Reversible Photocontrolled Swelling‐Shrinking Behavior of Micron Vesicles Self‐Assembled from Azopyridine‐Containing Diblock Copolymer

Poly(N‐isopropylacrylamide)‐block‐poly{6‐[4‐(4‐pyridyazo)phenoxy] hexylmethacrylate} (PNIPAM‐b‐PAzPy) was synthesized by successive reversible addition‐fragmentation chain transfer (RAFT) polymerization. In a water/tetrahydrofuran (H₂O/THF) mixture, amphiphilic PNIPAM‐b‐PAzPy self‐assembles into giant micro‐vesicles. Upon alternate ultraviolet (UV) and visible light irradiation, obvious reversible swelling‐shrinking of the vesicles was observed directly under an optical microscope. The maximum percentage increase in volume, caused by the UV light, reached 17%. Moreover, the swelling could be adjusted using the UV light power density. The derivation of this effect is due to photoinduced reversible isomerization of azopyridine units in the vesicles.

     

Self‐Assembly of Cylinder‐Forming ABA Triblock Copolymers under Cylindrical Confinement

The self‐assembly of two types of linear ABA triblock copolymers confined in cylindrical nanopores is studied using simulated annealing. The effects of pore size and block copolymer chain architecture on morphology, chain conformations and bridging fraction are investigated. For the bulk cylinder‐forming copolymers, novel structures such as helices and stacked toroids form, which depend sensitively on the pore size. Several significant differences between the two types of copolymers are predicted and explained based on the differences in their chain conformations and chain architectures. A simple model is proposed to explain the mean square radius of gyration for the bridge and loop chains.

     

Microstructure and Thermal and Tensile Properties of Poly(vinyl alcohol) Nanocomposite Films Reinforced by Polyacrylamide Grafted Cellulose Nanocrystals

Abstract

Polyacrylamide grafted cellulose nanocrystals (CNC-g-PAM) were incorporated into poly(vinyl alcohol) (PVA) by a solution casting method to fabricate nanocomposite films with enhanced thermal and tensile properties. The microstructure and the thermal and tensile properties of the PVA/CNC-g-PAM nanocomposite films were investigated as a function of CNC-g-PAM content. Infrared spectroscopy corroborated the presence of hydrogen bonds between PVA and the PAM on the surface of the CNC. Polarized optical microscopy and scanning electron microscopy revealed good dispersion of the CNC-g-PAM in the PVA matrix and good interfacial compatibility. Accordingly, the initial degradation temperature of the nanocomposite films was elevated slightly compared to pristine PVA film. The glass transition temperature, melting temperature, and crystallinity of the PVA also varied slightly after the incorporation of the CNC-g-PAM. At both 0% and 50% RH, the nanocomposite films showed an obvious increase of elastic modulus, no apparent change of breaking strength and a drastic reduction of elongation at break with increasing CNC-g-PAM content.     

Enthalpy Relaxation Study of Poly(Vinyl Chloride) Films Based on the Time-Temperature Superposition Principle

Abstract

In the enthalpy relaxation of poly(vinyl chloride), a decrease in enthalpy upon the isothermal ageing was measured using the differential scanning calorimetry method as a function of ageing time (t_A) and ageing temperature. The range of the ageing temperature was from 56?°C (T_g ? 25?°C) to 72?°C (T_g ? 9?°C) where T_g denotes the glass transition temperature. The limiting value of the decrease in enthalpy was determined by applying a stretched exponential function to the measured enthalpy data. The relaxation function (?) was derived from the measured enthalpy and the construction of a master curve was tried by shifting the ? ? t_A curves of the respective ageing temperatures horizontally. Although there was no agreement between the shift factors (a_T) and the relaxation times of the ? ? t_A curves, the superposition was successfully constructed and the a_T values obtained for the poly(vinyl chloride) sample were found to be comparable to those reported for viscoelastic experiments over a broad temperature range above and below T_g carried out for different polymers. The origin of the decrease in enthalpy was briefly discussed in terms of the chain dynamics in the isothermal condition.     

Free volume characteristics of 2,2-bistrifluoromethyl-4,5-difluoro-1,3-dioxole-co-tetrafluoroethylene copolymers: Effect of composition and molecular weight

2,2-bistrifluoromethyl-4,5-difluoro-1,3-dioxole-co-tetrafluoroethylene (PDD-TFE) copolymer is a good candidate to prepare gas separation membranes with excellent permeability due to its free volume characteristics. However, the influence of PDD-TFE copolymer structure on its free volume characteristics is less studied. In this paper, PDD-TFE copolymers with different compositions and molecular weights were synthesized, and their free volume characteristics were analyzed by positron annihilation lifetime spectroscopy and a molecular dynamics simulation. It indicated that the molar fraction of PDD in copolymers had a significant effect on free volume characteristics, while the molecular weight of copolymers exerted a slight influence on free volume when the molecular weight exceeded a critical region (intrinsic viscosity [η] > 68 ml g⁻¹). PDD-TFE copolymers with greater PDD molar fractions (i.e., 72% and 84%) showed bimodal distributions in positron lifetime and free volume size distributions, while PDD-TFE copolymers with lower PDD molar fractions (i.e., 27% and 35%) exhibited a single peak. The long-lifetime parameter τ₃ was assigned to micro-cavities formed by [-(TFE)_y-PDD-] segments and τ₄ was attributed to micro-cavities formed by [-(PDD)_x-TFE-] segments. The cis and trans transitions of PDD led to a local multilayer spiral structure with a 2.6–4.3 Å layer spacing, which would also increase the free volume of copolymers.     

Heterogeneous copper‐catalyzed oxidative coupling of oxime acetates with sodium sulfinates: An efficient and practical synthesis of β‐keto sulfones

An efficient and practical route to β‐keto sulfones has been developed through heterogeneous oxidative coupling of oxime acetates with sodium sulfinates by using an MCM‐41‐supported Schiff base‐pyridine bidentate copper (II) complex [MCM‐41‐Sb,Py‐Cu (OAc)₂] as the catalyst and oxime acetates as an internal oxidant, followed by hydrolysis. The reaction generates a variety of β‐keto sulfones in good to excellent yields. This new heterogeneous copper (II) catalyst can be easily prepared via a simple procedure from readily available and inexpensive reagents and exhibits the same catalytic activity as Cu (OAc)₂. MCM‐41‐Sb,Py‐Cu (OAc)₂ is also easy to recover and is recyclable up to eight times with almost consistent activity.     

Piezoelectric Nanogenerator Based on Electrospun Cellulose Acetate/Nanocellulose Crystal Composite Membranes for Energy Harvesting Application

Nanogenerators, as the typical conversion of mechanical energy to electrical energy devices, have great potential in the application of providing sustainable energy sources for powering miniature devices. In this work, cellulose acetate/cellulose nanocrystal(CA/CNC) composite nanofiber membranes were prepared by electrospinning method and then utilized to manufacture a flexible pressure-driven nanogenerator. The addition of CNC not only increased the content of piezoelectric cellulose I crystallization but also strengthened the mechanical deformation of the nanofiber membranes, which could greatly enhance the piezoelectric performance of CA/CNC composite membranes. The CA/CNC composite nanofiber membrane with 20%(mass fraction) of CNC(CA/CNC-20%) showed optimal piezoelectric conversion performance with the output voltage of 1.2 V under the force of 5 N(frequency of 2 Hz). Furthermore, the output voltage of the CA/CNC-20% nanogenerator device exhibited a linear relationship with applied impact force, indicating the great potential in pressure sensors.     

Recyclable carbon fiber‐reinforced plastics (CFRP) containing degradable acetal linkages: Synthesis,properties, and chemical recycling

Two epoxy resins containing degradable acetal linkages were synthesized by the reaction of cresol novolak‐type phenolic resin (CN) with vinyl ethers containing a glycidyl group [cyclohexane dimethanol vinyl glycidyl ether (CHDMVG) and 4‐vinyloxybutyl glycidyl ether (VBGE). Carbon fiber‐reinforced plastics (CFRPs) were prepared by heating laminated prepreg sheets with CN‐CHDMVG resin (derived from CN and CHDMVG) and CN‐VBGE resin (derived from CN and VBGE), in which carbon fibers are impregnated with epoxy resins containing curing agents [dicyandiamide (DICY)] and curing accelerator [3‐(3,4‐dichlorophenyl)‐1,1‐dimethylurea (DCMU)]. CN‐CHDMVG‐based CFRPs and CN‐VBGE‐based CFRPs exhibited almost the same tensile strength as the conventional bisphenol‐A‐based CFRPs. CN‐CHDMVG‐based CFRPs and CN‐VBGE‐based CFRPs underwent smooth breakdown with the treatment of hydrochloric acid in tetrahydrofuran at room temperature for 24 h to regenerate strands of carbon fibers. The surface conditions of the recovered carbon fibers had little changes during degradation and recovery processes on the basis of scanning electron microscopy (SEM) and X‐ray photoelectron spectroscopy (XPS). The recovered carbon fibers exhibited almost the same tensile strength as virgin carbon fibers and hence would be reused for the production of CFRPs. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1052–1059     

Synthesis,self-assembly and photo-responsive behavior of AB2 shaped amphiphilic azo block copolymer

In this work, we report the synthesis of AB2 shaped amphiphilic azo block copolymer by macromolecular azo coupling reaction. The product and intermediates were characterized by various methods. The selfassembly in selected solvents and photo-responsive behavior of the copolymer were studied by means of UV–vis spectrophotometry and TEM. Spherical aggregates can be obtained by gradually adding water into the solution of this amphiphilic azo block copolymer. Upon irradiation with polarized UV(365 nm)light, the aggregates can be elongated in the polarized direction.     

Effect of Butyl α-Hydroxymethyl Acrylate Monomer Structure on the Morphology Produced via Aqueous Emulsion Polymerization-induced Self-assembly

Polymerization-induced self-assembly(PISA) is an efficient and versatile method to afford polymeric nano-objects with polymorphic morphologies. Compared to dispersion PISA syntheses based on soluble monomers, the vast majority of emulsion PISA formulations using insoluble monomers leads to kinetically-trapped spheres. Herein, we present aqueous emulsion PISA formulations generating worms and vesicles besides spheres. Two monomers with different butyl groups, n-butyl(n BHMA) and tert-butyl(t BHMA) α-hydroxymethyl acrylate, and thus possessing different water solubilities were synthesized via Baylis-Hillman reaction. Photoinitiated aqueous emulsion polymerizations of n BHMA and t BHMA employing poly(ethylene glycol) macromolecular chain transfer agents(macro-CTAs, PEG45-CTA, and PEG113-CTA) at 40 °C were systematically investigated to evaluate the effect of monomer structure and solubility on the morphology of the generated block copolymer nano-objects. Higher order morphologies including worms and vesicles were readily accessed for t BHMA, which has a higher water solubility than that of n BHMA. This study proves that plasticization of the core-forming block by water plays a key role in enhancing chain mobility required for morphological transition in emulsion PISA.