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[Display omitted] Hypothesis: Micelles formed by copolymers with mixed solvophobic blocks have attracted much attention lately. It is expected that changing the mixed blocks sequence can be used as a tool to influence the micellization behavior in a way that is not equivalent to simply varying the incompatibility parameter for pure diblock-copolymers. Simulations: By using coarse-grained simulations, the micellization behavior of copolymers with twelve types of solvophobic blocks, which differed in the fraction f as well as the sequence of solvophilic units in the solvophobic blocks, was studied. To enable quantitative comparison of systems with different f , an "effective" incompatibility parameter was introduced. Findings: The micelles size distributions and dynamics were found to be significantly dependent on both f and the fine details of the sequence. When the solvophobic block sequences were obtained statistically using a model of copolymerization, a strong influence of the reactivity ratios on the resulting micelles was found. Even a moderate tendency to form gradient-like sequences resulted in a noticeable increase in the micelles size. The dynamic properties of the micelles were studied by investigating the rate at which the chains escape from them. The addition of soluble units into the solvophobic block was shown to dramatically decrease the tendency to form kinetically frozen states; gradient-like sequences demonstrated more sluggish dynamics. The physical reasons for the observed peculiarities are discussed in detail. [ABSTRACT FROM AUTHOR]

An organomagnesium complex containing an imino-phosphanamidinate ligand was found to be a competent catalyst for the ROP of rac-LA and ε-CL as well as their copolymerization via sequential addition of monomers, resulting in the formation of PCL-b-PLA diblock copolymer. The polymers obtained were characterized by 1H, 13C, DOSY NMR, DSC, TGA, POM, and SEM. [ABSTRACT FROM AUTHOR]

Bio-based PA5T/56 was successfully prepared by a self-developed and novel modulated polymerization on this condition when the relationship between temperature and pressure was strictly controlled during the process to render the reactivity ratio of each monomers basically the same. In this case, the obtained PA5T/56, with approximately alternating copolymerization structure, possesses better physical and chemical performance and melt flowing properties. Meanwhile, the real-time sampling and testing was operated during the process to get the experimental values of reactivity ratio. Furthermore, the chain growth process of the ternary polymerization reaction was also calculated and simulated by referring to the Mayo-Lewis formula as well as using the Monte Carlo method, and a probabilistic statistical treatment for estimating the reactivity ratio was given. Finally, by comparing the results, it could be found that the experimental values of the reactivity ratio in general accord in the calculated values with reference to the Mayo–Lewis formula and the simulated values of the mathematical model, the values of r12 and r13 are basically the same, which confirmed the successful synthesis of the bio-based PA5T/56 with approximately alternating copolymerization structure, and that the established mathematical model for estimating the reactivity ratio is relatively accurate and is applicable to the ternary polymerization. [ABSTRACT FROM AUTHOR]

In this work, a novel family of α,ω-diene carbonate monomers was synthesized via the alkoxy carbonylation reaction of bis(hydroxymethyl)furan (BHMF) with dialkyl carbonates (DACs) of varying chain lengths, containing terminal olefins, in the presence of 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD). These monomers were then subjected to acyclic diene metathesis (ADMET) polymerization with seven different ruthenium catalysts. The second-generation Hoveyda–Grubbs catalyst proved to be the most effective, yielding furan-based polycarbonates with molecular weights (Mn) up to 19 kDa. The resulting bio-based polymers exhibited thermal degradation temperatures (Td5%) ranging from 156 °C to 244 °C and glass transition temperatures (Tg) from −8 °C to −36 °C. NMR studies confirmed their polymeric structures and provided insights into the polymers organization, which influenced their properties. These novel polycarbonates were then compared to previously reported polyesters and polyethers derived from similar furan-based α,ω-diene monomers. Additionally, for the first time, co-polymerization studies were conducted on three families of furan-based α,ω-diene monomers—ester, ether, and carbonate—revealing the effect of incorporating different functional groups on the properties of the resulting materials. This unprecedented comparison and co-polymerization reactions highlight the versatility of furan-based monomers, but also underscores the possibility to expand their application in creating tailored bio-based materials for diverse applications. [ABSTRACT FROM AUTHOR]

A sequential self‐polymerization of phenolic compounds combined with alkanedithiol (ADT) crosslinkers is developed as a versatile surface‐independent coating and functionalization strategy. The resulting copolymer takes advantage of the diverse binding modes of catechol and gallol and the conformal substrate contact facilitated by the flexible aliphatic chain of ADT. Moreover, Michael addition and thiyl radical addition reactions between ADT and phenolic compounds produce crosslinked resulting polymer films, rendering solvent resistance to the surface coating. This approach is successfully employed using phenolic monomers, including dopamine, 3,4‐dihydroxybenzylamine, 4‐ethylcatechol, levodopa, tannic acid, caffeic acid, and 3,4‐dihydroxybenzylaldehyde, to functionalize glass (ceramic), aluminum (metal), polyethylene (polymer), and Teflon surfaces. The resulting copolymer prepared with a trifunctional thiol crosslinker demonstrated solvent resistance in NaOH (aq.), DMSO, and chloroform, overcoming the stability issues typically encountered by conventional surface coating from polydopamine derivatives. [ABSTRACT FROM AUTHOR]

This research focuses on the application of click chemistry to the synthesis of amphiphilic lipidic copolymers with a target number of oleyl, cholesteryl, and linoleic pendant groups. The synthesis was performed using a two‐step approach. In the first step, copolymerization of ε‐caprolactone (CL) and α‐azido‐caprolactone (N3CL) was carried out using enzymatic ring‐opening polymerization (eROP) catalyzed by Candida Antarctica lipase B (CALB). This resulted in copolymers with an average molecular weight of 9.53 kDa, each containing approximately seven azide groups per chain. Subsequently, click chemistry was utilized to react P(N3CL‐co‐CL) copolymers with propargylated lipidic compounds, achieving azide group consumption higher than 88%. These lipidic copolymers exhibited reduced crystallinity, as evidenced by their lower melting enthalpy values. In addition, these materials were evaluated for the fabrication of nanostructured vehicles for curcumin (Cur@NP) using the solvent emulsion‐evaporation methodology. The lipidic copolymers demonstrated enhanced encapsulation efficiencies and drug loading capacities of 25 and 12%, respectively, tunable particle sizes in the range of 260–420 nm, and controlled release profiles over 30 h. Cur@NPs demonstrated notable antioxidant and antibacterial activities, particularly against Gram‐positive bacteria such as Staphylococcus aureus, achieving efficiencies close to 50%. [ABSTRACT FROM AUTHOR]

The homopolymerization of norbornene and the copolymerization of norbornene and ethylene were carried out using the neutral α-sulfonate-β-diimine nickel catalyst SD-Ni. The neutral α-sulfonate-β-diimine catalyst is highly active in the homopolymerization of norbornene, producing vinyl-addition polynorbornene (PNB) with a high molecular weight. The copolymerization of norbornene (NB) and ethylene (E) using the catalyst SD-Ni was also investigated. The α-sulfonate-β-diimine catalyst SD-Ni shows distinctive catalytic copolymerization properties to produce high-molecular-weight E-NB copolymers with low norbornene incorporation. Importantly, microstructure analyses confirm that the resultant E-NB copolymers are branched cyclo-olefin copolymers (COCs) with branched polyethylene units. [ABSTRACT FROM AUTHOR]

Polyolefins are used widely due to their benefits such as being lightweight, chemical inertness, low cost, tunable properties, and easy processability. However, their nonpolar nature significantly limits their high-end applications. The non-bridged half-titanocenes exhibit remarkable catalytic activities with good comonomer incorporations in the olefin polymerization. The synthesis of functional polyolefins has attracted more and more attention recently. The non-bridged half-titanocenes have been used in the preparation of functional polyolefins, in particular the functional olefin copolymers. Herein, the recent advancements in the synthesis of functional polyolefins by non-bridged half-titanocenes were reviewed. The functional polyolefins have been synthesized by direct copolymerization of olefin with functional comonomers using half-titanocenes as precatalysts. In addition, polyolefins containing reactive groups could be synthesized by the olefin (co)polymerization using half-titanocenes as precatalysts. The functional polyolefins were synthesized successfully by the post-functionalization of polyolefin containing reactive groups. [ABSTRACT FROM AUTHOR]

In this study, well-known biodegradable poly [(β-butyrolactone-block-ethylene glycol methyl ether)-phthalocyanine- (β-butyrolactone-block-ethylene glycol methyl ether)] abbreviated as poly(BL-b-mEG)-Pc-poly(BL-b-mEG) copolymer was synthesised. In the first part, poly (β-butyrolactone-block-ethylene glycol methyl ether) [poly(BL-b-mEG)] block copolymer was prepared by ring-opening polymerisation (ROP) method of β-butyrolactone using poly (ethylene glycol) methyl ether. In the second part, poly(BL-b-mEG)-Pc-poly(BL-b-mEG) copolymer was obtained from the reaction poly(BL-b-mEG) block copolymer, SiPcCl2, and K2CO3. Axial binding of poly(BL-b-mEG) block copolymers to the phthalocyanine compound was achieved. The synthesised products were characterised by using multi-instruments such as1H-NMR, FT-IR, GPC, ve UV-visible. The electronic and singlet oxygen production capacity of poly(BL-b-mEG)-Pc-poly(BL-b-mEG) copolymer was investigated. [ABSTRACT FROM AUTHOR]

We employ the 1,4‐cyano group migration radical polymerization strategy to copolymerize acrylates with 2‐thiocyanate ethyl substituted acrylates. The radical copolymerization can be effectively controlled using reversible addition−fragmentation chain‐transfer (RAFT) polymerization. This approach can incorporate thiol‐acrylate‐based dynamic bonds within the polymer main chain. Utilizing these dynamic bonds, we degrade the polymers under mild basic conditions, achieved with the assistance of 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) to facilitate the reversible thiol‐Michael addition. Notably, high degradation efficiency is observed. This study exemplifies the application of 2‐thiocyanate ethyl substituted acrylate in radical copolymerization to produce degradable polymers. [ABSTRACT FROM AUTHOR]

AbstractThe research of copolymerization of ethylene with polar monomers catalyzed by group 4 metal complexes has gain substantial achievement, and the functional polyolefins, produced through the various structures of the catalysts and polar monomers, have already shown their unique applications in multiple fields. There are kinds of effective strategies to improve copolymerization activity and polar monomers incorporation: the structures of group 4 catalysts have been expanded from metallocenes to half-metallocenes and non-metallocenes; the new cocatalysts and catalytic systems have been developed; polar monomers are pretreated by masking agents; the functional groups of polar monomers have been largely enriched. In this review, the copolymerization of ethylene with polar monomers catalyzed by group 4 metal complexes are concluded and compared, and we are looking forward to summarizing the relationship between structure and reactivity of catalysts and providing advice for the design of catalysts. Moreover, the properties and potential applications of polar functionalized polyolefins are introduced. [ABSTRACT FROM AUTHOR]

Herein, we report the free radical copolymerization of 1,3-cyclooctadiene and maleic anhydride or N-substituted maleimides. The obtained alternating copolymers have a fine-tuned Tg (ranging from 62 °C to 300 °C) and excellent thermal resistance and optical properties (up to 90% transmissivity). [ABSTRACT FROM AUTHOR]

This study presents an in vivo optical hydrogel microneedle platform that measures levels of analytes in interstitial fluid. The platform builds on a previously published technique for molding hydrogel microneedles by developing a composite hydrogel (i.e., PEGDA and polyacrylamide) that is sufficiently stiff to penetrate skin in the hydrated state and whose fluorescence changes dynamically–via a conjugated aptamer–depending on level of analyte. In a demonstration relevant to hypercalcemia, the hydrogel microneedle distinguished varying concentrations of calcium (within a range of 0 to 2 mM, which spans physiologically meaningful variations for hypoparathyroidism) within 10 minutes. In rats, a compact CMOS sensor measuring fluorescence from microneedles distinguished low hypercalcemic (1.7 mM) from high hypercalcemic (2.3 mM) ionized calcium levels as determined from reference blood measurements. Overall, this work demonstrates in vivo feasibility of a concept–which we call mPatch–for an optical hydrogel microneedle to measure small changes in levels of analytes in interstitial fluid, which does not rely on extraction of interstitial fluid out of the dermis. [ABSTRACT FROM AUTHOR]

The development of new sustainable materials has been growing in the last few years, especially polymers derived from renewable monomers to replace petroleum‐derived monomers in adhesive applications. In this context, copolymerization of β‐Farnesene (Far) with n‐butyl acrylate (BA) using different ratios of BA and Far (100/0, 80/20, and 50/50 wt/wt) is investigated by semi‐bath emulsion polymerization for use in pressure‐sensitive adhesives (PSA). Latexes with different BA and Far contents are obtained with good colloidal stability and a hydrodynamic diameter range of 120–140 nm. The copolymerization between Far and BA is confirmed by FT‐IR and DSC analyses. As the Far content increases, both overall conversion, elongation at break, and loop tack decrease. On the other hand, the lass transition temperature (Tg), gel content, and shear strength increase. The glass transition temperature of copolymers is higher than the theoretical Tg values and is dependent on the Far contents. The use of Far provides additional insights for the production of bio‐based PSAs by emulsion polymerization, which is characterized by an increase in both shear strength and cohesion. Among the proportions of BA/Far studied, the most promising results for application in PSA tapes are 80 wt% of BA and 20 wt% of Far. [ABSTRACT FROM AUTHOR]

Heat-resistant semi-aromatic poly (decamethylene terephthalamide) acid (PA10T) and a series of poly (decamethylene terephthalamide/decamethylene furanamide) (PA10T/10F) with a high content of bio-based carbon were synthesized by a cost-effective high-pressure solution polycondensation method. The chemical structures of the obtained samples were evaluated by Fourier infrared spectroscopy (FT-IR). Moreover, the effect of the addition of copolymer 2,5-furandicarboxylic acid (FDCA) and the copolymerization ratios of FDCA for PA10T on thermal performances, crystallization behaviors, and mechanical properties of PA10T and PA10T/10F were studied in detail. In addition, the results of DSC indicate that the melting points of PA10T/10F copolyamides can be adjusted appropriately by varying the feed ratios of FDCA, suggesting the improvement of processabilities. Besides, with increasing the copolymerization ratios of FDCA, the sizes of spherulites decreased gradually analyzed by POM. Furthermore, the results of XRD showed that the PA10T homopolymer and PA10T/10F copolyamides possess similar shapes around 2θ = 21°. In addition, compared with pure PA10T, the tensile strength, breaking elongation, bending strength, bending modulus, and izod impact strength all increased obviously when the feed ratio of FDCA and terephthalic acid (PTA) was 5:95. Therefore, the crystallization behaviors, processing performances, and mechanical characteristics of PA10T can be improved significantly by introducing FDCA, to improve the bio-based carbon content of PA10T and meet the increasing demand for environmentally friendly materials all over the world. [ABSTRACT FROM AUTHOR]

Biomass-based and biodegradable poly(l-lactide) (PLLA) is synthesized by ring-opening polymerization of l-lactide (LLA), for which tin(II) 2-ethylhexanoate is a major catalyst. However, the potential toxicity of tin can be a problem, especially in biomedical applications. In this study, we focused on iron, which is a non-toxic metal and an abundant resource. We investigated the ring-opening homo- and copolymerization of cyclic esters such as LLA and ε-caprolactone (CL) catalyzed by iron(III) triflate, Fe(OTf)3, which is commercially available and known as a Lewis acid. In the polymerization of LLA in toluene at 110 °C, Fe(OTf)3 showed relatively high activity and yielded PLLA with unimodal molecular weight distribution. The addition of 1,8-bis(dimethylamino)naphthalene (proton sponge: PS) to the Fe(OTf)3 catalyst system increased the yield and molecular weight of the resulting polymer. In contrast, the polymerization of CL by Fe(OTf)3 was decelerated by the presence of PS. The Fe(OTf)3 system was found to have an exceptionally high preference for CL over LLA in the copolymerization of LLA and CL, with the reactivity ratio of rLLA = 0.51 and rCL = 6.9. In contrast, the Fe(OTf)3–2PS system exhibited an LLA preference with rLLA = 15 and rCL = 0.22, indicating that the comonomer selectivity changed depending on the presence or absence of PS. While the LLA polymerization rate by the Fe(OTf)3 system showed a second-order dependence on the Fe(OTf)3 concentration, that of the Fe(OTf)3–PS system showed a first-order dependence on the Fe(OTf)3–PS concentration. [ABSTRACT FROM AUTHOR]

Pure organic films consisting of polypyrrole, polyaniline and a composite of polypyrrole and polyaniline electrodeposited in the ionic liquid EMIM‐TFSI onto mesoporous carbon electrodes are tested for their hydrogen evolution reaction capabilities. The use of these intrinsically conducting polymers is seen as a way of stepping away from expensive and rare metallic catalysts. Co‐polymerisation of polypyrrole and polyaniline in a 1 : 10 ratio in EMIM‐TFSI was found to be doped with the TFSI− anion and be much more active to the hydrogen evolution reaction when compared to pure polymers. Tafel analysis of the composite gave a value of 144 mV/dec indicating that the Volmer step is the rate limiting step. However, stability tests showed an improvement in the composite's overpoential performance for the hydrogen evolution reaction. [ABSTRACT FROM AUTHOR]

This theoretical study investigates the high molecular weight (Mw) production in copolymerization of ethylene and 1-octene using heteroatom-substituted constrained geometry catalysts (CGCs). The research explores the correlation between chain termination reactions and polymer molecular weight, revealing that the Gibbs free energy barrier of the chain termination reactions is positively linked to the molecular weight. Quantitative structure–property relationship models were constructed, indicating that molecular descriptors such as atom charge, orbital energy, and buried volume significantly influence the polymer molecular weight. [ABSTRACT FROM AUTHOR]

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We report herein the photoinduced electron/energy transfer–reversible addition‐fragmentation chain transfer (PET‐RAFT) polymerization of styrene‐maleic anhydride (SMAnh) using the photocatalyst, zinc tetraphenylporphirine, under a white cool LED light. PET‐RAFT is an easy and convenient polymerization method that does not require deoxygenation unlike other radical polymerizations. Various parameters, for example, the amount of styrene in the feed or the solvent, and their influence on the polymerization were studied. After hydrolysis of the anhydride moieties, the resulting styrene‐maleic acid (SMA) copolymers obtained by PET‐RAFT copolymerization were evaluated for their solubilization efficiency of three different membrane proteins, BmrA and AcrB, overexpressed in Escherichia coli, and A2AR, expressed in insect cells (Sf9). The different copolymers provided similar solubilization rates to the commercially available SMA; however, a highly improved migration behavior on sodium dodecyl‐sulfate polyacrylamide gel electrophoresis was observed which could, facilitate downstream analyses. Overall, we demonstrated that PET‐RAFT is a versatile oxygen tolerant polymerization technique to yield SMA, a suitable polymer for biochemical applications. [ABSTRACT FROM AUTHOR]

The reversible addition‐fragment chain transfer (RAFT) alternating copolymerization of 2‐hydroxyethyl vinyl ether (HEVE) and dimethyl maleate (DMM) is achieved with S‐(cyanomethyl) O‐ethyl carbonodithioate (CMX) as medaitor and 2,2′‐azobis(2‐methylpropionitrile) (AIBN) as radical initiator. The effects of monomer concentrations, comonomer feeding ratios, molar ratio of monomer to CMX and solvent on the copolymerization and copolymer structure are systematically investigated. The living feature of the HEVE and DMM copolymerization is demonstrated by the linear increasement of the molecular weights with the monomer conversions, and relatively narrow molecular weight distributions of the copolymers. With dimethyl carbonate as solvent, poly(HEVE‐alt‐DMM) with Mn = 5200 and Mw/Mn = 1.34 are synthesized at [HEVE]/[DMM]/[CMX]/[AIBN] = 100/100/3/1. The alternating structure of the copolymer is demonstrated by matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry (MALDI‐TOF MS) and proton nuclear magnetic resonance spectroscopy (1H NMR). The both α, ω‐end groups are mainly originated from the moiety of CMX. To further demonstrate the living feature of the alternating copolymerization, chain extension and block copolymerization are also carried out. With poly(HEVE‐alt‐DMM) as macro‐CTA (Mn = 5200, Mw/Mn = 1.34), the chain‐extension reaction has been successfully realized (Mn = 9600, Mw/Mn = 1.70), and the block copolymer with vinyl neonanoate as monomer also successfully synthesized (Mn = 9800, Mw/Mn = 1.42). [ABSTRACT FROM AUTHOR]

A marine coral exoskeletons inspired bicontinuous hydrogel (PAD-iP) was synthesized by in-situ copolymerization of acrylic acid (AA) and dimethylaminpropyl methacrylamide (DMAPMA) in a poly(3, 4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) skeleton. It balanced the high sensitivity (GF=1049) and a wide working range (600%) of hydrogel strain sensor. [Display omitted] • The hydrogel strikes a balance between high sensitivity and a wide sensing range (GF=1049, strain=500–600%). • The hydrogel has high electrical conductivity (2.3±0.1 S/m) and mechanical properties (elongation at break of 603%). • The hydrogel has self-adhesion property and it can precisely monitored pulses. • The hydrogel exhibits excellent anti-freezing property and cyclic stability. Conductive hydrogel strain sensors demonstrate extensive potential in artificial robotics, human–computer interaction, and health monitoring, owing to their excellent flexibility and biocompatibility. Wearable strain sensors for real-time monitoring of human activities require hydrogels with self-adhesion, desirable sensitivity, and wide working range. However, balancing the high sensitivity and a wide working range remains a challenge. Herein, a marine coral exoskeleton inspired bicontinuous hydrogel (PAD-iP) for strain sensor was synthesized by in-situ copolymerization of acrylic acid (AA) and dimethylaminpropyl methacrylamide (DMAPMA) in the presence of poly(3, 4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) skeleton, using glycerol as water-retaining agent. Benefiting from the bicontinuous structure composed of electron-transported conductive, tough PEDOT:PSS skeleton and the ion-transported, flexible poly(AA -co -DMAPMA) hydrogel matrix, the strain sensor based on PAD-iP hydrogel struck an optimal balance between ultrahigh sensitivity (gauge factor up to 1049) and a broad sensing range (strain of 0–600 %). The strain sensors could be adhered directly to skin to monitor full-range human activities, physiological activities and physical vibrational signals of the local environment. The strain sensor also exhibited robustness and stable sensing properties across a wide temperature range (−20 ∼ 40 ℃). This work offers a fresh inspiration for preparation of high-performance hydrogel strain sensors. [ABSTRACT FROM AUTHOR]

In recent years, polymerization‐induced self‐assembly (PISA) has emerged as a powerful method for the straightforward synthesis of polymer nanoparticles at high concentration. In this study, we describe for the first time the synthesis of poly(2‐oxazoline) nanoparticles by dispersion cationic ring‐opening polymerization‐induced self‐assembly (CROPISA) in n‐dodecane. Specifically, a n‐dodecane‐soluble aliphatic poly(2‐(3‐ethylheptyl)‐2‐oxazoline) (PEHOx) block was chain‐extended with poly(2‐phenyl‐2‐oxazoline) (PPhOx). While the PhOx monomer is soluble in n‐dodecane, its polymerization leads to n‐dodecane‐insoluble PPhOx, which leads to in situ self‐assembly of the formed PEHOx‐b‐PPhOx copolymers. The polymerization kinetics and micellization upon second block formation were studied, and diverse nanoparticle dispersions were prepared, featuring varying block lengths and polymer concentrations, leading to dispersions with distinctive morphologies and physical properties. Finally, we developed a single‐step protocol for the synthesis of polymer nanoparticles directly from monomers via gradient copolymerization CROPISA, which exploits the significantly greater reactivity of EHOx compared to that of PhOx during the statistical copolymerization of both monomers. Notably, this approach provides access to formulations with monomer compositions otherwise unattainable through the block copolymerization method. Given the synthetic versatility and application potential of poly(2‐oxazolines), the developed CROPISA method can pave the way for advanced nanomaterials with favorable properties as demonstrated by using the obtained nanoparticles for stabilization of Pickering emulsions. [ABSTRACT FROM AUTHOR]

Multi‐component copolymerized donors (MCDs) hold great promise for improving both the efficiency and mechanical robustness of flexible organic solar cells (f‐OSCs) owing to their facile molecular tunability and advantageous one‐pot copolymerization. However, despite the excellent crystallinity imparted by their highly conjugated polymer backbone, MCDs often struggle to retain photovoltaic performance under large external deformations, limiting their applicability in wearable devices. Herein, we developed a novel series of flexible linker‐sequential block MCDs (Fs‐MCDs), specifically PM6‐Cl0.8‐b‐D18‐Cl0.2‐BTB, PM6‐Cl0.8‐b‐D18‐Cl0.2‐BTH, and PM6‐Cl0.8‐b‐D18‐Cl0.2‐BTD, by precisely incorporating flexible functional groups into the conjugated polymer skeleton. This design strategy introduced highly effective tensile active sites, resulting in remarkable mechanical durability, with PM6‐Cl0.8‐b‐D18‐Cl0.2‐BTD achieving crack‐onset strain (COS) values of 49.88 % in pristine films and 31.29 % in blends. The nearly 50 % COS in pristine films represents one of the highest values reported for Fs‐MCD‐based OSCs, marking a significant milestone in advancing f‐OSC. Additionally, PM6‐Cl0.8‐b‐D18‐Cl0.2‐BTD demonstrated excellent photovoltaic performance, with efficiencies of 18.09 % in rigid binary and 19.05 % in ternary, as well as 16.63 % in flexible OSCs. It also showed impressive device stability in invert OSC (T80=9,078 h). This unique molecular design strategy provides a promising avenue for synergistically improving the photovoltaic performance, mechanical properties, and device stability of f‐OSCs. [ABSTRACT FROM AUTHOR]

Although seeded reversible addition‐fragmentation chain transfer (RAFT) polymerization is explored as a unique method for the preparation of block copolymer nanoparticles with diverse structures, the preparation of nonlinear polymer nanoparticles by seeded RAFT polymerization is rarely reported. Herein, linear block copolymer nanoparticles are first prepared by RAFT dispersion copolymerization of benzyl methacrylate (BzMA) and 2‐(2‐(n‐butyltrithiocarbonate)propionate)ethyl methacrylate (BTPEMA) with different [BzMA]/[BTPEMA] ratios, and employed as seeds for seeded RAFT polymerization of isobornyl acrylate (IBOA) to prepare graft copolymer nanoparticles with different numbers of PIBOA side chains. Comparing with linear triblock copolymers with the same chemical composition, the graft copolymers can promote the formation of higher‐order morphologies (e.g., vesicles) under seeded RAFT polymerization conditions. Effects of reaction parameters on the morphology of graft copolymer nanoparticles are investigated in detail, and two morphological phase diagrams are constructed. It is expected that this study will not only expand the scope of seeded RAFT polymerization but also offer new opportunities for the preparation of unique polymer nanoparticles. [ABSTRACT FROM AUTHOR]

Achieving efficient circularly polarized white organic light‐emitting diode (CP‐WOLED) remains a significant challenge. In this study, a proof‐of‐concept for realizing CP‐WOLED is proposed using an electroplex emission strategy between a chiral thermally activated delayed fluorescence (TADF) emitter and hole‐transporting material. A series of chiral polymers (R/S)‐E‐x (x = 0.02, 0.05, and 0.1) are designed and prepared via random copolymerization of a chiral chromophore and styrene moiety, which shows typical TADF character. The neat film of (R/S)‐E‐0.1 presents distinct chiroptical properties with a dissymmetry factor (|glum|) of 2.8 × 10−3. Notably, solution‐processable, single‐emitting‐layer CP‐WOLEDs are fabricated using these chiral polymers in combination with 1,1‐bis[(di‐4‐tolylamino)phenyl]cyclohexane (TAPC) as the emitter, achieving a record maximum external quantum efficiency of 15.1% and Commission Internationale de lʹeclairage coordinate of (0.36, 0.40). Importantly, these CP‐WOLEDs exhibit an impressive |gEL| value of 2.4 × 10−3. This research provides a straightforward and effective strategy for the realization of high‐performance CP‐WOLED. [ABSTRACT FROM AUTHOR]

One possible way to store the excess CO2 present in atmosphere is to use it as a reagent for the synthesis of commodities. In particular, CO2 and epoxides can be copolymerized to produce a large variety of polycarbonates which appear very promising in various application fields. Further, the addition of an appropriate transfer agent in the reaction mixture promotes the formation of telechelic polycarbonates which can be used where specific functional polymers are necessary. In this work, (hydroxyethyl) methacrylate and 2‐hydroxyethyl‐2‐bromoisobutyrate species are exploited as transfer agents in the copolymerization of CO2 and cyclohexene oxide, in the presence of a macrocyclic phenolate dimagnesium catalyst. The effect of the transfer agent concentration on the polycarbonate characteristics is evaluated. Finally, the obtained telechelic polycarbonates are used as macromonomers and macroinitiators in the synthesis of statistical and block copolymers. [ABSTRACT FROM AUTHOR]

ABSTRACT The removal of antibiotic residues from environmental media is a significant challenge in the field of chemistry. In this work, we presented a simple and efficient method for eliminating tetracycline hydrochloride (TC) and chloramphenicol (CAP) from water. Initially, 1,4‐dichlorobenzene and ferrocene were employed as starting materials for the synthesis of hypercrosslinked polymers (HFDs) via Friedel–Crafts alkylation facilitated by a cross‐linking agent. Subsequent to this, an efficient magnetic adsorbent material (MHFD) was developed by the in situ oxidation of the iron source incorporated within the polymer matrix of HFDs. The resulting MHFDs demonstrated an impressive maximum Brunauer–Emmett–Teller (BET)–specific surface area of 1190 m2/g and exhibited a peak saturation magnetization of 11.8 emu/g. This work investigated the effects of four factors on the adsorption performance of MHFD‐10, including contact time, solution pH, dosage of MHFD‐10, and initial antibiotic concentration. The results revealed a remarkable conformity of the adsorption kinetics with the pseudo‐second‐order model and the adsorption isotherms with the Langmuir model. Thermodynamic analysis revealed that the adsorption process is spontaneous and exothermic. Specifically, at a temperature of 20°C, MHFD‐10 achieved maximum adsorption capacities of 193.95 mg/g for CAP and 268.60 mg/g for TC. Furthermore, these materials exhibited exceptional reusability, maintaining high adsorption capacities even after undergoing five consecutive reuse cycles. [ABSTRACT FROM AUTHOR]

Dialkyl fumarate polymers possess unique structures and outstanding properties such as the ability to modify the crystallization behavior of nparaffins, high thermal stability, chain rigidity, biocompatibility, and the ability of molecules to aggregate into a nematic liquid crystal-like structure. Fumarate homopolymers and copolymers have been widely studied and used in numerous fields. Herein, we critically present the structure–performance relationship and applications of polymers containing fumarate units. First, the fundamentals of synthesis and structure are briefly discussed. Furthermore, the properties of alkyl fumarate polymers are carefully discussed, focusing on the structure–performance relationship for their use as pour point depressants. Moreover, other properties and prospective applications in the electrical, industrial, and bioengineering fields are described. Finally, a brief review and summary of prospective novel methods for fumarate polymer synthesis are provided. This review presents instructions for molecular design and novel concepts for the future development of alkyl fumarate polymers. [ABSTRACT FROM AUTHOR]

The control of the microstructures of polymer materials derived from diene‐based monomers is crucial, and various synthetic methods, including anionic, radical, and coordination polymerization reactions, have been extensively explored. Here, we demonstrated the coordination polymerization of 2‐phenyl[3]dendralenes (P3D) as a diene monomer. The polymerization process using monocyclopentadienyltitanium trichloride (CpTiCl3) as a catalyst and modified methylaluminoxane (MMAO) as a cocatalyst (CpTiCl3/MMAO) yielded polymers with an exclusive 4,6‐structure that is distinct from those produced by anionic polymerization. Furthermore, the copolymerization of P3D with isoprene and styrene proceeded randomly. [ABSTRACT FROM AUTHOR]

The copolymerization of two or more monomers produces polymeric materials with unique properties that cannot be achieved with homopolymers. However, precise control over the polymer sequence remains challenging because the sequence is determined by the inherent reactivity of comonomers. Therefore, only limited methods using modified monomers or supramolecular interactions are reported. In this study, the sequence control of acrylate‐styrene copolymerization using multinuclear zinc complexes is reported. The copolymerization of the zinc acrylate complex with a polymeric sheet‐like structure and styrene in benzene affords a copolymer with a higher content of acrylate triad than calculated for the statistical random model, whereas tetranuclear zinc acrylate (TZA) affords a copolymer with fewer adjacent acrylate sequences. The copolymer with a higher content of acrylate triad exhibits a lower glass transition temperature because of the higher mobility of the longer polystyrene segments. These results highlight the promise of multinuclear zinc acrylate complexes as monomers for sequence‐controlled copolymerization. [ABSTRACT FROM AUTHOR]

Copolymerization stands as a versatile and potent method for tailoring polymer properties by adjusting structural unit composition and sequence distribution. However, achieving sequence‐controlled copolymerization in a one‐step and one‐pot process remains challenging. This study introduces a solvent‐dependent sequence‐controlled copolymerization strategy to produce block and statistical copolyesters from 4‐phenyl‐2‐oxabicyclo[2.1.1]hexan‐3‐one (4Ph‐BL) and ϵ‐caprolactone (ϵ‐CL). The distinct kinetics of the two monomers enable the facile synthesis of diblock and triblock copolyesters, PCL‐b‐P(4Ph‐BL) and P(4Ph‐BL)‐b‐PCL‐b‐P(4Ph‐BL), in non‐coordinating solvents, such as dichloromethane and toluene. Conversely, coordinating solvents like tetrahydrofuran, 2‐methyltetrahydrofuran, 2,5‐dimethyltetrahydrofuran, 1,4‐dioxane, and 1,2‐dimethoxyethane facilitate frequent transesterifications, yielding statistical copolyesters P[CL‐stat‐(4Ph‐BL)] with varying ratios of heterosequences. Density functional theory (DFT) calculations confirmed that coordinating solvents stabilize the transition state for transesterification, thereby validating their role in triggering this process. By varying the microstructures and compositions, the resultant copolyesters display tunable thermal and mechanical properties, evolving from robust plastics with an ultimate tensile strength of up to 46.3±3.1 MPa to tough elastomers with >99.3 % elastic recovery. All the copolyesters exhibit remarkable thermal stability (Td,5%=376 °C) and maintain desirable chemical circularity (>92 %), supporting a closed‐loop life cycle for sustainable material economy. [ABSTRACT FROM AUTHOR]

By virtue of the high reliability of click chemistry, polymers with clickable groups provide a useful platform for the rapid synthesis of polymer materials with diverse functionalities and architectures. However, the polymerization of clickable vinyl monomers with a concurrent regulation on tacticity remains underdeveloped. Herein, we report the successful development of a stereoselective cationic copolymerization of C−C triple bond‐containing vinyl ethers with simple alkyl vinyl ethers by employing confined Brønsted acid as catalyst, which allows for the synthesis of alkyne‐functionalized vinyl ether copolymers with high isotacticity (up to 90 % m), controlled molecular weight, and variable content of C−C triple bonds. Further transformation of the pendant clickable alkyne groups via thiol‐yne click reactions and copper(I)‐catalyzed alkyne‐azide cycloaddition reaction enables a modular access to isotactic polymers with various functional groups. [ABSTRACT FROM AUTHOR]

Polythioesters (PTEs) are emerging sustainable polymers for their degradability and recyclability. However, low polymerizability of monomers and extensive side reactions often hampered the polymerization process. Moreover, copolymers containing both thioester and other types of functional groups in the backbone are highly desirable but rarely accomplished owing to several synthetic challenges. Here, we report the ring‐opening cascade polymerization (ROCAP) of N‐(2‐(acetylthio)ethyl)‐glycine N‐carboxyanhydrides (TE‐NCA) to afford recyclable PTEs and unprecedented poly(thioester‐co‐peptoid)s (P(TE‐co‐PP)s) in a controlled manner. By developing appropriated carboxylic acid‐tertiary amine dual catalysts, intramolecular S‐to‐N acyl shift is coupled into the ROCAP process of TE‐NCA to yield products with dispersity below 1.10, molecular weight (Mn) up to 84.5 kDa, and precisely controlled ratio of thioester to peptoids. Random copolymerization of sarcosine NCA (Sar‐NCA) and TE‐NCA gives thioester‐embedded polysarcosine with facile backbone degradation while maintaining the water solubility. This work represents a paradigm shift for the ROP of NCAs, enriches the realm of cascade polymerizations, and provides a powerful synthetic approach to functional PTEs and P(TE‐co‐PP)s that are otherwise difficult or impossible to make. [ABSTRACT FROM AUTHOR]

Smart persistent organic room‐temperature phosphorescence (RTP) materials, capable of responding to microenvironmental changes, are critically important in various optoelectronic applications. However, conventional persistent RTP materials usually have not stretchability and flexibility, limiting some practical applications. This study reports a facile and one‐pot photo‐initiated copolymerization method to prepare photoactivated persistent RTP polymers with multicolored afterglow, excellent stretchability, self‐healable and recyclable properties. Impressively, the polymers can be stretched up to 500% without significant loss in RTP intensity and lifetime, and they possess a self‐healing ability with a healing efficiency of 69.6%. Utilizing these photoactivated and stretchable persistent RTP polymers, dual encryption can be achieved under UV irradiation and stretching conditions, thereby enhancing the security levels of the stored confidential information. Overall, this study represents the first example of self‐healable and recyclable stimuli‐responsive RTP materials, demonstrating their bright future for the flexible and wearable optoelectronics. [ABSTRACT FROM AUTHOR]

In this study, electrochemical copolymerization of 6,7-diphenyl-4,9-di(selenophen-2-yl)-[1,2,5]thiadiazolo[3,4-g]quinoxaline and 3,3'-didecyl-3,4-propylenedioxythiophene is carried out to obtain a copolymer namely poly(6,7-diphenyl-4,9-di(selenophen-2-yl)-[1,2,5]thiadiazolo[3,4-g]quinoxaline-co-3,3'-didecyl-3,4-propylenedioxythiophene). Two distinct copolymers, PC1 and PC2, were produced as a result of the utilization of two different feed ratios. Copolymers were examined electrochemically and spectroelectrochemically after the copolymerization procedure. This study's major goal is to combine the exceptional characteristics of homopolymers P1 and P2 (P1 has a low band gap but is not soluble, and P2 is soluble and has a larger band gap) into a single copolymeric material. [ABSTRACT FROM AUTHOR]

Often the errors in the measurement of copolymerizations are not accurately determined or included in the calculation of reactivity ratios. Some knowledge of the errors in the initial monomer ratio, conversion, and copolymer composition is however essential to obtain reliable (unbiased) reactivity ratios with a realistic uncertainty. It is shown that the errors serve a trifold purpose; they can serve as weighing factors in the fit, they can be compared with the fit residues to decide whether the chosen model is adequate for the data and they can be used to construct a realistic joint confidence interval for the reactivity ratios. The best approach is to have an estimate of the individual errors in the copolymer composition, either from a thorough error propagation exercise or from replicate measurements. With these errors, the χ2‐joint confidence intervals can then be constructed which gives a realistic estimate of the errors in the reactivity ratios. Utilizing the Errors in Variables Method (EVM) is correct and useful, but only if the individual errors in all the variables in each experiment are more or less known. [ABSTRACT FROM AUTHOR]

This report describes the grafting of methacrylic acid (MAA) onto Garcinia kola pods (GKP) and its utilization in the sequestration of methylene blue (MB) and malachite green (MG) from aqueous medium. The synthesis method involved the use of a simple reactor containing N2 gas inlet and outlet. Free radicals were initiated by ammonium persulfate. With 2 g MAA, 33% grafting yield was obtained after 2 h, at 60 ℃, and with 0.01 mol L−1 initiator. Material characterization was done by FTIR, SEM, XRD, and TGA, with all confirming the success of the grafting process. During the sorption process, solution pH, contact time, initial dye concentration, and temperature were varied. Rise in each of these parameters favored the sorption process up to their optimum states. With 0.1 g GKP-g-MAA, about 96% MB and 93% MG were removed. The adsorption process followed the pseudo-second-order kinetic model, while isothermal data fitted the Redlich-Peterson model best with R2 values of 0.9994 and 0.9991 for the sorption of MB and MG, respectively. This was followed by Langmuir, indicating a homogeneous system and a reaction-controlled process. Thermodynamic data portrayed the sorption process as being feasible, spontaneous, endothermic, and characterized with increased disorderliness. Elovich model suggested the contribution of chemisorption; mean free energies, E ˂ 8 k Jmol−1, indicated physisorption, while enthalpy change, ΔH°, depicted physisorption and the contribution of weak chemisorption in the sorption of MB and MG, respectively. Regeneration of the material was efficient, while high % dye removal showed a great adsorbent potential in the copolymer. [ABSTRACT FROM AUTHOR]

Long‐chain bio‐based polyamide has shown promising development prospects due to its excellent properties and green renewable characteristics; however, synthesizing inherently flame‐retardant long‐chain bio‐based polyamide remains a big challenge due to the lack of effective knowledge of the key polymerization process. Herein, intrinsicly flame‐retardant long‐chain bio‐based polyamide 512 (PA512) was synthesized in the presence of a reactive flame retardant with high thermal stability and good water solubility. The reaction conditions and existing problems in each stage of the copolymerization system have been clarified and optimized. By utilizing a two‐step pre‐polymerization approach, a series of intrinsicly flame‐retardant PA512 (FRPA512) with large molecular weight, high phosphorus element content and good mechanical properties were obtained. More importantly, the prepared FRPA512 with 5 wt % flame retardant loading exhibited good flame retardancy, showing a limiting oxygen index (LOI) of 28.1 % and a vertical burning rating of V‐0. This study provides a feasible solution to the common problem in the synthesis of flame‐retardant polyamides, while also offering new insights for future modification of polyamide copolymerization. [ABSTRACT FROM AUTHOR]

A new design policy to synthesize nanogel molecules having desired dimensions under unperturbed state is proposed. Miniemulsion copolymerization of vinyl and divinyl monomers, both conventional free‐radical polymerization and ideal living polymerization, is used to illustrate the method. For the network formation dynamics, the newly proposed model that takes into account the size and structure dependence of cross‐linking/cyclization reactions is employed. The master curve relationship that indicates the maximum average dimensions for randomly cross‐linked networks is used as a guideline and the network dimension is controlled by the magnitude of network maturity index NMI, which is the average number of cycle rank per primary chain. By appropriately sizing the NMI, it is possible to synthesize network polymers with dimensions equal to or greater than the maximum dimensions achievable with a homogeneous, randomly cross‐linked network polymer of the same cycle rank and molecular weight. The current strategy of designing and controlling 3D size is applicable regardless of the reaction mechanism of network formation and will also be applied to the synthesis of macro‐gels. [ABSTRACT FROM AUTHOR]

Reduction of non‐radiative energy loss (ΔEnr) in all‐polymer solar cells (all‐PSCs) is crucially important for achieving high power conversion efficiencies (PCEs). Herein, an efficient strategy is reported to reduce the ΔEnr by introducing luminescent unit into the backbone of polymer acceptors. Compared to the device based on PM6:PYDT, the ΔEnr in all‐PSC based on PM6:PYDT‐CzP‐9 has decreased from 0.188 to 0.183 eV. This reduction is attributed to the improvement in electroluminescence external quantum efficiency (EQEEL). The PM6:PYDT‐CzP‐9 device has shown an 18% increase in EQEEL compared to the device based on PM6:PYDT (8.4 × 10−4 vs 7.1 × 10−4), demonstrating that the incorporation of luminescent unit in polymer acceptors is highly effective in enhancing the electroluminescence performance of all‐PSCs. As a result, the PM6:PYDT‐CzP‐9 device yielded a high VOC of 0.967 V, without the sacrifice of short‐circuit current density (23.42 mA cm−2) and fill factor (77.5%), leading to a high PCE of 17.55%. [ABSTRACT FROM AUTHOR]