High Molecular Weight Polymers Research Articles

α-Trifluoromethylated Quinolines as Safe and Storable PET-Donor for Radical Polymerizations.

In the quest for powerful, safe, and storable photoinduced-electron transfer (PET) donors, the attention is turned to the α-trihalomethylated amine moiety that is not studied in the context of PET-reductants. The thermal and photophysical properties of α-trifluoromethylated quinolines are thus studied and their reducing abilities evaluated as initiators of polymerization reactions. Polymers of high molecular weights are obtained through a radical polymerization process and the PET-donor can be stored within the monomer for several months without losing its efficiency. Mechanistic investigations, combining spectroscopic analysis and theoretical calculations, confirm the mode of activation of these electron donors and the generation of radical intermediates through single electron transfer.

Elucidation of pineapple softening based on cell wall polysaccharides degradation during storage

The degradation of cell wall polysaccharides in pineapple fruit during softening was investigated in the present study. Two pectin fractions and two hemicellulose fractions were extracted from the cell wall materials of ‘Comte de Paris’ pineapple fruit at five softening stages, and their compositional changes were subsequently analyzed. The process of softening of the fruit corresponded to an increase in the water-soluble pectin (WSP) and 1 M KOH-soluble hemicellulose (HC1) fractions, and a decrease in the acid-soluble pectin (ASP) fraction, which suggested the solubilization and conversion of cellular wall components. However, the content of 4 M KOH-soluble hemicellulose (HC2) decreased and then returned to the initial level. Furthermore, WSP, ASP, and HC1 showed an increment in the content of low molecular weight polymers while a decline in the high molecular weight polymers throughout softening, and not significant change in the contents of different molecular polymers of HC2 was observed. Moreover, the galacturonic acid (GalA) content in the main chain of WSP was maintained at a relatively constant level, but the major branch monosaccharide galactose (Gal) in WSP decreased. Different from WSP, the molar percentages of Gal and GalA in ASP decreased. The Gal or Arabinose (Ara) in HC1 exhibited a gradual decline while the molar percentages of xylose (Xyl) and glucose (Glu) in the main chain increased. These suggested that the main chain of ASP degraded while the branched chains of ASP, WSP and HC1 depolymerized during pineapple softening. Overall, fruit softening of ‘Comte de Paris’ pineapple was found to be the result of differential modification of pectin and hemicellulose.

Anaerobic Degradation of Aromatic and Aliphatic Biodegradable Plastics: Potential Mechanisms and Pathways.

Biodegradable plastics (BDPs) have been widely used as substitutes for traditional plastics, and their environmental fate is a subject of intense research interest. Compared with the aerobic degradation of BDPs, their biodegradability under anaerobic conditions in environmental engineering systems remains poorly understood. This study aimed to investigate the degradability of BDPs composed of poly(butylene adipate-co-terephthalate) (PBAT), poly(lactide acid) (PLA), and their blends, and explore the mechanism underlying their microbial degradation under conditions of anaerobic digestion (AD). The BDPs readily depolymerized under thermophilic conditions but were hydrolyzed at a slow rate under conditions of mesophilic AD. After 45 days of thermophilic AD, a decrease in the molecular weight and significant increase in the production of methane and carbon dioxide production were observed. Network and metagenomics analyses identified AD as reservoirs of plastic-degrading bacteria that produce multiple plastic-degrading enzymes. PETase was identified as the most abundant plastic-degrading enzyme. A potential pathway for the anaerobic biodegradation of BDPs was proposed herein. The polymers of high molecular weight were subjected to abiotic hydrolysis to form oligomers and monomers, enabling subsequent microbial hydrolysis and acetogenesis. Ultimately, complete degradation was achieved predominantly via the pathway involved in the conversion of acetic acid to methane. These findings provide novel insight into the mechanism underlying the anaerobic degradation of BDPs and the microbial resources crucial for the efficient degradation of BDPs.

Mechanisms of efficient polyacrylamide degradation: From multi-omics analysis to structural characterization of two amidohydrolases

Polyacrylamide (PAM) is a high molecular weight polymer with extensive applications. However, inefficient natural degradation of PAM results in its environmental accumulation. Here, using multi-omics analysis, we constructed the PAM biodegradation pathway in Klebsiella sp. PCX, an efficient PAM-degrading bacterium. Subsequently, two unclassified amidohydrolases (PCX00451 and PCX04581) were identified as key factors for rapid PAM biodegradation, both of which possessed much higher hydrolysis efficiency for PAM than for small molecule amide compounds. Besides, crystal structures of PCX00451 and PCX04581 were solved. Both two amidohydrolases were consisted with a twisted triosephosphateisomerase (TIM)-barrel and a smaller β-sandwich domain. And their binding pockets were in the conserved metal center of TIM-barrel domain. Moreover, Asp267 of PCX00451 and Asp282 of PCX04581 were examined as active sites for acid/base catalysis. Our research characterized the molecular mechanisms of two efficient amidohydrolases, providing theoretical basis and valuable tools for PAM bioremediation.

Novel fracturing fluid made of low molecular weight polymer and surfactant achieves proppant full suspension and filling entire area of hydraulic fractures

In large-scale hydraulic fracturing of unconventional reservoirs, high viscosity friction reducers (HVFR) which employ high concentration polymers of high molecular weight can improve proppant suspension, but still lack long-distance and long-time proppant transport capability. Herein, for the first time, we report a fracturing fluid made of self- assembled low molecular weight polymer and a surfactant (LMPS). When using only 0.1 wt% of the polymer, LMPS has a viscosity of 29.6 mPa·s (170 s−1, 25 ℃) and can achieve full suspension of 40/70 mesh sand at 80 ℃. LMPS can form robust short molecular chain networks through numerous self-assembling association sites, rather than relying on entanglement. Notably, it achieves a minimum loss tangent as low as 0.1 in the viscoelastic response, demonstrating its strong elastic characteristics. According to the creep-recovery test, the strain recovery rate (87.9 %) of LMPS at 0.2 wt% polymer concentration far exceeds that of the HVFR with a concentration as high as 10.1 %. This indicates that LMPS has a stronger deformation-resisting ability, thereby preventing proppant settling. Taking advantage of LMPS’ superior proppant suspension capability, proppant can move with the slurry to the whole fracture for placement, while the HVFR provides only 48 % height support of the fractures in the form of dunes. A field trial shows that at a polymer concentration of 0.2 wt%, LMPS can stably transport 20/40 mesh quartz sand under a slurry rate of 2.8 m3/min and a proppant concentration of 635 kg/m3 during the fracturing process.

Constructing Multiscale Fibrous Morphology to Achieve 20% Efficiency Organic Solar Cells by Mixing High and Low Molecular Weight D18.

This study underscores the significance of precisely manipulating the morphology of the active layer in organic solar cells (OSCs). By blending polymer donors of D18 with varying molecular weights, a multiscale interpenetrating fiber network structure within the active layer is successfully created. The introduction of 10% low molecular weight D18 (LW-D18) into high molecular weight D18 (HW-D18) produces MIX-D18, which exhibits an extended exciton diffusion distance and orderly molecular stacking. Devices utilizing MIX-D18 demonstrate superior electron and hole transport, improves exciton dissociation, enhances charge collection efficiency, and reduces trap-assisted recombination compared to the other two materials. Through the use of the nonfullerene acceptor L8-BO, a remarkable power conversion efficiency (PCE) of 20.0% is achieved. This methodology, which integrates the favorable attributes of high and low molecular weight polymers, opens a new avenue for enhancing the performance of OSCs.

Synthesis and optimization of molecular weight of chitosan and carboxymethyl cellulose based polyurethanes

For the first time in this research, using a mixture design approach, polyurethanes (PUs) based on chitosan (CSN) and carboxymethyl cellulose (CMC) were synthesized to develop a high molecular weight polymer. In the synthesis process, a reaction between isophorone diisocyanate (IPDI) and hydroxyl-terminated polybutadiene was carried out to synthesize a prepolymer containing free NCO groups at the corners. This prepolymer was further reacted with changing moles ratio of CSN and CMC following the principles of statistical mixture design. The structural confirmation of the developed PUs was carried out through spectroscopic techniques (FTIR and NMR). The molecular weights of the PU specimens were characterized using gel permeation chromatography. The findings demonstrated that the interaction between CMC and CSN led to a notable increase in the molecular weights of the samples, supported by a significant p-value of 0.006. Additionally, the analysis of variance (ANOVA) disclosed that the employed mixture design and the resulting interaction model effectively account for 98 % of the total variation observed in the molecular weights. The sample labeled as PUS-3 (CMC0.50:CSN0.50) emerged as the most significant formulation, exhibiting a noteworthy 27.9 % improvement in the polymer molecular weight compared to the base sample, denoted as PUS-1 (CMC1.00:CSN0.00).

Humic acid: A promising bio-organic catalyst for green synthesis of phenol in aqueous medium at room temperature

A simple and mild catalytic protocol has been described using humic acid as a reusable catalyst for the synthesis of phenol in aqueous medium. Humic acid is an inexpensive, non-toxic and easily available high molecular weight polymer. The mentioned catalytic protocol utilizes hydrogen peroxide as a green oxidant and water: isopropanol as solvent which has several advantages like commercially available, cheap and reusable catalyst, high percentage yield, short reaction time, room temperature etc.

Large-scale floating polyacrylonitrile hybrid micro-/nanofiber membrane achieves efficient H/D isotope separation via photocatalytic proton transport

Advancements in isotope separation are both essential and challenging. The separation of water isotopes is vital in industrial production, biopharmaceuticals, and healthcare applications. This process is energy-intensive and complex due to the similarity of the isotopes. Pure polyacrylonitrile (PAN) is resistant to proton permeability, but neutral hydrogen radicals are capable of penetration. In this study, we report a novel approach using PAN macroscopic hybrid micro-/nanofibers in combination with a photocatalyst to separate hydrogen ion isotopes. Application of photocatalytic water splitting to generate protons results in significantly slower deuteron permeation in these fibers relative to protons, resulting in a separation factor of approximately 15 at room temperature. The composite PAN fibers exhibit a conductivity of 17.5 mS cm−1 at 25 °C and 95 % relative humidity. Our approach not only converts sunlight directly into storable hydrogen, but also enriches heavy water from H₂O/D₂O by H/D isotope separation. This study provides new insights into proton transport mechanisms in acidic media and demonstrates the significant potential of high molecular weight polymers for hydrogen isotope separation.

Extensional rheology of elastoviscous aqueous PEO/PEG or DMS Boger fluids and weakly elastic alternatives for investigating viscoelastic flows and instabilities

Boger fluids that exhibit a rate-independent shear viscosity (typically ∼ 1 Pa∙s = 1000x water viscosity) and elasticity measurable using torsional rheometers (modulus, relaxation time, or first normal stress difference) are considered as the realization of viscoelastic fluids described by the Oldroyd-B model. However, Boger fluids, conventionally formulated as dilute solutions of high molecular weight (Mw) polymers in relatively high viscosity solvents (or solutions of oligomers or lower Mw polymer), are unsuitable for emulating polymeric fluids used in coating formulations that are lower in viscosity, appear inelastic in torsional shear rheometry, and yet appear prone to viscoelastic instabilities. Therefore, Dontula, Macosko, and Scriven (DMS) (AIChE J, 1998) chose to create an alternative model of elastic fluids by dissolving ultrahigh molecular weight (UHMw) poly(ethylene oxide) (PEO) in an aqueous solution of its lower Mw analog, often referred to as poly(ethylene glycol) or PEG. Even though numerous studies of printing and coating flow instabilities use this aqueous PEO/PEG or DMS Boger fluids as model viscoelastic fluids, only a few explicitly measured elastic properties, especially using relaxation time, and hardly any characterized extensional rheology. In this contribution, we recreate the DMS Boger fluids to examine their elasticity and extensional rheology response using dripping-onto-substrate (DoS) rheometry that relies on an analysis of capillarity-driven pinching dynamics. Though the aqueous PEG solution is often treated as a viscous and Newtonian solvent, we discover that in DoS rheometry, both the PEG solution and the DMS Boger fluid display power law response followed by elastocapillary, in contradiction with the assumptions and the response expected of the Oldroyd-B model. Furthermore, the solution of entangled PEG chains influences specific viscosity, pinching dynamics, and measured extensional rheology response in striking contrast with Newtonian solvents of the same viscosity. Lastly, we describe the possibility of using dilute, aqueous solutions of UHMw PEO as model viscoelastic fluids for coating flows, for both elasticity and extensional viscosity can be determined using DoS rheometry. Due to their water-like viscosity, the aqueous PEO solutions appeal as model fluids that have elasticity, emulate Newtonian fluids in the early stages of pinching, and have a relaxation time tunable by changing polymer Mw or concentration.

Insights on influence of polymer molecular weight on gas sorption, transport and plasticization in glassy 6FDA-DAM polyimide membranes

It is well-known that spinning of defect-free asymmetric polyimide hollow fibers is promoted by using high polymer molecular weight. On the other hand, effects of polymer molecular weight on microstructure and separation performance of dense film 6FDA-based polyimide membranes relevant to sheath layers of composite membranes are less well-explored. In this work, gas sorption, diffusion and permeation of CO2, N2 and CH4 for 6FDA-DAM dense films are considered for 45 kDa and 176 kDa weight average molecular weights. Such molecular weights are relevant for practical hollow fiber spinning of membranes. Earlier results for polystyrene samples show similar trends in dual mode sorption model results like those noted here for the 6FDA-DAM polyimide case; however, effects on permeation like those considered here were not addressed for the polystyrene case. Here we also address actual pure and mixed gas CO2 and CH4 permeation and show higher free volumes, higher gas permeability but lower 50:50 CO2/CH4 selectivity associated with the higher molecular weight sample. Analysis using the self-consistent dual-mode sorption and transport models help understand the observed trends. Our results suggest denser packing of polymer segments exists in the Henry's law environment of the low molecular weight sample. Moreover, the higher polymer segmental packing in the Henry's law environment suppresses CO2 plasticization with a dual-mode microstructure controlling separation performance and plasticization behavior for this important member of the 6FDA polyimide family. We show evidence of effects of charge transfer complexes as possible main features in these trends. These dense film results help guide future work on dense sheath layers on composite hollow fiber membranes.

Selective aggregation of hematite from quartz using charged polyacrylamides: In-situ sizing

Recovering fine valuable material has been a significant challenge in minerals processing. This primarily stems from insufficient collision opportunities between fine particles and bubbles, specifically when utilising traditional recovery methods such as froth flotation. This research endeavours to address this challenge by exploring the use of various commercially available, high molecular weight polymers- specifically polyacrylamide (PAM)- to selectively aggregate hematite from quartz. Investigation of the conditions in which selective aggregation of hematite over quartz occurs, with the goal to achieve aggregate sizes of between 20 and 150 μm, were undertaken. Targeting this size range ensure that conditions are optimised for future use in conventional mechanical flotation cells as an efficient mineral recovery method. The study investigates the selectivity of charged PAM towards hematite and quartz at pH 10, using adsorption studies. Anionic PAM demonstrates a preference for hematite, with a range of charge density studies, highlighting stronger adsorption capacity with lower charge density polymers. Using BlazeMetrics probe technology for in-situ sizing and imaging, it was observed that conditioning 50–300 g APAM per t of hematite resulted in aggregates in the range of 30–230 μm after 5 min. Interestingly, the charge density of APAM does not markedly affect the size of the hematite aggregates, although altering the charge density of the polymer impacts the selectivity towards quartz. Additionally, cationic PAM results in the simultaneous aggregation of both hematite and quartz, not demonstrating selectivity. To mitigate heterocoagulation between minerals, a common dispersant, sodium hexametaphosphate (SHMP), was employed, which notably prevents quartz aggregation. Separation of aggregated hematite from quartz by sedimentation was only slightly effective with the majority of quartz settling with the hematite. Adding up to 1000 g of dispersant per t of hematite reduced the amount of quartz in the sediment bed by 23 %. The dispersant increased the magnitude of the negative zeta potential of the two minerals, particularly hematite, lowering heterocoagulation and improving effectiveness of hematite flocculation.

PREDICTIONS AND VERIFICATIONS OF UNIVERSAL COOPERATIVE RELAXATION AND DIFFUSION IN MATERIALS

ABSTRACT Since its inception in 1979, the coupling model has predictions on the dynamic properties of relaxation and diffusion that should be universal in materials with many-body interactions. The verifications of this bold prediction require studies of many different relaxation and diffusion processes in diverse kinds of material. These tasks, performed over the past four decades, have culminated in the overwhelming confirmation of the predictions as reported in my previous extensive review (Prog. Mater. Sci.139, 101130 [2023]). A large variety of relaxation and diffusion processes in widely different classes of materials are shown to have the predicted universal properties. In particular for polymers, the local segmental relaxation responsible for glass transition conforms to the universal properties. However, not known is whether diffusion of the entangled chains in high molecular weight polymers also follows the same properties. Published data of the diffusion of entangled polymer chains from experiments and simulations are reexamined and reevaluated to show indeed that they are in conformity with the universal properties. The same conclusion holds also for diffusion and rheology of entangled cyclic polymers. This paper is written as a tribute to C. Michael Roland for his scientific collaborations and camaraderie with me over many years.

Motility and pairwise interactions of chemically active droplets in one-dimensional confinement.

Self-propelled droplets serve as ideal model systems to delve deeper into understanding the motion of biological microswimmers by simulating their motility. Biological microorganisms are renowned for showcasing a diverse array of dynamic swimming behaviors when confronted with physical constraints. This study aims to elucidate the impact of physical constraints on swimming characteristics of biological microorganisms. To achieve this, we present observations on the individual and pairwise behavior of micellar solubilized self-propelled 4-cyano-4'-pentyl-biphenyl (5CB) oil droplets in a square capillary channel filled with a surfactant trimethyl ammonium bromide aqueous solution. To explore the effect of the underlying Péclet number of the swimming droplets, the study is also performed in the presence of additives such as high molecular weight polymer polyethylene oxide and molecular solute glycerol. The capillary confinement restricts droplet to predominantly one-dimensional motion, albeit with noticeable differences in their motion across the three scenarios. Through a characterization of the chemical and hydrodynamic flow fields surrounding the droplets, we illustrate that the modification of the droplets' chemical field due to confinement varies significantly based on the underlying differences in the Péclet number in these cases. This alteration in the chemical field distribution notably affects the individual droplets' motion. Moreover, these distinct chemical field interactions between the droplets also lead to variations in their pairwise motion, ranging from behaviors like chasing to scattering.

Enabling low molecular weight electrospinning through binary solutions of polymer blends

The formation of nanofibrous membranes via electrospinning is typically restricted to high molecular weight polymers in an appropriate solvent, correlated with the necessary formation of polymer chain entanglements that are needed to achieve successful production of electrospun fibers. The present work extends the electrospinning of low molecular weight polymers by investigating the electrospinning of a binary solution system consisting of two different low molecular weight polymers, using as a model system polycaprolactone (PCL) and gelatin in different ratios. The viscosities of the polymer solutions were characterized as a proxy for polymer chain entanglement and the resulting fibers were morphologically characterized by SEM imaging and further assessed water contact angle and molecular composition to determine the impact and homogeneity of the binary mixtures. We found that unitary solutions of either PCL or gelatin failed to generate proper fibers despite indications of chain entanglement. In contrast, binary solutions of low molecular weight PCL and gelatin generated different fiber quality and size distributions, depending on the ratio used, with direct correlations between fiber properties and the PCL:Gelatin ratio. It was discovered that the ratio of PCL to gelation was most predictive for successful fiber generation, with effective electrospinning occurring only for a define intermediate range of high blend ratios while both low and high blended binary solutions resulted in poor fiber production. Our study confirmed that this behavior was independent from absolute polymer concentration, indicating a unique interaction between these binary species which exists only under specific ratio concentrations and indicates promising new avenues to process low molecular weight polymers solutions.

Process dependent properties of glassy polymer films revealed by molecular dynamics simulations

A molecular dynamics (MD) framework has been proposed to systematically simulate process (but not cooling rate) dependent properties of glassy polymer films. With the coarse-grained (CG) polylactide (PLA) of low molecular weight (MW), the simulated thermal properties of glassy films are confirmed to be surely decided by the routes to prepare them. While the glassy films initially prepared from the melt bulk are stable, the glassy film initially constructed from the glassy bulk appears to be unstable, featuring highest potential energy among those films and different averaged heat capacity from the bulk counterparts. Inspired by physical vapour deposition (PVD), a surface formation process is further applied to the unstable film to generate stable glassy polymer films. Similar to the PVD, an optimal temperature at which the film is most stable can be identified with lower potential energy than the conventional films, for which free surface and enhanced order of the middle layer are responsible. This work paves a way for obtaining simulated models of stable glassy films and experimentally preparing advanced glassy films for high MW polymers, which otherwise are hard to be realized by the PVD process.

Effects of different protein cross-linking degrees on physicochemical and subsequent thermal gelling properties of silver carp myofibrillar proteins sol subjected to freeze-thaw cycles

Knowledge regarding the denaturation process and control methods for depolymerized sol-state myofibrillar proteins (MPs) during freezing remains scant. This study investigated the effects of protein cross-linking treatment before freezing on physicochemical and subsequent gelation properties of MPs sol subjected to freeze-thaw (F-T) cycles. Results indicated that after five F-T cycles, cross-linked MPs sols showed increased high molecular weight polymers and bound water (T21a and T21b) mobility, suggesting enhanced protein-protein interactions at the expense of protein-water interactions. Upon heating after F-T cycles, gels formed from cross-linked sols exhibited significantly higher hardness, springiness, and cooking loss (P < 0.05), alongside more contracted gel networks. Correlation analysis revealed that the formation and properties of thermal gel after freezing closely relate to changes in molecular conformation and chemical bonds of cross-linked MPs sol during freezing. This study provides new insights into regulating the freezing stability and post-thawed thermal processing properties of sol-based surimi products.

Development of Ring-Expansion RAFT Polymerization of tert-Butyl Acrylate with a Cyclic Trithiocarbonate Derivative toward the Facile Synthesis of Cyclic Polymers.

Polymers with cyclic topology have no terminal structure and, therefore, exhibit various unique physical and functional properties compared to those of linear analogs. In this paper, we report an innovative methodology for the synthesis of cyclic polymers via ring-expansion RAFT (RE-RAFT) polymerization of vinyl monomers using a cyclic trithiocarbonate derivative (CTTC) as a RAFT agent. RE-RAFT of tert-butyl acrylate (TBA) was performed to yield a mixture of polymers exhibiting a bimodal size exclusion chromatography (SEC) trace. Both the peak top molecular weights shifted to higher-molecular-weight regions as the monomer conversion increased. The structure of the resulting polymer mixture was examined by 1H NMR and MALDI-TOF-MS. Detailed studies indicated that the obtained polymer of higher molecular weight was one of the large-sized cyclic polymers generated by the fusion of smaller-sized cyclic polymers during the RE-RAFT polymerization process. This approach opens the door to the simple synthesis of well-controlled cyclic polymers with complex structures, such as alternating and multi-block repeat unit sequences.

Genomic characterization and related functional genes of γ- poly glutamic acid producing Bacillus subtilis.

γ- poly glutamic acid (γ-PGA), a high molecular weight polymer, is synthesized by microorganisms and secreted into the extracellular space. Due to its excellent performance, γ-PGA has been widely used in various fields, including food, biomedical and environmental fields. In this study, we screened natto samples for two strains of Bacillus subtilis N3378-2at and N3378-3At that produce γ-PGA. We then identified the γ-PGA synthetase gene cluster (PgsB, PgsC, PgsA, YwtC and PgdS), glutamate racemase RacE, phage-derived γ-PGA hydrolase (PghB and PghC) and exo-γ-glutamyl peptidase (GGT) from the genome of these strains. Based on these γ-PGA-related protein sequences from isolated Bacillus subtilis and 181 B. subtilis obtained from GenBank, we carried out genotyping analysis and classified them into types 1-5. Since we found B. amyloliquefaciens LL3 can produce γ-PGA, we obtained the B. velezensis and B. amyloliquefaciens strains from GenBank and classified them into types 6 and 7 based on LL3. Finally, we constructed evolutionary trees for these protein sequences. This study analyzed the distribution of γ-PGA-related protein sequences in the genomes of B. subtilis, B. velezensis and B. amyloliquefaciens strains, then the evolutionary diversity of these protein sequences was analyzed, which provided novel information for the development and utilization of γ-PGA-producing strains.

High Molar Mass Polycarbonates as Closed-Loop Recyclable Thermoplastics.

Using carbon dioxide (CO2) to make recyclable thermoplastics could reduce greenhouse gas emissions associated with polymer manufacturing. CO2/cyclic epoxide ring-opening copolymerization (ROCOP) allows for >30 wt % of the polycarbonate to derive from CO2; so far, the field has largely focused on oligocarbonates. In contrast, efficient catalysts for high molar mass polycarbonates are underinvestigated, and the resulting thermoplastic structure-property relationships, processing, and recycling need to be elucidated. This work describes a new organometallic Mg(II)Co(II) catalyst that combines high productivity, low loading tolerance, and the highest polymerization control to yield polycarbonates with number average molecular weight (Mn) values from 4 to 130 kg mol-1, with narrow, monomodal distributions. It is used in the ROCOP of CO2 with bicyclic epoxides to produce a series of samples, each with Mn > 100 kg mol-1, of poly(cyclohexene carbonate) (PCHC), poly(vinyl-cyclohexene carbonate) (PvCHC), poly(ethyl-cyclohexene carbonate) (PeCHC, by hydrogenation of PvCHC), and poly(cyclopentene carbonate) (PCPC). All these materials are amorphous thermoplastics, with high glass transition temperatures (85 < Tg < 126 °C, by differential scanning calorimetry) and high thermal stability (Td > 260 °C). The cyclic ring substituents mediate the materials' chain entanglements, viscosity, and glass transition temperatures. Specifically, PCPC was found to have 10× lower entanglement molecular weight (Me)n and 100× lower zero-shear viscosity compared to those of PCHC, showing potential as a future thermoplastic. All these high molecular weight polymers are fully recyclable, either by reprocessing or by using the Mg(II)Co(II) catalyst for highly selective depolymerizations to epoxides and CO2. PCPC shows the fastest depolymerization rates, achieving an activity of 2500 h-1 and >99% selectivity for cyclopentene oxide and CO2.