Glasses-shaped triblock copolymer prepared by combination of atom transfer radical polymerization and ring opening polymerization

A glasses-shaped triblock copolymer of poly(ε-caprolactone)-b-polystyrene-b-poly(ε-caprolactone) (PCL-b-PS-b-PCL) is prepared by combining atom transfer radical polymerization (ATRP) and ring opening polymerization (ROP). Polystyrene (PS) star polymers are prepared via ATRP using a tetra-functional initiator, followed by azidation to yield azide end-functionalized star polymers. An alkyne-functionalized coupling agent, 2,2-bis[(2-propyn-1-yloxy)methyl]-1-propanol is employed to produce hydroxy 8-shaped PS via copper(I)-catalyzed alkyne-azide cycloaddition. Herein, hydroxy 8-shaped PS with high purity is obtained through preparative size exclusion chromatography (Prep SEC) and high-performance liquid chromatography, followed by the characterizations using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS), size exclusion chromatography (SEC), infrared, and proton nuclear magnetic resonance (¹H NMR) spectroscopy. The hydroxy groups of the 8-shaped PS are utilized as initiators for the ROP of ε-caprolactone to obtain linear chains attached to the 8-shaped architecture. After SEC fractionation, the glasses-shaped triblock copolymer is characterized using ¹H NMR and SEC. This unprecedented topology possesses two free chain-ends and two cycles; thus, both the properties of linear and cyclic polymers may be expected to be observed.     

Cyclic polymers swollen in a good solvent dynamic scattering properties

A general formalism for the dynamic scattering properties of cyclic polymers in good solvent conditions is presented. Single-chain dynamics are investigated in the framework of the Oseen tensor model with and without the preaveraging approximation. The chain swelling due to excluded volume interactions is introduced by a renormalization of the internal chain statistics of cyclic polymers. The relaxations of the concentration fluctuations are also described for both ring homopolymers and copolymers. © 1994 John Wiley & Sons, Inc.     

A molecular thermodynamic model for random copolymer solutions

A new Helmholtz energy model of mixing for random copolymer solutions based on a close-packed lattice has been developed. The model contains three terms: the contribution of the athermal mixing of polymer chain and solvent, the Helmoltz energy of mixing in a multi-component Ising lattice where the interactions between segments is accounted for, and the contribution of the dissociation of the polymer and the association of monomers. The Guggenheim model, Yang et al.'s model and the sticky-point model of Cummings, Zhou and Stell are used respectively, for the above three contributions. Comparisons between Monte Carlo simulated coexistence curves with those predicted by various theories for random copolymer solutions with various chain lengths, chain compositions and inter-segment interaction parameters show that the agreement between simulations and the predictions of this work is nearly perfect. The model can be used satisfactorily to correlate the liquid–liquid equilibria of practical random copolymer solutions.     

Interaction between star-like block copolymer and sodium oleate in aqueous solutions

The interaction between a star-like block copolymer (AP432) and an anionic surfactant sodium oleate (C₁₇H₃₃COONa) was investigated in detail both at the air/water interface and in bulk aqueous solutions. The results of surface tension show that AP432 and C₁₇H₃₃COONa could form mixed micelles. The results obtained from the oscillating barrier measurements at low dilational frequencies (0.01-0.1 Hz) reveal that the maximum values of the dilational modulus for AP432/C₁₇H₃₃COONa mixed system moved to lower concentrations compared to those of single AP432 or C₁₇H₃₃COONa aqueous solutions. Steady-state fluorescence measurements indicate that after mixing, the I₁/I₃ values of AP432/C₁₇H₃₃COONa system above the cmc are higher than those of single AP432 or C₁₇H₃₃COONa solutions. This is probably due to a looser pack of the molecules within micelles for the AP432/C₁₇H₃₃COONa mixture, which is also consistent with the results obtained from TEM observations. For comparison, the interaction between a commercially available linear PEO-PPO-PEO copolymer (Pluronics L64) and C₁₇H₃₃COONa was also studied. All experimental results give clear evidence that the interaction between L64 and C₁₇H₃₃COONa is different from that between AP432 and C₁₇H₃₃COONa.     

Viscoplastic flow and shear thickening in concentrated diblock copolymer solutions

Concentrated (typically 6%) solutions of a polystyrene-polyisoprene diblock copolymer in low viscosity paraffinic solvents form a micelle system by precipitating the polystyrene blocks, whereas the polyisoprene blocks are in solution. Besides viscoplastic behavior without thixotropy, this system exhibits a pronounced shear thickening in steady-state shear flow. The micelles are stable up to shear rates of more than 10⁵ s^–1. The properties of the solutions, especially the shear-thickening behavior, depend on the thermal history of the samples as well as on the solvent properties and are sensitive to flow field disturbances occurring in rotational viscometer devices with a profiled surface structure as commonly used to avoid wall slip in dispersed materials. The shear thickening is found to be related to the formation of a long-range ordered structure which also gives rise to the yield point. This long-range order enables aggregate flow with less energy dissipation at low shear rates. Shear-induced break-up of the aggregates appears as a shear-thickening transition which is observed in different types of flow fields.     

Hydrodynamic microelectrode voltammetry

This review provides a detailed overview of the progress made in the last 25 years in the field of hydrodynamic microelectrodes (HMEs) with particular application to the study of electrochemical kinetics. A survey is made of the various types of HMEs that have been reported in the literature, with summaries of theoretical and experimental details along with the results published by each methodology. Conclusions are drawn regarding the comparative advantages and disadvantages of these techniques, and the channel and microject electrodes found to be preferred. Published in Russian in Elektrokhimiya, 2008, Vol. 44, No. 4, pp. 397–421. The text was submitted by the authors in English.     

Molecular interaction in some polymeric additive solutions containing styrene-hydrogenated butadiene copolymer

The miscibility of styrene-hydrogenated butadiene copolymer (SHB) with different constituents of polymer additives for lubricating mineral oils was studied in dilute solution regime, using xylene as model solvent, at 30 °C, in a wide range of polymer blend compositions. The systems studied were SHB/poly(ethylene-co-propylene) (EPC), SHB/poly(methyl methacrylate) (PMMA), SHB/poly(dodecyl methacrylate) (PDDMA) and SHB/polystyrene (PS). The viscometric interaction parameters were calculated according to the Krigbaum–Wall and Catsiff–Hewett models of ideal viscometric behavior. Strong repulsive interactions were found in SHB/PMMA and SHB/PDDMA systems pointing to immiscibility. SHB/EPC and SHB/PS deviated much less from ideality. The results were compared to the theoretical estimation of interaction in polymer blends in the absence of solvent, using the Coleman–Graf–Painter approach. No correlation was observed between the interaction in the bulk and in solution.     

Characterization of the ground state pyrene complex in ethylene-propylene copolymer solutions

Pyrene-labeled functionalized ethylene-propylene (EP) copolymer was prepared by grafting 1-pyrenebutyrylhydrazine onto EP copolymer through maleic anhydride pendants. The EP copolymer contained 60 mol % ethylene; its weight-average molecular weight (M^w) was 148,000. The pyrene-labeled amide functionalized EP copolymer, PA-EP(60/40), was made to simulate the amine functionalized EP copolymers that are commonly used as dispersant additives in motor oils. UV absorption spectra, fluorescence emission and excitation spectra, and fluorescence decay profiles of the pyrene were studied to determine the copolymer conformation and dynamics in methylcyclohexane and tetrahydrofuran (THF). The pyrene fluorescence characteristics of PA-EP(60/40) were highly dependent on the solvent. The dependence of fluorescence emission intensity on the excitation wavelength was large in methylcyclohexane and moderate in THF. A frequency shift of about 2 nm was observed between the excitation spectrum obtained with the emission line at 377 nm and that at 550 nm in the methylcyclohexane solutions, but no shift was found in the corresponding tetrahydrofuran solutions. The ratios of the preexponential factors (a₂₁/a₂₂) of the excimer decays obtained in both methylcyclohexane and THF solutions were different from ?1.0. However, the deviation of the excimer formation process from the Birks scheme is small in THF but large in methylcyclohexane. In addition, the Huggins constants obtained from intrinsic viscosity measurements of the PA-EP(60/40) copolymer solutions suggest that copolymer aggregation occurs in methylcyclohexane but not in THF. H-bonding between two pyrene-containing pendants is apparently the main driving force for the formation of the ground state pyrene complex. THF is found to be effective in inhibiting the H-bonding formation. © 1995 John Wiley & Sons, Inc.     

Cosolvency effects on copolymer solutions at high pressure

Cloud-point data to 180°C and 2800 bar are presented for polyethylene, poly(methyl acrylate), and two poly(ethylene-co-methyl acrylate) copolymers (10 and 31 mol % methyl acrylate) in propane and chlorodifluoromethane with two cosolvents, acetone and ethanol. The addition of small amounts of either cosolvent to the copolymer–solvent mixtures shifts the cloud-point curve to lower pressures and temperatures, as both cosolvents provide favorable polar interactions with the acrylate group in the backbone of the copolymer. Ethanol has a larger effect than acetone since ethanol hydrogen bonds to the acrylate group. However, if the concentration of ethanol is increased above ca. 10 wt %, it self-associates and reverts to antisolvent behavior, forcing the copolymer out of solution. For nonpolar polyethylene–propane mixtures, the polar cosolvents behave as traditional an-tisolvents. In poly(methyl acrylate)–chlorodifluoromethane mixtures, both polar cosolvents enlarge the single-phase region. The cloud-point curves for the (co)polymer–propane–acetone mixtures are modeled reasonably well using the Sanchez–Lacombe equation of state with two adjustable mixture parameters. No attempt is made to model the mixtures that exhibit hydrogen bonding. © 1993 John Wiley & Sons, Inc.     

Blends of a siloxane/urea/urethane-segmented copolymer with an IPDI-based polyetherurethane

A series of copolymer blends have been prepared using a poly(ether urethane) and a poly(siloxane–urea–urethane). The copolymers were prepared by a hardsegment first, two-step polymerization method. The hard segments of the copolymers were derived from isophorone diisocyanate (IP) and 1,4-benzenedimethanol (B), and the soft segments were based on polytetrahydrofuran (PTMO, M_w = 2000), and polydimethylsiloxane (PDMS, M_w =27,000), respectively. The siloxanecontaining copolymer, PDMS27K-IP-B2 (2 moles diol chain extender/mole PDMS27K), was used as the minor component (1.6, 2.5 and 6.0 wt%) in a series of blends. These blends were found to preserve the mechanical properties of the poly(ether–urethane) as well as the surface properties of the poly(siloxane–urea–urethane).     

Hyperbranched block copolymer from AB2 macromonomer: Synthesis and its reaction‐induced microphase separation in epoxy thermosets

In this contribution, we reported the synthesis of a hyperbranched block copolymer composed of poly(ε‐caprolactone) (PCL) and polystyrene (PS) subchains. Toward this end, we first synthesized an α‐alkynyl‐ and ω,ω′‐diazido‐terminated PCL‐b‐(PS)₂ macromonomer via the combination of ring‐opening polymerization and atom transfer radical polymerization. By the use of this AB₂ macromonomer, the hyperbranched block copolymer (h‐[PCL‐b‐(PS)₂]) was synthesized via a copper‐catalyzed Huisgen 1,3‐dipolar cycloaddition (i.e., click reaction) polymerization. The hyperbranched block copolymer was characterized by means of ¹H nuclear magnetic resonance spectroscopy and gel permeation chromatography. Both differential scanning calorimetry and atomic force microscopy showed that the hyperbranched block copolymer was microphase‐separated in bulk. While this hyperbranched block copolymer was incorporated into epoxy, the nanostructured thermosets were successfully obtained; the formation of the nanophases in epoxy followed reaction‐induced microphase separation mechanism as evidenced by atomic force microscopy, small angle X‐ray scattering, and dynamic mechanical thermal analysis. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 368–380     

良溶剂中环形高分子单链的结构与动力学性质的模拟研究

本文采用多粒子碰撞动力学与分子动力学耦合的模拟方法研究了环形高分子单链在良溶剂中的静态与动态性质,并与线形分子进行了对比.研究发现,环形高分子链内粒子之间的平均距离小于线形链,即粒子排列得更加紧密;相应的均方回转半径也小于线形链,线形链与环形链的均方回转半径的比值为1.77;同时,环形链扩散的速度也比线形链快,两者比值为1.10.模拟结果揭示了扩散行为是排斥体积作用和流体力学相互作用耦合的结果,在扩散过程中,流体力学相互作用消减了排斥体积作用对扩散行为的贡献.此外,通过对有和没有流体力学相互作用的多粒子碰撞动力学得到的结果作对比,研究了流体力学相互作用对高分子静态和动态行为的影响,结果表明,流体力学相互作用使高分子链在极稀溶液中的扩散速度变快.     

Phase behavior and surface tensions of amphiphilic fluorinated random copolymer aqueous solutions

Phase behavior and surface tension of aqueous solutions of fluorinated random copolymers [perfluoroalkylacrylate]–[poly(ethyleneoxide)methacrylate], [C_mRf-acrylate]-[EO_n-methacrylate] with fluroalkyl carbon number m = 8, 6, 4, 2 and number of ethyleneoxide unit, n = 9 and 4.5 were investigated as a function of composition and different combinations of m and n. Isotropic solutions are formed at lower temperatures over wide concentration range of copolymer but at higher temperature phase separation occurs. The cloud point of copolymer decreases with decreasing n as well as m, and also with decreasing the number of poly(ethyleneoxide)methacrylate chain per perfluorinatedalkylacrylate chain, suggesting that the copolymers become more hydrophobic on decreasing m and n. Equilibrium and dynamic surface tension measurements show that copolymers become increasingly surface active as m as well as n decrease but the adsorption at the air–water interface is very slow due to bulkiness of the molecules. No clear evidence of the formation of micellar aggregates could be obtained from surface tension–composition curves.     

流体力学关联对胶体簇团大小的影响

用计算机模拟的方法研究了流体力学关联对胶体簇团大小的影响．研究表明,流体力学关联可使簇团尺寸大大增加,约为无流体力学关联时簇团大小的２～２０倍（在研究情况下）．把该结果与前人的研究作了对照,并解释了其中可能的原因     

Conductivity of diblock copolymer system filled with conducting nano-particles: Effect of copolymer morphology

We explore the effect of temperature-induced morphological changes in insulating diblock copolymer system (DBC) filled with conductive fillers on the conductivity of this composite. By making use of the developed method that relies on the consistent phase-field model of DBC, Monte-Carlo simulations of the filler distribution in DBC, and resistor network model, we quantitatively relate the morphology of filled DBC and its conductivity. In particular, we demonstrate that the order–disorder transition between the random and ordered microphases of DBC causes the conductor-insulator transition in the network of conductive fillers immersed in this system. The order–order transition between the ordered lamellae and cylindrical microphases of DBC is found to co-occur with a jump in the composite conductivity caused by restructuring of the conductive filler network.     

Controlled phase separations in solutions of soluble polyelectrolyte complex of DIVEMA (copolymer of divinyl ether and maleic anhydride)

Copolymer of divinyl ether and maleic anhydride (DIVEMA) is known to possess some anti-tumor and immune-stimulating activity and use as a drug carrier in anti-tumor drug delivery systems. Samples of DIVEMA of different degrees of polymerization were synthesized and characterized. Interaction of the hydrolyzed water-soluble DIVEMA polyanions with poly(N-ethyl-4-vinylpyridinium) cations (PEVP) has been studied. According to the potentiometry data, almost all carboxylic groups of the polyanions were able to form ion pairs with PEVP. In aqueous and water-salt solutions, formation of either soluble or insoluble polyelectrolyte complexes occurred depending on pH, ratio of the oppositely charged groups, and degree of polymerization of PEVP and/or DIVEMA. The phase separations followed general rules revealed by studying mixtures of PEVP and polycarboxylic acids. However in the case of DIVEMA, a significant broadening of the region for insoluble complexes at the expense of the region of soluble complexes was established. The data obtained demonstrate plausible advantages of the complex formation as the non-covalent modification of the polymeric carrier that endow DIVEMA with the ability for reversible soluble-insoluble transformation, in particular at physiological pH and ionic strength.     

Behavior of thermo- and pH-responsive copolymer of N-isopropylacrylamide and maleic acid in aqueous solutions

A thermo- and pH-responsive copolymer of N-isopropylacrylamide with maleic acid was studied using light scattering and turbidimetry methods. Aqueous solutions with pH values from 1.8 to 10.9 and in the concentration range from 0.001 to 0.015 g/cm³ were investigated. At all pH values and concentrations, phase separation was observed at temperatures T > 33°C. The temperatures of the start and the width of the phase separation interval increased with decrease of copolymer concentration and increase in pH. The redistribution of scattering entities, namely, macromolecular unimers, micelle-like structures, and loose aggregates, and growth of aggregate hydrodynamic radius took place during heating.     

Hydrodynamic properties and conformation of poly(3‐hexylthiophene) in dilute solutions

Conducting polymers demonstrate low solubility in organic solvents. Introducing aliphatic substituents into polymer chains improves their solubility, but may also lead to changes in conformational characteristics of macromolecules. In the present work, the studies of hydrodynamic properties and conformational characteristics of comb‐shaped poly(3‐hexylthiophene) with aliphatic side substituents were carried out in chloroform solutions. Conformational analysis of the studied macromolecules was performed for the first time using homologous series with a wide range of molecular weights of the polymers in dilute solutions. The hydrodynamic properties of these macromolecules were interpreted using the worm‐like spherocylinder model and the straight spherocylinder model. The projection of the monomer unit in the direction of the main polymer chain λ = 0.37 nm was determined experimentally. The following parameters of poly(3‐hexylthiophene) were characterized and quantified: equilibrium rigidity (Kuhn segment length) А = 6.7 nm and hydrodynamic diameter of a polymer chain d = 0.6 nm. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 875–883     

Cleavable multiblock copolymer synthesized by ring‐opening metathesis copolymerization of cyclooctene and macrocyclic olefin and its hydrolysis to give carboxyl‐telechelic polymer

A novel cleavable multiblock copolymer was synthesized by ring‐opening metathesis polymerization (ROMP) of cyclooctene (COE) and a flexible 27‐membered macrocyclic olefin (MCO), which is acted as the spacer to collect the polymer structure block by block. MCO 2 was prepared via ring‐closing metathesis of the long chain alkyldiene, and then 2 was well‐ conducted ROMP with COE to provide the multiblock copolymer [Poly(COE)‐ 2 ]_m consisting of homo‐Poly(COE) blocks and ring‐opened 2 segments with different molecular weights (M_n = 30.0 – 249.6 × 10³) and polydispersity index (PDI) within 1.45–1.67 as variation of the feed ratio of COE to 2 . The multiblock copolymer chain containing weak ester linkage can be cleaved under alkali condition to afford the carboxyl‐telechelic Poly(COE) blocks with much lower molecular weights (M_n,h = 3.6–35.7 × 10³) and slight higher PDIs (1.65–1.88). The average block number on multiblock copolymer chain was obtained from the ratio of M_n to M_n,h and was reached up to the value of 7–16. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 380–388, 2010