Properties Of Copolymers Research Articles

Structure, morphology and crystallization of isodimorphic random copolymers: Copolyesters, copolycarbonates and copolyamides

Random copolymerization is used to prepare new polymeric materials that combine the desirable properties of different homopolymers. The covalent bonds between the comonomers enable miscibility and the formation of random copolymers with specific properties tailored for various applications. The crystallization behavior of random copolymers is intricate, encompassing up to three crystallization modes, i.e., total comonomeric exclusion, isomorphism, and isodimorphism. Isomorphism and isodimorphism allow for crystallization across the entire composition range, resulting in unique and potentially advantageous properties for each composition. These characteristics have garnered significant attention, as evidenced by the multiple publications that have appeared in the last decade.This contribution reviews the progress made in several aspects of isodimorphic copolymers, including new cases and applications. The initial section focuses on the factors influencing the pseudo-eutectic position, which is crucial for understanding the crystallization behavior of these copolymers. Subsequently, advancements in determining the degree of comonomer inclusion are discussed. Another section highlights studies that have raised new questions about the concepts of isodimorphism and isomorphism, particularly their presence in blends and terpolymers. These findings have opened up new avenues for research.In the final part of this review, selected examples are presented to illustrate the relationship between structure and properties in random copolymers. Furthermore, practical applications, such as using random copolymers as hot melt adhesives, are showcased. Despite significant progress in understanding the crystallization modes in random copolymers, this contribution emphasizes that new phenomena continue to emerge, providing further opportunities for exploration and shedding light on novel applications related to these intriguing crystallization modes.

Effect of hydrophobic nano‐silica/β‐nucleating agent on the crystallization behavior and mechanical properties of polypropylene random copolymers

AbstractIn this work, hydrophobic nano‐silica (SiO2) and β‐nucleating agent are incorporated into polypropylene random copolymer (PP‐R) matrix by melt blending. The effect of the content of nano‐SiO2/β‐nucleating agent on the crystallization and mechanical behaviors of PP‐R was investigated in detail. For a nano‐SiO2 content of 0.5 wt% and a β‐nucleating agent content of 0.5 wt%, the tensile strength and impact strength of the composite were in a more balanced position. Regarding isothermal and non‐isothermal crystallization experiments, nano‐SiO2/β‐nucleating agent significantly accelerated the nucleation and growth of crystallites with a synergistic nucleation effect. Also, the crystallization kinetics of PP‐R/nano‐SiO2/β‐nucleating agent, PP‐R/nano‐SiO2 and PP‐R/β‐nucleating agent composites were analyzed and compared using the Avrami equation. The results showed that the PP‐R/nano‐SiO2/β‐nucleating agent composites have better crystallization rate and shorter semi‐crystallization time. This study shows far‐reaching theoretical and practical implications for accelerating the development of new high‐performance PP‐R materials. © 2023 The Authors. Polymer International published by John Wiley & Sons Ltd on behalf of Society of Industrial Chemistry.

Controlled synthesis and solution properties of copolymers of methacrylic esters and ammonium-containing methacrylamide

Copolymers based on oligo(ethylene glycol) methacrylate, dodecyl methacrylate, and the cationic monomer N-methacryloylaminopropyl-N,N-dimethyl-N-propylammonium bromide have been obtained by reversible addition−fragmentation chain-transfer polymerization in high yields and in a controlled mode. The influence of the composition of the obtained polymers on the solubility in water and organic solvents, distribution in the water-octanol system, and interfacial tension at the water-oil interface is shown. The presence of thermoresponsive properties for polymers in water was found, and their aggregation in aqueous media was also studied.

Tailoring the Nucleation and Crystallization Rate of Polyhydroxybutyrate by Copolymerization.

In the polyester family, the biopolymer with the greatest industrial potential could be poly(3-hydroxybutyrate) (PHB), which can be produced nowadays biologically or chemically. The scarce commercial use of PHB derives from its poor mechanical properties, which can be improved by incorporating a flexible aliphatic polyester with good mechanical performance, such as poly(ε-caprolactone) (PCL), while retaining its biodegradability. This work studies the structural, thermal, and morphological properties of block and random copolymers of PHB and PCL. The presence of a comonomer influences the thermal parameters following nonisothermal crystallization and the kinetics of isothermal crystallization. Specifically, the copolymers exhibit lower melting and crystallization temperatures and present lower overall crystallization kinetics than neat homopolymers. The nucleation rates of the PHB components are greatly enhanced in the copolymers, reducing spherulitic sizes and promoting transparency with respect to neat PHB. However, their spherulitic growth rates are depressed so much that superstructural growth becomes the dominating factor that reduces the overall crystallization kinetics of the PHB component in the copolymers. The block and random copolymers analyzed here also display important differences in the structure, morphology, and crystallization that were examined in detail. Our results show that copolymerization can tailor the thermal properties, morphology (spherulitic size), and crystallization kinetics of PHB, potentially improving the processing, optical, and mechanical properties of PHB.

Biodegradable Polyhydroxyalkanoates with a Different Set of Valerate Monomers: Chemical Structure and Physicochemical Properties.

The properties, features of thermal behavior and crystallization of copolymers containing various types of valerate monomers were studied depending on the set and ratio of monomers. We synthesized and studied the properties of three-component copolymers containing unusual monomers 4-hydroxyvalerate (4HV) and 3-hydroxy-4-methylvalerate (3H4MV), in addition to the usual 3-hydroxybutyrate (3HB) and 3-hydroxyvalerate (3HV) monomers. The results showed that P(3HB-co-3HV-co-4HV) and P(3HB-co-3HV-co-3H4MV) terpolymers tended to increase thermal stability, especially for methylated samples, including an increase in the gap between melting point (Tmelt) and thermal degradation temperature (Tdegr), an increase in the melting point and glass transition temperature, as well as a lower degree of crystallinity (40-46%) compared with P(3HB-co-3HV) (58-66%). The copolymer crystallization kinetics depended on the set and ratio of monomers. For terpolymers during exothermic crystallization, higher rates of spherulite formation (Gmax) were registered, reaching, depending on the ratio of monomers, 1.6-2.0 µm/min, which was several times higher than the Gmax index (0.52 µm/min) for the P(3HB-co-3HV) copolymer. The revealed differences in the thermal properties and crystallization kinetics of terpolymers indicate that they are promising polymers for processing into high quality products from melts.

Partial crystalline organosilicon-based polysiloxane-polyurethane copolymers

Partial crystalline polysiloxane-based polyurethane copolymers were prepared by using hydroxyethoxypropyl capped polydimethylsiloxane (PDMS) as soft segment and α,ω-(bis (hydroxyethylthioether) ethyl)-disiloxane as chain extender. Due to this partial crystalline structure, the copolymer shows fairly good tensile properties and multiple shape deformation property. Repeated tensile tests revealed that stretch led to crystal destruction, and the microstructure of samples became stable after twice stretches. The lost crystallinity got 85.1% recovered upon treated at 60 °C for 1 h. It was proved that partial crystallization properties of the polysiloxane-polyurethane copolymer were from combined effects of polysiloxane soft segment and disiloxane chain extender. This unique crystallization kinetics of -(Si-O-Si)x- structure coexisting in soft and hard segments is regarded as one main reason to form crystalline hard segment domains in a common two-step synthesis.

Effect of Octene Block Copolymer (OBC) and High-Density Polyethylene (HDPE) on Crystalline Morphology, Structure and Mechanical Properties of Octene Random Copolymer.

Blending octene random copolymer (ORC) with other polymers is a promising approach to improving ORC mechanical properties, such as tensile strength and elongation. In this study, octene block copolymer (OBC) with lower density than ORC and high-density polyethylene (HDPE) were used to blend with ORC. The effect of both OBC and HDPE on ORC was analyzed using scanning electron microscopy (SEM), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA) and small-angle X-ray scattering (SAXS). For ORC/OBC blends, a small amount of OBC can improve the crystallization ability of ORC. Meanwhile, for ORC/HDPE blends, the crystallization ability of ORC was significantly suppressed, attributed to good compatibility between ORC and HDPE as indicated by the homogeneous morphology and the disappearance of the α transition peak of ORC in ORC/HDPE blends. Therefore, the tensile strength and elongation of ORC/HDPE blends are significantly higher than those of ORC/OBC blends. For ORC/OBC/HDPE ternary blends, we found that when ORC:OBC:HDPE are at a ratio of 70:15:15, cocrystallization is achieved. Although HDPE improves the compatibility of ORC and OBC, the three-phase structure of the ternary blends can be observed through SAXS when HDPE and OBC exceed 30 wt%. Blending HDPE and OBC (≤30 wt%) could improve the mechanical property of ORC.

Controlled Radical Polymerization of Acrylates and Isocyanides Installs Degradable Functionality into Novel Copolymers.

Installing ketones into a polymer backbone is a known method for introducing photodegradability into polymers; however, most current methods are limited to ethylene-carbon monoxide copolymerization. Here we use isocyanides in place of carbon monoxide in a copolymerization strategy to access degradable nonalternating poly(ketones) that either maintain or enhance the thermal properties. A cobalt-mediated radical polymerization of acrylates and isocyanides synthesizes nonalternating poly(acrylate-co-isocyanide) copolymers with tunable incorporation using monomer feed ratios. The kinetic product of the polymerization is a dynamic β-imine ester that tautomerizes to the β-enamine ester. Hydrolysis of this copolymer affords a third copolymer microstructure─the elusive nonalternating poly(ketone)─from a single copolymerization strategy. Analysis of the copolymer properties demonstrates tunable thermal properties with the degree of incorporation. Finally, we show that poly(acrylate-co-isocyanide) and poly(acrylate-co-ketone) are photodegradable with 390 nm light, enabling chain cleavage.

Crystallization, structure and properties of PP-b-PE block copolymer

In recent years, a commercialized polypropylene (PP) and polyethylene (PE) block copolymer has been synthesized using chain-shuttling polymerization, but its molecular structure and properties are still limitedly understood. In this work, we analyzed the chain composition, mechanical properties, and structural transformations occurring during the deformation of commercial PP-PE block copolymer obtained via chain-shuttle technology. The chain composition and crystallization properties of PP-PE block copolymers obtained by chain shuttling technique were analyzed using nuclear magnetic resonance (NMR), temperature-rising elution fractionation (TREF), and differential scanning calorimetry (DSC) techniques. The sample has a mass ratio of 49:51 of PE chains to PP chains, but the crystallinity of the two components differs significantly. The PP displays limited crystallinity, indicating short PP chain segments. Some PE sequences are incorporated into the PP matrix as random copolymers, resulting in elastomeric behavior. We investigated the In-situ structural changes of crystals during stretching using synchrotron radiation 2D X-ray diffraction/scattering. In the elastic deformation region, the strain has a significant influence on the orientation of PE crystals but has little effect on the orientation of PP crystals. After the yield point, the strain-induced PE crystal failure resulting in a decrease in stress. In the strain hardening region, the orientation of PE induces recrystallization, forming a layered structure with tensile orientation. At the same time, the PP crystals are disoriented under the action of strain until they break. The results from this work provide significant insight into the design of PP-PE block copolymer products to meet the performance requirements needed for engineering applications.

Boronate affinity imprinted organo/hydro copolymers fabricated from Pickering emulsions reactor for specific recognition of Luteolin

To date, the flexiable organo/hydro copolymer materials have made of interest for separation, but the utilize of Pickering emulsion from such macroporous monoliths is challenging. A new kind of flexible boronate affinity imprinted organo/hydro copolymer sorbents (UiO-66-NH2@MIPs-FPS) were firstly fabricated via Pickering emulsion interfacial polymerization. This strategy allowed the formation of the organo/hydro imprinted copolymer matrix with multiple hydrogen bonded interactions, which can efficiently adjusting the mechanical property of copolymers supporting matrix. In addition, this method provided the effective boronate affinity imprinted recognizing sites and abundant porous structure based on Pickering emulsion reactor. As the novel solid emulsifier, UiO-66-NH2@MIPs, molecularly imprinted polymers (MIPs) based on UiO-66-NH2 could greatly improves the number of boronic acid recognizing sites and mechanical performance of the copolymer matrix. As excepted, the porous boronate affinity imprinted copolymer sorbents showed fast adsorption kinetics towards LTL, and the adsorption capacity could obtain 23.67 mg g−1. Meanwhile, the UiO-66-NH2@MIPs-FPS exhibited fast adsorption kinetics (60 min), high adsorption amounts (46.66 mg g−1), and excellent regeneration after six reuse cycles (4.92% loss in adsorption amounts) for LTL. The abundant imprinted recognizing sites such as boronic acid played a significant role on adsorption, and the emulsion interface polymerization of copolymer matrix avoided from the leakage of nanosize imprinted sorbents (UiO-66-NH2@MIPs). This work provided a new avenue on the construction of organo/hydro imprinted imprinted copolymer through inserting nanosize imprinted sorbents for selective capture of targeted flavonoid molecules.

Investigating the Impact of Hydrophobic Polymer Segments on the Self-Assembly Behavior of Supramolecular Cyclic Peptide Systems via Asymmetric-Flow Field Flow Fractionation.

The present study examines the behavior of cyclic peptide polymer conjugates that have been designed to combine their self-assembling ability via H-bonding with the properties of amphiphilic diblock copolymers. Using a combination of asymmetric flow-field flow fractionation (AF4) and small-angle neutron scattering (SANS), we have uncovered unique insight based on the population of structures established at a 24 h equilibrium profile. Our results determine that by introducing a small quantity of hydrophobicity into the conjugated polymer corona, the resulting nanotube structures exhibit low unimer dissociation which signifies enhanced stability. Furthermore, as the hydrophobicity of the polymer corona is increased, the elongation of the nanotubes is observed due to an increase in the association of unimers. This encompasses not only the H-bonding of unimers into nanotubes but also the self-assembly of single nanotubes into segmented-nanotube structures with high aspect ratios. However, this influence relies on a subtle balance between the hydrophobicity and hydrophilicity of the polymer corona. This balance is proposed to determine the solvent entropic penalty of hydrating the system, whereby the cost scales with the hydrophobic quantity. Consequently, it has been suggested that at a critical hydrophobic quantity, the solvation penalty becomes high enough such that the self-assembly of the system deviates from ordered hydrogen bonding. The association behavior is instead dominated by the hydrophobic effect which results in the undesirable formation of disordered aggregates.

Abstract P1022: Synthetic Copolymer-Based Membrane Stabilizers Confer Protection To Dystrophin-Deficient Striated Muscle In Vitro And In Vivo

Duchenne muscular dystrophy (DMD) is a chronic and progressive muscle wasting disease resulting from the inability to produce the cytoskeletal protein dystrophin. The absence of dystrophin increases the susceptibility of the sarcolemma to mechanical damage and ultimately contributes to muscle degeneration and fibrosis. A growing body of evidence suggests that synthetic membrane stabilizing copolymers can be an effective strategy to limit contraction-induced sarcolemma damage. First-in-class copolymer-based membrane stabilizer Poloxamer 188 (P188) is a linear, amphiphilic triblock copolymer demonstrated to protect dystrophic cardiac and skeletal muscle in a wide variety of in vitro and in vivo models. However, the architectural features of P188 responsible for its membrane protective effects remain to be fully elucidated. Additionally, various other membrane-stabilizing copolymers differing in their size, architecture, and composition have been useful in structure-function studies. Here we sought to elucidate the properties of synthetic copolymers that confer stabilization to the dystrophin-deficient membrane. Using newly developed techniques, we designed and investigated an innovative class of branched “bottlebrush” copolymers at the single skeletal muscle fiber and organismal levels. Our results identify an intriguing, novel bottlebrush copolymer effective at previously unreported nanomolar concentrations in vitro . We also show in preliminary studies that bottlebrush copolymers may further confer protection during isoproterenol-induced cardiac stress testing in dystrophin deficient mice in vivo . These findings will be discussed in terms of copolymer-based membrane-interfacing molecules in the context of stabilizing dystrophin-deficient striated muscle.

Stress Chain Analysis for an ABA Triblock Copolymer Using Principal Component Scores.

Researchers characterize the mechanical properties of ABA triblock copolymers by structures such as chain conformation. During elongation, bridge chains are stretched and act as a stress chain. Some loop chains also act as a stress chain because of the transmission of stress through an entanglement of loop chains. The stress chain, including the entangled loop chains, in an ABA triblock copolymer that exhibits a body-centered cubic structure was analyzed by principal component analysis (PCA), using the physical data for the B block obtained by coarse-grained molecular dynamics simulations. Local deformation of the A domains caused by the stress chains was also analyzed by PCA of the A block. The dynamics of the stress chain strongly corresponded to the recombination of the A domains; shrinkage because of domain breakage, replacement of stress chains, and biased stress distribution as well as its time dependence were observed.

Ethylene Copolymerization with Linear and End-Cyclized Olefins via a Metallocene Catalyst: Polymerization Behavior and Thermal Properties of Copolymers

Olefin solution polymerization can be used to obtain high-performance polyolefin materials that cannot be obtained via other polymerization processes. Polyolefin elastomers (POE) are a typical example. Due to cost, only a few linear α-olefins (e.g., 1-butene, 1-hexene, and 1-octene) are used as comonomers in solution polymerization in industry. However, α-olefin comonomers with other structures may have different effects on polymerization in comparison with common linear ones. Moreover, the properties of the corresponding materials may differ significantly. In this work, copolymers of ethylene with linear and end-cyclized α-olefins are synthesized using a metallocene catalyst. The copolymerization of ethylene with linear α-olefins results in a higher turn-over frequency (TOF) and lower incorporation than copolymerization with end-cyclized α-olefins, which may indicate that end-cyclized α-olefins have a higher coordination probability and lower insertion rate. In this reaction, the comonomer is distributed randomly in the polymer chain and efficiently destroys crystallization. End-cyclized α-olefins exhibit a much stronger crystallization destructive capacity (CDC) in the copolymer than linear α-olefins, possibly because linear α-olefins act mainly in the radial direction of the main chain of the polymer, while end-cyclized α-olefins act mainly in the axial direction of the main chain.

Microstructure similarity analysis between synthetic phase-separated block copolymers and natural spider silk

This papers primary purpose is to explore why the microstructure of synthetic block copolymers and natural spider silk is similar at the nanoscale. This paper analyses the main chain segments and secondary structures of natural spider silk, clarifies the aggregation order, and introduces the contribution of secondary systems to the properties of natural block copolymers. Secondly, combined with the synthesis mechanism of natural spider silk, this paper summarizes and analyzes the general process of the synthesized block copolymer. Finally, the conditions of self-assembly of artificial fragments to form the structure are analyzed by employing mean-field theory and a phase diagram. Natural and ideal synthetic spider silk block copolymers have high similarity in performance. To achieve this, scientists can only start from the primary segment to understand their arrangement order in the secondary structure. Then the influence of each block on the properties of the silk fiber is analyzed. At the same time, the size and shape of self-assembled block copolymers are controlled at the micro-scale, thereby changing their properties. The mechanism above shows that the synthesized spider silk block copolymer is similar to natural spider silk in microscopic morphology.

Influence of Molecular Weight on the Enzymatic Degradation of PLA Isomer Blends by a Langmuir System.

Polylactides (PLAs) and lactide copolymers are biodegradable, compostable, and derived from renewable resources, offering a sustainable alternative to petroleum-based synthetic polymers owing to their advantages of comparable mechanical properties with commodity plastics and biodegradability. Their hydrolytic stability and thermal properties can affect their potential for long-lasting applications. However, stereocomplex crystallization is a robust method between isomer PLAs that allows significant amelioration in copolymer properties, such as thermal stability, mechanical properties, and biocompatibility, through substantial intermolecular interactions amid l-lactyl and d-lactyl sequences, which have been the key approach to initial degradation rate and further PLA applications. It was demonstrated that the essential parameters affecting stereocomplexation are the mixing ratio and the chain length of each unit sequence. This study deals with the molecular weight, one of the specific interactions between isomers of PLAs. A solution polymerization method was applied to control molecular weight and chain architecture. The stereocomplexation was monitored with DSC. It was confirmed that the lower molecular weight polymer showed a higher degradation rate, as a hydrolyzed fragment having a molecular weight below a certain length dissolves into the water. To systematically explore the critical contribution of molecular weights, the Langmuir system was used to observe the stereocomplexation effect and the overall degradation rate.

Thermal property of polyacrylate copolymers and their application in multilayer ceramic capacitor

Thermal property of polyacrylate copolymers and their application in multilayer ceramic capacitor

Complementary Supramolecular Functionalization Enhances Antifouling Surfaces: A Ureidopyrimidinone-Functionalized Phosphorylcholine Polymer.

Fibrosis of implants remains a significant challenge in the use of biomedical devices and tissue engineering materials. Antifouling coatings, including synthetic zwitterionic coatings, have been developed to prevent fouling and cell adhesion to several implantable biomaterials. While many of these coatings need covalent attachment, a conceptually simpler approach is to use a spontaneous self-assembly event to anchor the coating to a surface. This could simplify material processing through highly specific molecular recognition. Herein, we investigate the ability to utilize directional supramolecular interactions to anchor an antifouling coating to a polymer surface containing a complementary supramolecular unit. A library of controlled copolymerization of ureidopyrimidinone methacrylate (UPyMA) and 2-methacryloyloxyethyl phosphorylcholine (MPC) was prepared and their UPy composition was assessed. The MPC-UPy copolymers were characterized by 1H NMR, Fourier transform infrared (FTIR), and gel permeation chromatography (GPC) and found to exhibit similar mol % of UPy as compared to feed ratios and low dispersities. The copolymers were then coated on an UPy elastomer and the surfaces were assessed for hydrophilicity, protein absorption, and cell adhesion. By challenging the coatings, we found that the antifouling properties of the MPC-UPy copolymers with more UPy mol % lasted longer than the MPC homopolymer or low UPy mol % copolymers. As a result, the bioantifouling nature could be tuned to exhibit spatio-temporal control, namely, the longevity of a coating increased with UPy composition. In addition, these coatings showed nontoxicity and biocompatibility, indicating their potential use in biomaterials as antifouling coatings. Surface modification employing supramolecular interactions provided an approach that merges the simplicity and scalability of nonspecific coating methodology with the specific anchoring capacity found when using conventional covalent grafting with longevity that could be engineered by the supramolecular composition itself.

Efficient Removal of Carcinogenic Azo Dyes from Water Using Iron(II) Clathrochelate Derived Metalorganic Copolymers Made from a Copper-Catalyzed [4 + 2] Cyclobenzannulation Reaction

A novel synthetic strategy is disclosed to prepare a new class of metalorganic copolymers that contain iron(II) clathrochelate building blocks by employing a mild and cost-effective copper-catalyzed [4 + 2] cyclobenzannulation reaction, using three specially designed diethynyl iron(II) clathrochelate synthons. The target copolymers CBP1-3 were isolated in high purity and excellent yields as proven by their structural and photophysical characterization, namely, Fourier transform infrared (FTIR), X-ray photoelectron spectroscopy (XPS) and UV–VIS absorption and emission spectroscopies. The thermogravimetric analysis (TGA) of CBP1-3 revealed an excellent chemical stability. Investigation of the adsorption properties of the target copolymers towards the carcinogenic methyl red dye from aqueous solution revealed a quantitative uptake in 30 min. Isothermal adsorption studies disclosed that methyl red uptake from aqueous solution followed the Langmuir model for all of the target copolymers, reaching a maximum adsorption capacity (qm) of 431 mg g−. Kinetic investigation revealed that the adsorption followed pseudo-first-order with an equilibrium adsorption capacity (qe,cal) of 79.35 mg g− and whose sorption property was sustained even after its reuse several times.

Biobased Copolymers via Cationic Ring-Opening Copolymerization of Levoglucosan Derivatives and ε-Caprolactone.

Simultaneous ring-opening copolymerization is a powerful strategy for the synthesis of highly functional copolymers from different types of cyclic monomers. Although copolymers are essential to the plastics industry, environmental concerns associated with current fossil-fuel-based synthetic polymers have led to an increasing interest in the use of renewable feedstock for polymer synthesis. Herein, we report a scalable synthetic platform to afford unique polysaccharides with different pendant functional groups from biomass-derived levoglucosan and ε-caprolactone via cationic ring-opening copolymerization (cROCOP). Biocompatible and recyclable bismuth triflate was identified as the optimal catalyst for cROCOP of levoglucosan. Copolymers from tribenzyl levoglucosan and ε-caprolactone, as well as from tribenzyl and triallyl levoglucosan, were successfully synthesized. The tribenzyl levoglucosan monomer composition ranged from 16% to 64% in the copolymers with ε-caprolactone and 22% to 79% in the copolymers with triallyl levoglucosan. The allylic levoglucosan copolymer can be utilized as a renewably derived scaffold to modify copolymer properties and create other polymer architectures via postpolymerization modification. Monomer reactivity ratios were determined to investigate the copolymer microstructure, indicating that levoglucosan-based copolymers have a gradient architecture. Additionally, we demonstrated that the copolymer glass transition temperature (Tg, ranging from -44.3 to 33.8 °C), thermal stability, and crystallization behavior could be tuned based on the copolymer composition. Overall, this work underscores the utility of levoglucosan as a bioderived feedstock for the development of functional sugar-based copolymers with applications ranging from sustainable materials to biomaterials.