Controlled synthesis of poly(acetone oxime acrylate) as a new reactive polymer: Stimuli-responsive reactive copolymers

Acetone oxime acrylate has been synthesized as a new active ester monomer. Free radical polymerization yielded a reactive polymer soluble in various organic solvents, such as chloroform, dioxane, DMSO, acetone, methanol, dichloromethane, DMF, and ethanol. Controlled radical polymerization of acetone oxime acrylate was successfully conducted using the RAFT, NMP and Iniferter method. Partly polymer analogous reaction with N-isopropylamine resulted in the reactive copolymer poly(N-isopropylacrylamide-co-acetone oxime acrylate), which featured a lower critical solution temperature (LCST) of 61 °C in water. Further, the reactivity of the copolymer was exemplary proven by complete reaction with ammonia yielding poly(N-isopropylacrylamide-co-acrylamide), which does not possess a LCST.     

Polyaniline nanofibers fabricated by electrochemical polymerization: A mechanistic study

Polyaniline (PANI) nanofibers with interconnected network-like structures were electropolymerized on stainless steel substrates by galvanostatic electrolysis. The samples were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV-visible spectroscopy (UV-vis) and Fourier transform infrared spectroscopy (FTIR). The results show that PANI and gels (mixtures of oligomer, dopant and aniline) form simultaneously during the electrochemical deposition. The gels play an important role in the formation of PANI nanofibers. The PANI formed in the early stage of polymerization is subject to secondary growth along one dimension, since the nucleation sites are suppressed by the wrapped gels. The dendritic degree of PANI nanofibers is related to dopants, and the order is as follows: PANI-H₃PO₄ > PANI-H₂SO₄ > PANI-HNO₃. No nanofibers are obtained using CH₃COOH as dopants due to the high solubility of PANI-CH₃COOH.     

Synthesis and crystallization behaviors of poly(styrene-b-isoprene-b-ε-caprolactone) triblock copolymers

The triblock copolymers, poly(styrene-b-isoprene-b-ε-caprolactone)s (PS-b-PI-b-PCL) have been synthesized successfully by combination of anionic polymerization and ring-opening polymerization. Diblock copolymer capped with hydroxyl group, PS-b-PI-OH was synthesized by sequential anionic polymerization of styrene and isoprene and following end-capping reaction of EO, and then it was used as macro initiator in the ring-opening polymerization of CL. The results of DSC and WAXD show big effect of amorphous PS-b-PI on the thermal behaviors of PCL block in the triblock copolymers and the lower degree of crystalline in the triblock copolymer with higher molecular weight of PS-b-PI was observed. The real-time observation on the polarized optical microscopy shows the spherulite growth rates of PCL₂₇, PCL₃₂₈ and PS-b-PI-b-PCL₃₄₄ are 0.71, 0.46 and 0.07 μm s⁻¹, respectively. The atomic force microscopy (AFM) images of the PS₉₀-b-PI₆₆-b-PCL₂₈ show the columns morphology formed by it’s self-assembling.     

Radiation-induced polymerization of methyl methacrylate in microemulsion with high monomer content

γ-Ray-induced polymerization of methyl methacrylate was conducted in a microemulsion stabilized by a mixture of sodium of 12-acryloxy-9-octadecenoic acid (AOA) and sodium dodecyl sulfate (SDS) with various weight ratios at room temperature. The experimental data showed that the mixture of AOA and SDS with a weight ratio 2 was an efficient surfactant system for the microemulsion containing 38.6 wt% MMA and 5.5 wt% surfactant. The effects of MMA concentration and dose rate on the polymerization kinetics and particle size are discussed.     

Continuous process for ATRP: Synthesis of homo and block copolymers

Continuous ATRP of MMA was carried out in a flow tubular reactor with varying flow rate, temperature, and [monomer]/[initiator] ratios. Changing the flow rate directly relates to the reaction time. This process produces polymer continuously with the conversion increasing with decreasing flow rate. The molecular weight (relating to the flow rate) increases linearly with conversion which is also observed when the [monomer]/[initiator] ratio was changed. The effect of altering the reaction temperature was studied and the apparent activation energy of the propagation reaction of MMA in this system was calculated to be ∼56.9 kJ mol⁻¹, close to the values reported previously. Preparation of diblock copolymers is also reported with varying comonomers and the conversion, and SEC results suggested that this continuous system is an excellent and facile way to have a continuous ATRP process.     

Polyaniline and polypyrrole: A comparative study of the preparation

Aniline and pyrrole have been oxidized with ammonium peroxydisulfate in aqueous solutions, in the presence of equimolar quantities of hydrochloric acid. The oxidation of pyrrole was faster; the induction period typical of aniline oxidation was absent in the case of pyrrole. As the proportion of oxidant-to-monomer molar concentration increased up to 1.5, the yield increased in both cases. Similarities between the two oxidations are illustrated and discussed. The oxidant-to-monomer molar ratio 1.25 is proposed to be the optimum stoichiometry, in the accordance with the data published in the literature. The conductivities of the polymers prepared were only slightly dependent on the oxidant-to-monomer ratio in the range 0.3-1.5, and were of the order of 10⁰ S cm⁻¹ for polyaniline and ∼10⁻²-10⁻¹ S cm⁻¹ for polypyrrole. Outside this interval, the conductivity of both polymers was reduced. Polyaniline having conductivity ∼10 S cm⁻¹ was produced in solutions of phosphoric acid of various concentrations. On the contrary, the conductivity of polypyrrole was reduced as the concentration of phosphoric acid became higher. The type of protonation is discussed with the help of FTIR spectra by analyzing the ammonium salts obtained after deprotonation. Sulfate or hydrogen sulfate anions produced from peroxydisulfate always constitute a part of the counter-ions.     

Synthesis of PDMAEMA-PCL-PDMAEMA triblock copolymers

The synthesis of ABA triblock copolymers of the type PDMAEMA-PCL-PDMAEMA was achieved by atom transfer radical polymerization (ATRP) of DMAEMA using difunctional polycaprolactone (PCL) as macroinitiator. First, ring-opening polymerization (ROP) of ε-caprolactone (ε-CL) was carried out in the presence of 1,2-diaminoethane/tin (II) octanoate. Dihydroxy PCL thus obtained was end-functionalized in a quantitative manner using 2-bromoisobutyryl bromide. The resulting Br-PCL-Br was used as macroinitiator in the ATRP of DMAEMA leading to triblock copolymers with PCL as the central block and PDMAEMA sequences of different lengths. NMR and SEC analyses confirmed the formation of ABA triblocks.     

Unraveling Inter‐ and Intrachain Electronics in Polythiophene Assemblies Mediated by Coordination Nanospaces

Strong interchain interactions render unsubstituted polythiophene un‐fusible, non‐melting, and insoluble. Therefore, control of the packing structure, which has a profound effect on the optical and electronic properties of the polymer, has never been achieved. Unsubstituted polythiophene was prepared in the one‐dimensional channels of [La(1,3,5‐benzenetrisbenzoate)]_n, where polymer chains form unprecedented assembly structures mediated by the host framework. It is noteworthy that the emission and carrier transport properties were drastically changed by varying the number of chains within a particular assembly. The response of the composite to additional guests is also examined as a method to use the composites as low‐concentration sensors. Our findings show that the encapsulation of polymer chains in host materials is a facile method for understanding the intrinsic properties of conjugated polymers, along with controlling and enhancing their functions.     

Visible‐Light‐Induced Photoredox Catalysis of Dye‐Sensitized Titanium Dioxide: Selective Aerobic Oxidation of Organic Sulfides

TiO₂ photoredox catalysis has recently attracted much interest for use in performing challenging organic transformations under mild reaction conditions. However, the reaction scheme is hampered by the fact that TiO₂ can only be excited by UV light of wavelengths λ shorter than 385 nm. One promising strategy to overcome this issue is to anchor an organic, preferably metal‐free dye onto the surface of TiO₂. Importantly, we observed that the introduction of a catalytic amount of the redox mediator TEMPO [(2,2,6,6‐tetramethylpiperidin‐1‐yl)oxyl] ensured the stability of the anchored dye, alizarin red S, thereby resulting in the selective oxidation of organic sulfides with O₂. This result affirms the essential role of the redox mediator in enabling the organic transformations by visible‐light photoredox catalysis.     

Synthesis of Calcium(II) Amidinate Precursors for Atomic Layer Deposition through a Redox Reaction between Calcium and Amidines

We have prepared two new Ca^II amidinates, which comprise a new class of ALD precursors. The syntheses proceed by a direct reaction between Ca metal and the amidine ligands in the presence of ammonia. Bis(N,N′‐diisopropylformamidinato)calcium(II) ( 1 ) and bis(N,N′‐diisopropylacetamidinato)calcium(II) ( 2 ) adopt dimeric structures in solution and in the solid state. X‐ray crystallography revealed asymmetry in one of the bridging ligands to afford the structure [(η²‐L)Ca(μ‐η²:η²‐L)(μ‐η²:η¹‐L)Ca(η²‐L)]. These amidinate complexes showed unprecedentedly high volatility as compared to the widely employed and commercially available Ca^II precursor, [Ca₃(tmhd)₆]. In CaS ALD with 1 and H₂S, the ALD window was approximately two times wider and lower in temperature by about 150 °C than previously reported with [Ca₃(tmhd)₆] and H₂S. Complexes 1 and 2 , with their excellent volatility and thermal stability (up to at least 350 °C), are the first homoleptic Ca^II amidinates suitable for use as ALD precursors.