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The bicyclic amidinium iodide effectively catalyzed the reaction of carbon dioxide and the epoxy‐containing oxetane under ordinary pressure and mild conditions with high chemoselectivity to give the corresponding oxetane monomer containing five‐membered cyclic carbonate quantitatively. The cationic ring‐opening polymerization of the obtained monomer by boron trifluoride diethyl ether proceeded to give linear polyoxetane bearing five‐membered cyclic carbonate pendant group in high yield. The molecular weight of the polyoxetane was higher than that of polyepoxide obtained by the cationic ring‐opening polymerization of epoxide monomer containing five‐membered cyclic carbonate. The cyclic carbonate functional crosslinked polyoxetanes were also synthesized by the cationic ring‐opening copolymerization of cyclic carbonate having oxetane and commercially available bisoxetane monomers. Analyses of the resulting polyoxetanes were performed by proton nuclear magnetic resonance, size exclusion chromatography, thermogravimetric analysis, and differential scanning calorimetry. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2606–2615 [ABSTRACT FROM AUTHOR]

The anionic ring‐opening polymerization of a five‐membered cyclic urethane, 2‐amino‐4,6‐O‐benzylidene‐2‐N,3‐O‐carbonyl‐2‐deoxy‐α,d‐glucopyranoside (MBUG), which was prepared from naturally abundant d‐glucosamine, was examined. Potassium tert‐butoxide (t‐BuOK) was the most effective initiator among the evaluated bases and produced polyurethane with the Mn of 7800 without any elimination of CO2. The equimolar reaction of MBUG and t‐BuOK in the presence of CH3I produced N‐methylated MBUG and suggested that the initiation reaction involves proton abstraction from the NH group. This N‐methylated compound did not undergo the polymerization. Therefore, the mechanism of propagation in the ROP of MBUG should involve the proton abstraction and nucleophilic substitution of the resulting amide anion. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2491–2497 [ABSTRACT FROM AUTHOR]

Graft copolymers show microphase separated structure as seen in block copolymers and have lower intrinsic viscosity than block copolymers because of a branching structure. Therefore, considering molding processability, especially for polymers containing rigid segments, graft copolymers are useful architectures. In this work, graft copolymers containing rigid poly(diisopropyl fumarate) (PDiPF) branches were synthesized by full free‐radical polymerization process. First, synthesis of PDiPF macromonomers by addition‐fragmentation chain transfer (AFCT) was investigated. 2,2‐Dimethyl‐4‐methylene‐pentanedioic acid dimethyl ester was found to be an efficient AFCT agent for diisopropyl fumarate (DiPF) polymerization because of the suppression of undesired primary radical termination, which significantly took place when common AFCT agent, methyl 2‐(bromomethyl)acrylate, was used. Copolymerization of PDiPF macromonomer with ethyl acrylate accomplished the generation of the graft copolymer having flexible poly(ethyl acrylate) backbone and rigid PDiPF branches. The graft copolymer showed a microphase separated structure, high transparency, and characteristic thermal properties to PDiPF and poly(ethyl acrylate). © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2474–2480 [ABSTRACT FROM AUTHOR]

The cationic polymerization of n‐hexyloxyallene was investigated by using halogen‐bonding organocatalysts (Cat A–Cat D). Although the neutral catalyst Cat C showed a poor polymerization activity, iodine‐carrying bidentate cationic catalyst Cat A brought about the smooth polymerization giving rise to a polymer with Mn of 2710 under [Cat A]:[IBVE‐HCl]:[monomer] = 10:10:500 in mM concentrations. Judging from the color change of polymerization system and electrospray ionization mass spectra of recovered catalyst, the decomposition of organocatalyst was suggested. When α‐bromodiphenylmethane was used as an initiator, the relatively controlled polymerization proceeded at the low monomer conversion likely due to the weak halogen‐bonding interaction of Cat A with the bromide anion. On the other hand, bromine‐carrying bidentate catalyst Cat D gave low‐molecular‐weight polymers (Mn < 1550) to be less suitable for polymerization. From the 1H‐NMR spectrum, it was found that the 1,2‐polymerization unit and 2,3‐polymerization unit are included in 75:25. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2436–2441 [ABSTRACT FROM AUTHOR]

Anionic hydrogen‐transfer homopolymerization of N‐isopropylacrylamide (NIPAAm) was carried out using t‐BuOK as an initiator in DMF under microwave irradiation. After 100 W of microwave was irradiated to the reaction mixture at 140°C for 6 h in the temperature control mode, corresponding polymer was obtained in 10% yield. In the case of conventional oil bath heating, by contrast, corresponding polymer was not obtained in similar anionic polymerization conditions. With 100 W and 2.45 GHz of microwave irradiation, formation of the polymer was obtained. Microwave‐assisted anionic hydrogen‐transfer copolymerization of NIPPAm and acrylamide (AAm) led to the formation of thermo‐sensitive copolymers whose thermo‐sensitivity was controlled by the NIPAAm/AAm unit ratio. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2415–2419 [ABSTRACT FROM AUTHOR]

Preparation of functional domains with a spacing of 10 nm is a benchmark set to fabricate next‐generation electronic devices. Organic–inorganic block copolymers form well‐ordered microphase separations with very small domain sizes. The design and preparation of a novel block copolymer consisting of syndiotactic polymethyl methacrylate (st‐PMMA) and polyhedral oligomeric silsesquioxane (POSS)‐functionalized polymethacrylate, designated as st‐PMMA‐b‐PMAPOSS, which can recognize functional molecules, are reported. The st‐PMMA segments form a helical structure and encapsulate C60 in the helical nanocavity, leading to the formation of an inclusion complex. Although the ordering of the domains is not high, C60 domains that are in a quasi‐equilibrium state, with about 10‐nm domain spacings, are generated using st‐PMMA‐b‐PMAPOSS that can recognize functional molecules. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2181–2189 [ABSTRACT FROM AUTHOR]

This article describes the syntheses of various functional star‐shaped polymers via monomer‐selective living cationic polymerization of a vinyl ether (VE) and a divinyl compound with alkoxystyrene moieties by a one‐shot method. An aqueous solution of the resulting star‐shaped polymers with oxyethylene pendants exhibits thermally induced phase separation behavior. To achieve domino synthesis from various monomers, we investigated the optimum reactivity difference using a functional VE and a monofunctional alkoxystyrene. Moreover, the one‐shot copolymerization of a bifunctional VE and an alkoxystyrene is also conducted to yield a star‐shaped polymer via the core‐first method. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2166–2174 [ABSTRACT FROM AUTHOR]

The kinetics of isothermal anionic homopolymerization of ß–myrcene (MYR) and 4–methylstyrene (4MS) in cyclohexane, initiated by n–butyllithium was studied at different temperatures (55, 63, and 71 ° C). The kinetic information obtained from the homopolymerizations was used to estimate the parameters of the Eyring equation, ΔH‡= 84080 J/mol and ΔS‡= −21.9 J/mol·K for the MYR, and ΔH‡= 51250 J/mol and ΔS‡= −116.8 J/mol·K for the 4MS, to calculate the apparent propagation coefficients kpapp as a function of temperature. Finally, the parameters obtained for the Eyring equation were validated by applying them in a mathematical model representing the kinetics of nonisothermal (quasi‐adiabatic) polymerization experiments of MYR and 4MS. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2157–2165 [ABSTRACT FROM AUTHOR]

In this article, new compounds based on the carbazole scaffold (DMs = DM1 and DM2, constituted by a carbazole unit connected on positions 3 and 6 to a two 4,4′‐dimethoxydiphenylamine groups and differing by the substituent present on the nitrogen heteroatom of the carbazole core) were synthesized and proposed as high‐performance visible light photoinitiators/photosensitizers for both the free‐radical polymerization of methacrylates and the cationic polymerization of epoxides upon visible light exposure using LED@405 nm. Remarkably, DM2 leads to higher final conversions than DM1. In order to study the photophysical and photochemical properties of the carbazole derivatives, different parameters were taken into account such as the light absorption, the steady‐state photolysis, and the fluorescence spectroscopy. Using different techniques such as fluorescence quenching, redox behavior, and cyclic voltammetry, we are able to discuss the photosensitization/photoinitiation reactions providing a full coherent picture of the involved chemical mechanisms. The photosensitization of the carbazole derivatives occurred predominantly via singlet excited states at the rate of the diffusion limit. Upon exposure to laser diode at 405 nm, DMs show high performance in initiating systems for 3D resins. Remarkably, DM2 can also be used in photocomposite synthesis using light‐emitting diode conveyor. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2081–2092 [ABSTRACT FROM AUTHOR]

Hyperbranched poly(2‐ethyl‐2‐oxazoline) was synthesized by a combination of cationic ring‐opening polymerization and the oxidation of thiol to disulfide groups. A three‐arm star poly(2‐ethyl‐2‐oxazoline) (PEtOx) was first synthesized using 1,3,5‐tris(bromomethyl) benzene as an initiator. The star PEtOx was end‐capped with potassium ethyl xanthate. Similarly, a linear PEtOx was synthesized and end‐capped with potassium ethyl xanthate using benzyl bromide as an initiator. Hyperbranched PEtOx was then obtained by in situ cleaving and subsequent oxidation of the star PEtOx and linear PEtOx mixture with n‐butylamine as both a cleaving agent and a base in tetrahydrofuran. The linear PEtOx was used to prevent the formation of gel. The hyperbranched PEtOx can be cleaved with dithiothreitol to trithiol and monothiol polymer. The hyperbranched PEtOx shows no remaining thiols using Ellman's assay. The resulting hyperbranched PEtOx was hydrolyzed to a novel hyperbranched polyethyleneimine with degradable disulfide linkages. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2030–2037 [ABSTRACT FROM AUTHOR]

The catalyst structure–property relationships of the phenoxyimine complexes in controlled cationic polymerization of vinyl ethers were investigated based on the Hammett correlation. The correlation analyses of a series of experiments using the phenoxyimine ligands/TiCl4 initiating systems indicated that the substituents on the N‐aryl phenoxyimine ligands affected the polymerization rate and stereoselectivity. Importantly, a linear correlation was observed between the Hammett substituent constants and the polymerization rates, which indicates that the Lewis acidity of the complex is affected by the electron‐withdrawing and ‐donating effects of the substituents. The tacticity of product polymers correlated to the Hammett substituent constants. Unlike the relationship with the polymerization rates, the σ– values, which account for the enhanced resonance effects, were more appropriate for the relationship with the tacticity than the normal σ values. In contrast, the polymerization behavior using o‐substituted ligands exhibited a trend different from those using p‐ or m‐substituted ligands. The structural change, which was caused by the rotation of the CN bonding, most likely triggered the acceleration effect in the case of the o‐substituents. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2021–2029 [ABSTRACT FROM AUTHOR]

Keywords: alkyl iodide; aqueous polymerization; degenerative transfer; iodide salt; PAA; reverse iodine transfer polymerization In contrast to conventional RITP, we report a one-step, aqueous polymerization of AA based on readily available and inexpensive iodide salts, oxidants, and common thermal initiators to generate the alkyl iodide chain-transfer agent in situ [see Fig. A set of polymerizations employing varied [AA]/[NaI] ratios ranging from 25 to 150 were carried out, and in all cases, the polymerizations afforded PAA with high monomer conversion (>90%) within 15 min (Fig. Alkyl iodide, aqueous polymerization, degenerative transfer, iodide salt, PAA, reverse iodine transfer polymerization. [Extracted from the article]

A templating method is developed to produce porous nanocrystalline anatase materials for negative electrodes in lithium‐ion batteries (LIBs). Amphiphilic diblock copolymers are used to generate template films with phase‐separated internal structure. Subsequent swelling with acidified titanium(IV) bis(ammonium lactato) dihydroxide (TALH) solution yielded structured hybrid films. Upon heating, the formation of TiO2 nanocrystals is induced, resulting in a three‐dimensional mesoporous structure directed by the bulk morphology of the polymer template. In comparison to commercial nanosized anatase, the structured anatase shows significant performance improvements in lithium‐ion coin cell batteries in terms of capacity, stability, and rate capability. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1890–1896 [ABSTRACT FROM AUTHOR]

Biodegradability and biocompatibility are two crucial prerequisites for a promising therapeutic vehicle. Herein, a novel biocompatible copolymer has been synthesized using glycogen and polylactide (PLA). Glycogen, a naturally occurring biopolymer has been functionalized by methacrylation. On the other hand, lactide has been polymerized through ring opening polymerization (ROP), initiated by hydroxyethyl methacrylate (HEMA) and catalyzed by tin (II) 2‐ethyl hexanoate. Finally, the synthesized two substrates (i.e., glycogen methacrylate and PLA‐HEMA) are covalently connected by free‐radical polymerization, initiated by AIBN. The structure of the developed copolymer has been confirmed using 1H and 13C NMR spectral analyses. The gel characteristics have been evaluated by rheological studies, while the morphological assessment has been investigated by FESEM analysis. In vitro cytocompatibility study reveals that the hydrogel (Gly‐co‐PLA) is biocompatible. The in vitro and in vivo release studies demonstrate the excellent pH‐sensitive control release profile of dual drugs: ornidazole and ofloxacin. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1697–1703 [ABSTRACT FROM AUTHOR]

Oligo(spiroorthocarbonate)s 1, which were synthesized by the polycondensation of pentaerythritol derivatives with tetraethylorthocarbonate, were employed as comonomers in the cationic polymerization of epoxide initiated by sulfonium salt. In the copolymerization, the spiroorthocarbonate moiety of 1 underwent double ring‐opening reaction, leading to the efficient diminution of the volume shrinkage upon the copolymerization. Thermal properties of the resulting networked polymers were evaluated by TGA. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1564–1568 [ABSTRACT FROM AUTHOR]

Silyl glyoxylates are proposed here as high‐performance photoinitiators (PIs) for the hybrid polymerization of cationic and radical monomers. Recently, silyl glyoxylates were reported as a new class of high‐performance Type I photoinitiators for free radical polymerization under air upon exposure to different near‐UV and blue LEDs. In this article, we report this new class of photoinitiators to initiate cationic polymerization in combination with an iodonium salt. This system can also be used to initiate simultaneously free radical and cationic polymerizations, for example, for the free radical/cationic hybrid polymerization and for the synthesis of interpenetrating polymer networks. The system silyl glyoxylate/iodonium exhibits excellent polymerization performances and exceptional bleaching properties compared to other well established photoinitiators (e.g., camphorquinone). Furthermore, a hybrid monomer is also introduced in this article (2‐vinyloxyethoxyethyl methacrylate [VEEM]) leading to a huge improvement of the mechanical properties of the final polymer through hybrid polymerization. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1420–1429 [ABSTRACT FROM AUTHOR]

Various PS‐based graft copolymers including polystyrene‐graft‐poly(methyl methacrylate) and poly(styrene‐graft‐poly(ethylene glycol) methacrylate) are prepared via subsequent visible light radical photopolymerization and iniferter processes. Thus, poly(styrene‐co‐4‐chloromethylstyrene) P(S‐co‐VBC) is synthesized by light induced free‐radical polymerization. Then, chloride moieties are substituted with triphenylmethyl (trityl) groups to give trityl‐substituted PS (PS‐trityl) under visible light irradiation using dimanganese decacarbonyl (Mn2(CO)10) photochemistry. Side chains are then grafted from PS‐trityl backbone via iniferter process to give desired graft copolymers in a controlled manner. The precursor intermediates and the final graft copolymers are analyzed by 1H NMR, FT‐IR, and GPC measurements. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1344–1348 [ABSTRACT FROM AUTHOR]

Highlights from the article: A visible light-induced metal-free atom transfer radical polymerization strategy for the efficient synthesis of polyacrylonitrile (PAN) with predictable molecular weights and low dispersities has been developed. While no absorbance of the phenothiazines at visible region can be observed, high energy ultraviolet (UV) light is necessary in this process, leaving a space for improvement of using the abundant and "green" visible light to achieve the controlled polymerization of AN. (a) Plot of monomer conversion versus time demonstrating the dependency of light on the polymerization: light on (blue regions) and light off (white regions). The results of polymerization kinetics, light on/off switching experiments and chain extension polymerizations together proved the living nature of the visible light catalytic system.

Light‐responsive crosslinked structures were prepared by a straightforward quaternization strategy using chloride functional polystyrene copolymers and commercially available Michler's ketone with varying feed ratios. Resulting organogels demonstrated excellent solvent absorption and their swelling characteristics were altered by UV‐light irradiation. According to scanning electron microscope images, UV‐illuminated samples showed an obvious photodecomposition, which enhanced their solvent uptake capacity with increase of UV exposure. Additionally, release behavior of eosin Y as a model compound was determined by UV–vis and fluorescence spectrometers. Achieved photoactive gels were also employed as the reusable heterogeneous initiators for photoinduced free‐radical polymerization of methyl methacrylate. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1275–1282 [ABSTRACT FROM AUTHOR]

We proposed a thought of active capture of particles by improving the interaction force between fibers and particles. Nanoparticle‐enhanced tubular nanofibers (Ag‐SPNTs) were prepared by template‐free cationic polymerization followed by surface modification. Ag‐SPNTs have coarse surface and bamboo‐like tubular structure with a diameter of approximately 80‐150 nm. Ag nanoparticles were embedded on the nanofibers surface, and the content of Ag nanoparticles in the nanofibers could be tuned by changing the concentration of [Ag(NH3)2]+ in the preparation process. f‐d curve measured by AFM showed that increasing the content of Ag nanoparticles in the nanofibers resulted in the enhanced interaction force between the nanofiber surface and particles. Particle matter capture test showed that the number of captured microscaled/naonoscaled particles on the fiber surface increased obviously for the nanoparticle‐enhanced tubular nanofibers (Ag‐SPNTs) compared to the nanofibers without nanoparticle (SPNTs), probably due to the increased interaction force and adhesion energy between fiber surface and particles. Filtration property test showed that the Ag‐SPNTs fiber films had a better filtration performance with a higher filter efficiency and QF value than that of SPNTs. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 [ABSTRACT FROM AUTHOR]

Recently, we reported that dimethylsilanolate‐initiated anionic ring opening polymerization of dimethylsiloxy‐ and diphenylsiloxy‐cyclic siloxanes results in polymer chain branching by dimethylsilanolate‐induced cleavage of only one Si‐CAr side bond in diphenylsiloxy repeat units, leading to formation of "Ph‐T‐branches", and not extending to the cleavage of the second phenyl group. We attributed this behavior to electronic structures of the participating dimethylsiloxy‐, diphenylsiloxy and Ph‐T‐branch silicons and predicted that copolymers prepared by this synthetic route from dimethylsiloxy‐ and methylphenylsiloxy‐cyclics should not undergo branching at all but should have perfect linear chain configuration. Here, we describe results of a study of two such dimethylsilanolate‐initiated ring opening polymerizations of dimethylsiloxy‐ and methyphenylsiloxy‐cyclic tetramers and characterization of the resulting polymers by SEC‐MALS‐VIS, Mark‐Houwink‐Sakurada relationship and 29Si NMR. The results obtained clearly confirmed our prediction of expected linearity of these polymer chains and also indicated that the resulting polymers were completely amorphous even at as low methylphenylsiloxy‐content as 3.9 mol %. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1122–1129 [ABSTRACT FROM AUTHOR]

In order to break through the bottleneck of anionic polymerization, polar monomers such as methyl methacrylate (MMA), ethyl methacrylate, butyl methacrylate, and hexyl methacrylate are subjected to anionic polymerization at room temperature in tetrahydrofuran (THF) using potassium tert‐butoxide (t‐BuOK) as the initiator. The polymerization of alkyl methacrylates is studied by multidetector gel permeation chromatography, proton nuclear magnetic resonance (1H‐NMR) and 13C‐NMR spectroscopy, and dynamic laser light scattering. It is found that t‐BuOK can initiate the living anionic polymerization of polar alkyl methacrylate, and the polymerization conversion almost reaches up to 100%. t‐BuOK exists into two kinds of agglomerates, whose hydrodynamic volumes are 10 and 80 nm, respectively. t‐BuOK in THF is similar to emulsion and has a critical active species concentration of about 0.0265 mol L−1 and does not depend on how much t‐BuOK is added. After the initiation of the polymerization, the large agglomerates of a loose and less regular structure that have occupied the main part of t‐BuOK are greatly reduced, but they do not continue to decrease until they disappear according to the equilibrium theory. Similarly, the active chain after initiation also will not aggregate again. Furthermore, t‐BuOK also has an active species with smaller average vibration size between cation and anion pairs, which can only initiate the polymerization of MMA with rather slow rate but cannot initiate other alkyl methacrylates. At last, because t‐BuOK can make the dormant species caused by side reactions to be revived, the anionic polymerization of MMA could obtain a high yield. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1130–1139 [ABSTRACT FROM AUTHOR]

We investigated the cationic polymerization of vinyl ethers using metal complex catalysts with salen and salphen ligands. Metal complexes were generated in situ from the reaction of a ligand and a metal chloride. The choice of a ligand and a central metal was crucial for tuning the catalyst function such as catalytic activity and controllability of the polymerization. Among metal chlorides employed, ZrCl4 was the most efficient for controlled polymerization. Cationic polymerization of isobutyl vinyl ether (IBVE) proceeded using the salen and salphen‐type ligand/ZrCl4 initiating systems, yielding polymers with predetermined molecular weights and narrow molecular weight distributions. Importantly, the structural effects of the complex catalysts were responsible for the polymerization behavior. For example, the polymerization using the salen‐type ligand/ZrCl4 system was much slower than that using the salphen‐type ligand/ZrCl4 system. In addition, the polymerization of IBVE using the salen‐type ligand/FeCl3 system proceeded in a controlled manner, which was in contrast to uncontrolled polymerization using the salphen‐type ligand/FeCl3 system. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 989–996 This research investigates the structural effect of ligands on the catalytic property and scope of metal chlorides available for the in situ complexation method. The in situ complexation method has a dual role: the readily prepared metal complex is used as a catalyst, and in situ generated hydrogen chloride is used as an initiator. Salen‐ and Salphen‐type ligands/metal chlorides systems exhibit the different catalyst functions, such as catalytic activity and controllability of the polymerization. [ABSTRACT FROM AUTHOR]

2,5‐Diketopiperazines (DKPs) are the smallest cyclic dipeptides found in nature with various attractive properties. In this study, we have demonstrated the successful modification of proline‐based DKPs using anionic ring‐opening polymerization (AROP) as a direct approach. Four different proline‐based DKPs with various side chains and increasing steric hindrance were used as initiating species for the polymerization of 1,2‐epoxybutane or ethoxyethyl glycidyl ether in the presence of t‐BuP4 phosphazene base. The addition of a Lewis acid, tri‐isobutyl aluminum, to the reaction mixture strongly decreased the occurrence of side reactions. Impact of the DKP side‐chain functionalities on molar mass control and dispersity was successfully evidenced. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1008–1016 Proline‐based 2,5‐diketopiperazines (cyclic dipeptides) are used in the presence of aphosphazene base as anionic ring‐opening polymerization initiators of two epoxide monomers, 1,2‐epoxybutane or protected glycidol (ethoxyethylglycidyl ether). Addition of Lewis Acid to the reaction mixture strongly decreases the occurrence of side reactions and allows the synthesis of 100% DKP‐functionalized polymer chains. [ABSTRACT FROM AUTHOR]

We present new side‐chain quaternized polyurethanes as antibacterial adhesives made by polyaddition polymerization followed by quaternization for different time intervals. The degree of quaternization of N‐diol units in the polymer is changed from 13.6 to 99.0 mol % (almost complete) for tuning the antibacterial action (leaching/contact type) and studying effect on adhesive strength. The degree of quaternization of about 26 mol % provided the nonleaching antibacterial effect with adhesive strength more than 60 N cm−2 on aluminum and glass substrates. The increase in the degree of quaternization enhanced polymer polarity shifting nonleaching (contact type) antibacterial behavior to the leaching type but maintaining the high adhesive strengths. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 752–757 Antibacterial side‐chain quaternized polyurethanes appropriate as strong adhesives are developed. The antibacterial effect can vary from leaching to non‐leaching type depending upon the degree of quaternization. [ABSTRACT FROM AUTHOR]

An asymmetric bifunctional monomer having both an unprotected alkynyl group and a vinyl ether (VE) group (3‐[2‐(2‐vinyloxyethoxy)‐ethoxy]‐propyne [VEEP]) was newly designed and found that the polymerization of VEEP smoothly proceeded in a controlled manner under a living cationic polymerization condition to give alkyne‐substituted polyVE (polyVEEP) without any protection of the pendant alkynyl function. Next, the use of an initiator with a methacryloyl moiety for the living cationic polymerization of VEEP afforded macromonomer‐type polyVE (MA‐PVEEP) carrying pendant alkynyl groups. The potential ability of the resultant macromonomer as an alkyne‐substituted polymer for the copper(I)‐catalyzed alkyne‐azide cycloaddition (CuAAC) was also confirmed. A novel macromonomer‐type glycopolymer [MA‐P(VE‐Mal)] having pendant maltose residues and a terminal methacryloyl group was successfully synthesized by CuAAC of MA‐PVEEP with maltosyl azide. Thus, a new pathway to the controlled synthesis of macromonomer‐type glycopolymers of free from any protecting/deprotecting processes was demonstrated. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 681–688 A macromonomer (MA‐(3‐[2‐(2‐vinyloxyethoxy)‐ethoxy]‐propyne [VEEP])) having a terminal methacryloyl moiety and pendant alkynyl groups was synthesized by living cationic polymerization of an asymmetric bifunctional monomer containing both an unprotected alkynyl group and a vinyl ether group. The resultant polymer was proved to be useful as the precursor for CuAAC‐based modification with maltosyl azide, afforded the novel macromonomer‐type glycopolymer [MA‐P(VE‐Mal)] with a terminal polymerizable group and pendant maltose residues. [ABSTRACT FROM AUTHOR]

The anionic polymerization of styrenic monomers with phosphazene bases as promoters, utilizing "seeding" technique in a nonpolar solvent and at room temperature was studied. In all experiments, the phosphazene base (t‐BuP4, t‐BuP2, and t‐BuP1) was added in an equimolar amount to the organolithium initiator after the formation of oligomers (2 min) by conventional anionic polymerization. When t‐BuP4 was used, the polymerization of styrene and 4‐methylstyrene was extremely fast (100 % conversion within 5 min) and the final homopolymers exhibited narrow molecular weight distribution and controlled molecular characteristics. Likewise, when weaker bases were employed, the polymerization was also controlled but showing slower reaction rate. To examine the "livingness" of this system, block copolymers were synthesized by sequential monomer addition. Further studies were conducted in order to extend this novel method to the anionic polymerization of dienes. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 456–464 The anionic polymerization of styrene by organolithium compounds in the presence of t‐BuP4 is uncontrolled. By using the "seeding technique," meaning that t‐BuP4 is added 2 min after the initiation, the polymerization of styrene and 4‐methylstyrene was extremely fast (5 min) and the final homopolymers exhibited narrow molecular weight distribution and controlled molecular characteristics. When t‐BuP2 and t‐BuP1 were used, the polymerization was also controlled but exhibited slower rates due to the lower basicity. [ABSTRACT FROM AUTHOR]

Diphenylethylene (DPE) is a monomer which has attracted significant interest from academia and industry both in terms of copolymerization kinetics and for the potential to extend and tune the range of glass transition temperatures accessible for DPE‐containing copolymers. DPE can undergo (co)polymerization with a variety of other monomers by living anionic polymerization but is incapable of forming a homopolymer due to steric hindrance. DPE, being a sterically bulky monomer, results in dramatic increases in the glass transition temperature (Tg) of resulting copolymers, with a perfectly alternating copolymer of styrene and DPE having a Tg of ~180 °C. Herein we report for the first time, the outcome of the statistical terpolymerization of butadiene, styrene, and DPE—a one‐pot, one‐shot, commercially scalable reaction using monomers of wide industrial importance. This extremely facile approach produces copolymers with a block‐like structure, which undergo microphase separation, possess a high Tg glassy "block" and are virtually indistinguishable from analogous block terpolymers made by the traditional sequential addition of monomers approach. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 382–394 This study reports for the first time the outcome of the statistical terpolymerization of butadiene, styrene, and DPE—a one‐pot, one‐shot, commercially scalable reaction using monomers of wide industrial importance. This extremely facile approach produces copolymers with a block‐like structure, which undergo microphase separation, possess a high Tg glassy "block," and are virtually indistinguishable from analogous block terpolymers made by the traditional sequential addition of monomers approach. [ABSTRACT FROM AUTHOR]

Controlled cationic polymerization of trans‐1‐methoxy‐1,3‐butadiene was achieved through the design of appropriate initiating systems, yielding soluble polymers with controllable molecular weights. The combined use of SnCl4 or GaCl3 as a Lewis acid catalyst and a weak Lewis base in conjunction with HCl as a protonogen resulted in efficient and controlled polymerization. The Mn values of the product polymers increased linearly along the theoretical line, which indicates that intermolecular crosslinking reactions negligibly occurred. In addition, the polymer microstructure was critically dependent on the weak Lewis base employed. In particular, the use of tetrahydrofuran as an additive resulted in the highest 4,1/4,3‐structure ratio (96/4). Weak Lewis bases also affected the polymerization rates but exhibited unique trends that differed from their effects on the cationic polymerization of alkyl vinyl ethers. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 288–296 Controlled cationic polymerization of trans‐1‐methoxy‐1,3‐butadiene was achieved with the use of SnCl4 or GaCl3 as a Lewis acid catalyst and a weak Lewis base such as ester and ether. The products had molecular weights that agreed with theoretical values. Interestingly, the polymer microstructure was found to depend crucially on the weak Lewis bases employed. The highest 4,1/4,3‐structure ratio, 96/4, was attained when tetrahydrofuran was used as an additive. [ABSTRACT FROM AUTHOR]

A new approach was developed for synthesis of certain A3B3‐type of double hydrophilic or amphiphilic miktoarm star polymers using a combination of "grafting onto" and "grafting from" methods. To achieve the synthesis of desired miktoarm star polymers, acetyl protected poly(ethylene glycol) (PEG) thiols (Mn = 550 and 2000 g mol−1) were utilized to generate A3‐type of homoarm star polymers through an in situ protective group removal and a subsequent thiol–epoxy "click" reaction with a tris‐epoxide core viz. 1,1,1‐tris(4‐hydroxyphenyl)ethane triglycidyl ether. The secondary hydroxyl groups generated adjacent to the core upon the thiol–epoxy reaction were esterified with α‐bromoisobutyryl bromide to install atom transfer radical polymerization (ATRP) initiating sites. ATRP of N‐isopropylacrylamide (NIPAM) using the three‐arm star PEG polymer fitted with ATRP initiating sites adjacent to the core afforded A3B3‐type of double hydrophilic (PEG)3[poly(N‐isopropylacrylamide)] (PNIPAM)3 miktoarm star polymers. Furthermore, the generated hydroxyl groups were directly used as initiator for ring‐opening polymerization of ε‐caprolactone to prepare A3B3‐type of amphiphilic (PEG)3[poly(ε‐caprolactone)]3 miktoarm star polymers. The double hydrophilic (PEG)3(PNIPAM)3 miktoarm star polymers showed lower critical solution temperature around 34 °C. The preliminary transmission electron microscopy analysis indicated formation of self‐assembly of (PEG)3(PNIPAM)3 miktoarm star polymer in aqueous solution. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 146–156 An approach involving a combination of thiol–epoxy "click" reaction and atom transfer radical polymerization/ring‐opening polymerization methods for the synthesis of A3B3‐type miktoarm star polymers was developed for the first time. The synthesis of double hydrophilic (PEG)3 (PNIPAM)3 and amphiphilic (PEG)3(PCL)3, A3B3‐type miktoarm star polymers was demonstrated. [ABSTRACT FROM AUTHOR]

The synthesis of two new conjugated polymers based on the relatively under‐exploited monomer, 5,8‐dibromo‐2‐[5‐(2‐hexyldecyl)‐2‐thienyl]‐1H‐dithieno[3,2‐e:2′,3′‐g]benzimidazole (dithienobenzimidazole, DTBI), and either 4,7‐bis[4‐hexyl‐5‐(trimethylstannyl)‐2‐thienyl]‐2,1,3‐benzothiadiazole (BTD) or 2,6‐bis(trimethylstannyl)‐4,8‐bis(5‐(2‐ethylhexyl) thiophen‐2‐yl)benzo[1,2‐b:4,5‐b′]dithiophene (BDT) is described. The polymers were synthesized via Stille polycondensation and characterized by traditional methods (1H NMR, gel‐permeation chromatography, matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry, thermal gravimetric analysis, differential scanning calorimetry, ultraviolet–visible spectroscopy, photoluminescence, and cyclic voltammetry). Prior to their synthesis, trimer structures were modeled by DFT calculations facilitating a further understanding of the systems' electronic and geometric structure. Polymers were titrated with acid and base to take advantage of their amphiprotic imidazole moiety and their optical response monitored with ultraviolet–visible spectroscopy. Finally, pristine polymer thin‐films were treated with acid and base to evaluate (de)protonation's effect on system electronics, but thin‐film degradation was encountered. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 60–69 This report describes the synthesis and characterization of two new semiconducting conjugated polymers. The polymers' structure is scrutinized using matrix‐assisted laser desorption/ionization‐time of flight spectroscopy and the effect of adding acid and base to the amphiprotic polymers is assessed. These analyses reveal interesting observations regarding these unique systems, which shed light upon areas in need of improvement in conjugated polymer synthesis. [ABSTRACT FROM AUTHOR]

ABSTRACT: Herein the stereoselective two‐step synthesis of pure exo‐5‐trimethylsilylnorbornene is reported. The monomer proved to be highly reactive in both metathesis and addition polymerization. ROMP polymerization was catalyzed by the first‐generation Grubbs catalyst. High‐molecular‐weight saturated addition polymers were prepared using nickel or palladium complexes as precatalysts and Na+[B(3,5‐(CF3)2C6H3)4]− and/or MAO as cocatalysts. The obtained addition polynorbornenes are highly gas permeable and microporous materials possessing large free volume and BET surface area (up to 540 m2/g). The influence of the substituent orientation (exo‐ vs. exo‐/endo‐mixture) on polymer properties was established. The metathesis polymer based on exo‐isomer exhibits 1.5‐ to 2‐fold increase of permeability coefficients for all gases in comparison to the similar polymer based on the mixture of exo‐ and endo‐isomers. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 1234–1248 [ABSTRACT FROM AUTHOR]

ABSTRACT: Four D‐π‐A‐type nonionic oxime sulfonate photoacid generators (PAGs) have been designed and synthesized for use in light‐emitting diode (LED) excitable cationic photoinitiators, in which N,N‐diphenylamino was used as electron donor with trifluoroacetophenone‐based oxime sulfonates (trifluoromethanoesulfonate and p‐toluenesulfonate) as electron acceptor and substituted fluorene and biphenyl groups as the π‐conjugated systems. PAG‐Ben‐Tol (with biphenyl and p‐toluenesulfonate) and PAG‐Flu‐Tol (with fluorene and p‐toluenesulfonate) showed high quantum yields of photoacid generation (0.33–0.50) and very good thermal stability (over 250 °C). The absorbance spectra of these PAGs were consistent with the emission spectra of commercially gained UV–visible LED light sources. The potential of these PAGs for cationic photoinitiators was tested in two cationic monomer systems. These PAGs needed low light intensity and low concentration for photopolymerization with high conversions of monomer, for example, over 80%, gained at 3.0 mW cm−2 from 365 to 470 nm LEDs. The photochemical mechanisms of these PAGs are comprehensively investigated and discussed in detail. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 1146–1154 [ABSTRACT FROM AUTHOR]

ABSTRACT: Allyl‐telechelic polyisobutylene (A‐PIB‐A) produced by the bis‐benzocyclobutane dichloride (bBCB‐diCl) initiator contains the bis‐benzocyclobutane (bBCB) fragment at the center of the macromolecule (A‐PIB‐bBCB‐PIB‐A). Thermolysis of A‐PIB‐bBCB‐PIB‐A quantitatively converts the central bBCB fragment to a substituted conjugated tetraene (A‐PIB‐tetraene‐PIB‐A). The structure of A‐PIB‐tetraene‐PIB‐A was anticipated from small molecule models and identified/quantitated by 1H NMR spectroscopy. This is the first time a reactive functional group was introduced at the statistical center of a (telechelic) PIB. Subsequently, the A‐PIB‐tetraene‐PIB‐A was peroxidized to an epoxy derivative. Reaction of the A‐PIB‐tetraene‐PIB‐A with HSCH2CH2OH produced HOCH2‐telechelic PIB containing a central CH2OH function, and hydrosilation with HSi(Me2)‐O‐Si(Me2)H produced SiH‐telechelic PIB with a central SiH function. Reactions with maleic anhydride, tetracyanoethylene, butyl lithium, and potassium permanganate have also been examined. In sum, A‐PIB‐bBCB‐PIB‐A and A‐PIB‐tetraene‐PIB‐A are useful intermediates for the synthesis of novel PIB‐based materials for various end uses under investigation. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 1140–1145 [ABSTRACT FROM AUTHOR]

ABSTRACT: Polymeric networks are produced by step‐growth polyaddition and co‐polyaddition reactions of 1‐ethylimidazoline in combination with various diisocyanates. Five aromatic, two aliphatic diisocyanates and a polyurethane prepolymer are used as particular reactant in N,N‐dimethylformamide as solvent at room temperature. Obviously, 1‐ethylimidazoline can serve as trifunctional monomer, which enables a crosslinking reaction with diisocyanates. Molecular structure elements of the polymeric networks were studied by solid state 13C‐NMR spectroscopy revealing that detailed molecular structure formations are determined whether aromatic or aliphatic diisocyanates are used. Quantum chemical calculations were used as supporting method to elucidate the complex reaction cascades. Hence, it can be shown that beside 3:1 stoichiometric structures 2:1 based structures are formed as well. These structures are observed as kinetically controlled products only when aromatic diisocyanate monomers are used. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 977–985 [ABSTRACT FROM AUTHOR]

ABSTRACT: Three novel types of thiophene‐containing oxime sulfonates with a big π‐conjugated system were reported as non‐ionic photoacid generators. The irradiation of the newly synthesized photoacid generators using near UV–visible light‐emitting diodes (LEDs) (365–475 nm) results in the cleavage of two weak NO bonds in single molecules, which lead to the generation of different sulfonic acids in good quantum and chemical yields. The mechanism for the NO bond cleavage for acid generation was supported by the UV–visible spectra and real‐time 1H NMR spectra. They are developed as high‐performance photoinitiators without any additives for the cationic polymerization of epoxide and vinyl ether upon exposure to near‐UV and visible LEDs (365–475 nm) at low concentration. In the field of photopolymerization, especially visible light polymerization, it has great potential for application. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 776–782 [ABSTRACT FROM AUTHOR]

ABSTRACT: Both bifunctional initiators, the new low cost bBCB‐diCl [4,9‐dichloro,2,4,7,9‐tetramethyl‐tricyclo[6.2.0.036]deca‐1(8),2,6‐triene] and the universally used “hindered” HDCCl [1‐(tert‐butyl)‐3,5‐bis(2‐chloropropan‐2‐yl)benzene] induce the living bidirectional block copolymerization of isobutylene (IB) followed by styrene (St), and produce PSt‐b‐PIB‐b‐PSt (SIBS) triblocks. We discovered that the molecular weights of triblocks kept significantly increasing long after St conversion reached completion during syntheses. Results were explained by the formation of blends consisting of the expected linear SIBS plus hyperbranched SIBS, HB(SIBS)n. The structure of high molecular weight (>106 g/mol) HB(SIBS)n was characterized by various techniques, and key properties of SIBS/HB(SIBS)n blends were investigated. The mechanism of HB(SIBS)n formation and the synthesis of SIBS/HB(SIBS)n blends was elucidated. The properties of SIBS/HB(SIBS)n blends are superior to those of SIBS. Thus, whereas SIBS exhibits ∼25 MPa tensile strength and ∼450% elongation, SIBS/HB(SIBS)n blends exhibit 25–27 MPa tensile strength and >400% elongation; deformation under constant load of SIBS is ∼12%, whereas that of SIBS/HB(SIBS)n is <1%; permanent set of SIBS is 1.3% whereas that of SIBS/HB(SIBS)n is <0.5%. SIBS/HB(SIBS)n blends also exhibit higher yield, yield strength, and toughness than SIBS. The microstructure/property relationship of HB(SIBS)n is discussed and the reasons for enhanced properties of SIBS/HB(SIBS)n blends are analyzed. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 705–713 [ABSTRACT FROM AUTHOR]

ABSTRACT: Water soluble monomer like sodium p‐styrene sulfonate (SSS) is copolymerized with hydrophobic and reactive monomer glycidyl methacrylate (GMA). The polymerization proceeds as dispersion and forms gels. The gel forming nature prevails even with other hydrophobic and hydrophilic monomers to form ternary polymeric systems. The swelling is dependent on polymer composition as well as the treatment history of polymers. SSS also induces ring opening of GMA to form 1,2‐diols as confirmed independently by various model reactions. The ability of hydrogels to absorb various dyes indicates that owing to the anionic nature, hydrogels absorb cationic dyes nearly quantitatively. Because of their strong affinity to cationic species these hydrogel forming polymers are potentially useful in water purification applications as well as purification of proteins. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 626–634 [ABSTRACT FROM AUTHOR]

ABSTRACT Diphenylphenacylsulfonium tetrafluoroborate (DPPS+BF4-) salt possessing both phenacyl and sulfonium structural units was synthesized and characterized. DPPS+BF4- absorbs light at relatively higher wavelengths. The direct and sensitized initiation activity of the salt in both cationic and free radical photopolymerizations was investigated and compared with that of its analogue triphenylsulfonium tetrafluoroborate (TPS+BF4-). Differential scanning photocalorimetry and conventional gravimetric studies revealed that DPPS+BF4- showed higher efficiency for direct and sensitized photopolymerizations of most of the monomers investigated. Although, principally both homolytic and/or heterolytic cleavage is possible, theoretical studies suggested that homolytic pathway is more favored for the generation of reactive initiating species. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 451-457 [ABSTRACT FROM AUTHOR]

ABSTRACT The microstructure of polybutadiene synthesized via cationic polymerization using TiCl4-based initiating systems has been investigated using 1D (1Н, 2Н, and 13С) and 2D (HSQC and HMBC) NMR spectroscopy. It was found that trans-1,4-unit is predominant structure of unsaturated part of polymer chain. Besides, the small amount of 1,2-structures was also detected, while cis-1,4-units were totally absent. The signals of carbon atoms of three types of head groups ( trans-1,4-, 1,2-, and tert-butyl) and two types of end groups ( trans-1,4-Cl and 1,2-Cl) were identified for the first time in macromolecules of cationic polybutadiene. It was showed that tert-butyl head groups were formed due to the presence in monomer of admixtures of isobutylene. The new methodology for calculation of the content of different structural units in polybutadiene chain as well as the head and end groups was proposed. It was established that main part of 1,2-units distributed randomly along the polybutadiene chain as separate units between trans-1,4-structures. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 387-398 [ABSTRACT FROM AUTHOR]

ABSTRACT Superhydrophobic surfaces (SHS) find versatile applications as coatings due to their very high water-repellency, self-cleaning, and anti-icing properties. This investigation describes the preparation of a SHS from surfactant-free hybrid fluoropolymer latex. In this case, reversible addition-fragmentation chain transfer (RAFT) polymerization was adopted to prepare a copolymer of 4-vinyl pyridine (4VP) and vinyl triethoxysilane (VTES), where the pyridine units were quaternized to make the copolymer soluble in water. The copolymer was further used as a macro-RAFT agent to polymerize 2,2,2-trifluoroethyl methacrylate (TFEMA) in a surfactant-free emulsion via polymerization-induced self-assembly (PISA). The macro-RAFT agent contained a small amount of VTES as co-monomer which was utilized to graft silica nanoparticles (SNPs) onto the P(TFEMA) spheres. The film prepared using the nanocomposite latex exhibited a nano-structured surface as observed by SEM and AFM analyses. Surface modification of the film with fluorinated trichlorosilane produced an SHS with a water contact angle (WCA) of 151.5°. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 266-275 [ABSTRACT FROM AUTHOR]

ABSTRACT A base amplifier (BA) that autocatalytically generates a diamine having a disulfide bond has been developed. Diamines generated from this BA are integrated into cross-linked networks of epoxy resins that also have disulfide bonds. Anionic UV curing is performed using a photobase generator, the BA and the epoxy resins, and cured films are obtained after UV irradiation and subsequent heating at 160 °C. Furthermore, this curing system is applied successfully to adhesion of two stainless substrates, which is cancelled with gentle heating and a shear force. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 237-241 [ABSTRACT FROM AUTHOR]

ABSTRACT Frontal polymerization of deep eutectic solvents (DESs) made with acrylic or methacrylic acid as the monomer and hydrogen bond donor was studied. Fronts with acrylic acid and choline chloride propagated more uniformly than with pure acrylic acid, so an exploration into how the DES affected frontal polymerization was performed. The hydrogen bond acceptor of the DES was replaced by several analogs to determine the effect on the DES front behavior. The analogs used were talc, DMSO, lauric acid, and stearic acid, which acted as a heat sink, inert diluent, hydrogen bonding diluent, and inert phase change material, respectively. None of the methacrylic acid-analog systems were able to sustain a front. While the acrylic acid-analog systems did sustain a front (with the exception of stearic acid), none of the fronts replicated the acrylic acid DES behavior. The acrylic acid-talc sample behaved more violently-like pure acrylic acid polymerization-than the acrylic acid DES, and the DMSO and lauric acid samples produced slower fronts than that of the acrylic acid DES. We propose that the reactivity of the acrylic acid and methacrylic acid is enhanced in the DES. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 4046-4050 [ABSTRACT FROM AUTHOR]

ABSTRACT We describe the discovery of novel low cost bifunctional initiators 2,4,7,9-tetramethyl-tricyclo[6.2.0.036]deca-1(8),2,6-triene-4,9-diol (bBCB-diOH) and 4,9-dichloro,2,4,7,9-tetramethyl-tricyclo[6.2.0.036]deca-1(8),2,6-triene (bBCB-diCl), for living cationic bidirectional polymerization of olefins, for example, isobutylene. bBCB-diOH was quantitatively synthesized in one step by UV radiation of commercially available diacetyl durene (DAD) and bBCB-diCl by hydrochlorination of bBCB-diOH. These molecules, in conjunction with TiCl4 coinitiator, initiate the living polymerization of isobutylene. Livingness was demonstrated by linear conversion versus molecular weight (MW) plots and narrow MW distributions. Polymerizations are slower than those initiated by the universally used 'hindered' bifunctional initiator 5-tert-butyl-1,3-bis(1-chloro-1-methyl)benzene and are suitable for rate studies. Herein, we report the synthesis, by the use of bBCB-diCl, of relatively low MW ( Mn < 3000 g mol−1) allyl-telechelic polyisobutylene (PIB) used for the synthesis of PIB-based polyurethanes and that of relatively high MW ( Mn > 30,000) living PIB telechelics for the synthesis of thermoplastic elastomers. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 3716-3724 [ABSTRACT FROM AUTHOR]

ABSTRACT Two one-component, double-chromophoric thioxanthone photoinitiators, namely TX-EDA and TX-DETA were synthesized by the reaction of thioxanthone aldehyde (TX-A) with ethylenediamine (EDA) and diethylenetriamine (DETA), respectively via a facile Schiff base reaction. Both photoinitiators were characterized by spectral analysis and photobleaching studies. DFT calculations are employed to reveal the contribution of the different orbitals to the excitation of the initiators. The double-chromophoric nature of the initiators gives rise to an increased absorption in the near UV region when compared with the pristine TX-A. Photoinitiated polymerization of various vinyl monomers with TX-EDA and TX-DETA has been investigated in the presence and absence of a co-initiator and compared for formulations consisting of precursor TX-A. In addition, real-time FTIR spectroscopic studies were performed in methyl methacrylate polymerization with both initiators. The higher efficiency observed with TX-DETA may be attributed to the additional hydrogen donating sites adjacent to nitrogen atoms. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 3475-3482 [ABSTRACT FROM AUTHOR]

ABSTRACT Using atom transfer radical polymerization (ATRP) and macromolecular azo coupling reaction, both o-nitrobenzyl (ONB) group and azobenzene group were efficiently incorporated into the center of the amphiphilic diblock copolymer chain. The prepared diblock copolymer was well characterized by UV-vis, 1H NMR, and GPC methods. Self-assembly of the amphiphilic copolymer in selected solvents can result in uniform self-assembly aggregates. In the presence of external stimuli [upconversion nanoparticles (UCNPs)/NIR light or enzyme], the amphiphilic diblock copolymer chain could be broken by the cleavage of ONB or azobenzene group, which would lead to the disruption of the self-assembly aggregates. This photo- and enzyme-triggered disruption process was proved by using transmission electron microscopy (TEM) and GPC method. Fluorescence emission spectra measurements indicated that the release of Nile red, a hydrophobic dye, encapsulated by the self-assembly aggregates, could be successfully realized under the NIR light and enzyme stimuli. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 2450-2457 [ABSTRACT FROM AUTHOR]

ABSTRACT Liquid crystalline block copolymers (LCBCPs) are fascinating for their combining molecular level liquid crystalline orders and microphase separated multidomain morphologies. Here in this article, a series of PEG-containing side-chain discotic LCBCPs of PEG- b- Pm- n with variant spacer length m = 6, 10 and degree of polymerization (DP) of discotic LC block from n = 10 to 45, have been well-synthesized via reversible addition-fragmentation chain-transfer (RAFT) polymerization. The RAFT process mediated by macromolecular chain transfer agent (macroCTA) shows remarkable monomer concentration dependence. The influence of the introduced PEG block on the nano-scale microphase-segregation and mesophase organization is closely related to the side-chain triphenylene (TP) discogens stacking mode dependent on the spacer length. Wherein, the PEG- b- P6- n series with a six-methylene spacer exhibit consistent microphase separation with slightly disturbed yet ordered columnar structures. While for PEG- b- P10- n series with a longer ten-methylene spacer, the columnar organization in the copolymers is even improved in contrast with the low order of randomly TP stacking in their corresponding homopolymers. This work offers a viable and inspiring pathway for controlled synthesis of block copolymers with bulky side groups, as well as enhances in-depth understanding of the hierarchical superstructure organization in discotic units involved complex block copolymers. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 2544-2553 [ABSTRACT FROM AUTHOR]