and characterization of integrated photonic devices using a new class of high refractive index polymers, chalcogenide hybrid inorganic/organic polymers (CHIPs), which possess high refractive indices and lower optical losses compared to traditional hydrocarbon‐based polymers, are reported. These optical polymers are derived from elemental sulfur via the inverse vulcanization process, which allows for inexpensive monomers to be used for these materials. A facile fabrication strategy using CHIPs via lithography is described for single‐mode optical waveguides, Y junction splitters, multimode interferometers (MMIs), and high Q factor ring resonators, along with device characterization. Furthermore, propagation losses of 0.4 dB cm⁻¹near 1550 nm wavelength, which is the lowest measured loss in non‐fluorinated optical polymer waveguides, coupled with the benefits of low cost materials and manufacturing are reported. Ring resonators with Q factor on the order of 6 × 10⁴and cavity finesse of 45, which are some of the highest values reported for optical polymer‐based ring resonators, are also reported. 

Abstract The production of elemental sulfur from petroleum refining has created a technological opportunity to increase the valorization of elemental sulfur by the creation of high‐performance sulfur based plastics with improved thermomechanical properties, elasticity and flame retardancy. We report on a synthetic polymerization methodology to prepare the first example of sulfur based segmented multi‐block polyurethanes (SPUs) and thermoplastic elastomers that incorporate an appreciable amount of sulfur into the final target material. This approach applied both the inverse vulcanization of S₈with olefinic alcohols and dynamic covalent polymerizations with dienes to prepare sulfur polyols and terpolyols that were used in polymerizations with aromatic diisocyanates and short chain diols. Using these methods, a new class of high molecular weight, soluble block copolymer polyurethanes were prepared as confirmed by Size Exclusion Chromatography, NMR spectroscopy, thermal analysis, and microscopic imaging. These sulfur‐based polyurethanes were readily solution processed into large area free standing films where both the tensile strength and elasticity of these materials were controlled by variation of the sulfur polyol composition. SPUs with both high tensile strength (13–24 MPa) and ductility (348 % strain at break) were prepared, along with SPU thermoplastic elastomers (578 % strain at break) which are comparable values to classical thermoplastic polyurethanes (TPUs). The incorporation of sulfur into these polyurethanes enhanced flame retardancy in comparison to classical TPUs, which points to the opportunity to impart new properties to polymeric materials as a consequence of using elemental sulfur. 

Abstract Optical technologies in the long‐wave infrared (LWIR) spectrum (7–14 μm) offer important advantages for high‐resolution thermal imaging in near or complete darkness. The use of polymeric transmissive materials for IR imaging offers numerous cost and processing advantages but suffers from inferior optical properties in the LWIR spectrum. A major challenge in the design of LWIR‐transparent organic materials is that nearly all organic molecules absorb in this spectral window which lies within the so‐called IR‐fingerprint region. We report on a new molecular‐design approach to prepare high refractive index polymers with enhanced LWIR transparency. Computational methods were used to accelerate the design of novel molecules and polymers. Using this approach, we have prepared chalcogenide hybrid inorganic/organic polymers (CHIPs) with enhanced LWIR transparency and thermomechanical properties via inverse vulcanization of elemental sulfur with new organic co‐monomers.