Highly Monodisperse Sub‐microspherical Poly(glycidyl methacrylate) Nanocomposites with Highly Stabilized Gold Nanoparticles

Sub‐micrometer spheres of poly(glycidyl methacrylate) (PGMA) with a layer of poly(allylamine hydrochloride) (PAH) film are prepared by an easily controlled assembly method. The gold nanoparticles (Au NPs) exhibit a discontinuous structure on the PGMA@PAH particle surface, exhibiting a surface interaction between the PGMA spheres and the Au NPs. PAH not only modifies the surface of the PGMA particles but also affirmatively affects the crystallite of the PGMA particles. The real permittivity of the nanocomposite spheres is much higher than that of pure PGMA spheres. An improved thermal stability is observed in the nanocomposite spheres. The calculated bandgap (0.91 eV) of the nanocomposite spheres is observed to be lower than that (4.92 eV) of pure PGMA spheres.

     

Enhancement of Anhydrous Proton Conductivity of Poly(vinylphosphonic acid)–Poly(2,5‐benzimidazole) Membranes via In Situ Polymerization

Polymer electrolyte membranes (PEMs) are synthesized via in situ polymerization of vinylphosphonic acid (VPA) within a poly(2,5‐benzimidazole) (ABPBI) matrix. The characterization of the membranes is carried out by using Fourier transform infrared (FTIR) spectroscopy for the interpolymer interactions, thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) for the thermal properties, and scanning electron microscopy (SEM) for the morphological properties. The physicochemical characterizations suggest the complexation between ABPBI and PVPA and the formation of homogeneous polymer blends. Proton conductivities in the anhydrous state (150 °C) measured by using impedance spectroscopy are considerable, at up to 0.001 and 0.002 S cm^?1 for (1:1) and (1:2) molar ratios, respectively. These conductivities indicate significant improvements (>1000×) over the physically blended samples. The results shown here demonstrate the great potential of in situ preparation for the realization of new PEM materials in future high‐temperature and non‐humidified polymer electrolyte membrane fuel cell (PEMFC) applications.

     

Investigation of Chain Dynamics in Poly(n‐alkyl methacrylate)s by Solid‐State NMR: Comparison with Poly(n‐alkyl acrylate)s

PnAMAs exhibit a local nanophase separation associated with intriguing chain dynamics (Macromol. Chem. Phys. 2005 , 206, 142). PnAMAs of high molar mass, as determined by SEC and MHKS parameters, were investigated in the melt with a recently‐developed solid‐state NMR method (NOE with dipolar filter; Solid State Nucl. Magn. Res. 2005 , 28, 160). The correlation times are assigned to the relaxation of the alkyl nanodomains, as coupled motions of the main chain and hindered local modes in the side chain. Comparison with poly(n‐alkyl acrylates) shows a higher anisotropy of the main chain motions and a better organized local nanophase separation in PnAMAs.

     

Chain Dynamics of Poly(oxyethylene) in Nanotubes of α‐Cyclodextrin by Solid‐State 2H NMR

Summary: Solid‐state ²H NMR spectroscopy was used to examine the chain dynamics of perdeuterated poly(oxyethylene) (d‐POE) inside α‐cyclodextrin (α‐CD) nanotubes. The nanotubes were prepared by aqueous self‐assembly of α‐CD onto either low‐molecular‐weight (1.5 kg/mol) or high‐molecular‐weight (25.8 kg/mol) monodisperse d‐POE. At a given temperature, POE chain segments exhibit faster dynamics when included inside the CD nanotubes as compared to the bulk. Even at 150 K, when no large‐angle dynamics are detected in bulk POE, evidence for chain motions in the nanotube‐confined POE is observed. The ²H line shapes representing this motion were modeled by a discrete 3‐site jump using a ln‐Gaussian distribution of correlation times. An activation energy of 15 ± 1 kJ/mol was determined and the motion envisioned as gauche defects propagating along the primarily trans chains included within CD nanotubes. As the nanotube length decreased, the jump angle became much less defined and more isotropic motions were observed for POE segments at elevated temperatures (>270 K).

     

A New Approach for the Synthesis of pH‐Responsive Cross‐Linked Micelles from a Poly(glycidyl methacrylate)‐Based Functional Copolymer

An amphiphilic poly(ethylene glycol)methyl ether‐block‐poly(glycidyl methacrylate) (MPEG‐b‐PGMA) diblock copolymer is first synthesized via atom transfer radical polymerization. Epoxy groups of this precursor block copolymer are converted to hydroxyl and tertiary amine residues by reacting with diethyl amine over a ring‐opening reaction. The resulting diblock copolymer is poly(ethylene glycol)methyl ether‐block‐poly(3‐diethylamino‐2‐hydroxypropyl methacrylate) (MPEG‐b‐PDEAHPMA). Micellar solution of this diblock copolymer is prepared at pH 12.0 in aqueous media. At high pH (12.0), core – shell micelles are formed with PDEAHPMA‐core and MPEG‐shell. PDEAHPMA blocks have both hydroxyl and tertiary amine groups that provide reactivity against divinyl sulfone (DVS) and a response to solution pH, respectively. Cross‐linking of hydroxyl groups of PDEAHPMA chains in the micelle core is successfully achieved by adding DVS. At pH 2.0, the DEAHPMA‐core of core cross‐linked (CCL) micelles becomes protonated and hence swelling is observed. The effect of varying the DVS concentrations is also studied. The micelle formation of diblock copolymer and its response to solution pH are investigated by using surface tensiometer, ¹H NMR spectroscopy, and dynamic light scattering (DLS) techniques. CCL micellar structure and its response to solution conditions are investigated with transmission electron microscopy and DLS studies, respectively.

     

Electrospinning of Poly[acrylonitrile‐co‐(glycidyl methacrylate)] Nanofibrous Mats for the Immobilization of Candida Antarctica Lipase B

PANGMA nanofibers and nanomats with fiber diameters of 200–300 nanometers were fabricated by electrospinning. Cal‐B was covalently immobilized onto the PANGMA nanomats via three different immobilization routes. The properties of the Cal‐B‐immobilized PANGMA nanomats were assayed and compared with the free Cal‐B. The observed Cal‐B loading on these nanomats is up to ≈50 mg · g^?1, and their hydrolytic activity is up to ≈2 500 nmol · min^?1 · mg^?1, much higher than free enzyme powder and also slightly higher than Novozyme 435. Cal‐B immobilized PANGMA nanomats have better reusability, thermal stability, and storage ability than free Cal‐B. They retain over 50% of their initial activity after 15 cycles, over 65% after 10 h heat incubation, and over 75% after 30 d storage.

     

Proton‐Conducting Poly(phenylene oxide)–Poly(vinyl benzyl phosphonic acid) Block Copolymers via Atom Transfer Radical Polymerization

Block copolymers containing poly(phenylene oxide) (PPO) and poly(vinyl benzyl phosphonic acid) segments are synthesized via atom transfer radical polymerization (ATRP). Monofunctional PPO blocks are converted into ATRP active macroinitiators, which are then used to polymerize a diethyl p‐vinylbenzyl phosphonate monomer in order to obtain phosphonated block copolymers bearing pendent phosphonic ester groups. Poly(phenylene oxide‐b‐vinyl benzyl phosphonic ester) block copolymers are hydrolyzed to corresponding acid derivatives to investigate their proton conductivity. The effect of the relative humidity (RH) is investigated. The proton conductivity at 50% RH and one bar of vapor pressure approaches 0.01 S cm^?1.     

Temperature and pH Dual‐Responsive Behavior of Dendritic Poly(N‐isopropylacrylamide) with a Polyoligomeric Silsesquioxane Core and Poly(2‐hydroxyethyl methacrylate) Shell

Novel temperature and pH dual‐responsive dendritic polyoligomeric silsesquioxane (POSS)–poly(N‐isopropylacrylamide) (PNIPAm)–poly(2‐hydroxyethyl methacrylate) (PHEMA) copolymers are prepared via atom transfer radical polymerization and click reactions. The cloud points (T_c) decrease with decreasing pH from 10.0 to 5.0 due to the weakened inter‐molecular interactions and enhanced intra‐molecular hydrogen bonding, whereas the T_c exhibits a small increase from pH 5.0 to 4.0 because of the better solvation of PHEMA at highly acidic conditions. The above findings are corroborated by the different sizes of aggregates observed by dynamic light scattering. The encapsulation of a fluorescent dye and stimulated release by temperature and pH changes are also demonstrated.     

Synthesis of a Poly(vinyl alcohol)‐Based Graft Copolymer Having Poly(ε‐caprolactone) Side Chains by Solution Polymerization

Poly(vinyl alcohol)‐graft‐poly(ε‐caprolactone) (PVA‐g‐PCL) was synthesized by ring‐opening polymerization of ε‐caprolactone with poly(vinyl alcohol) in the presence of tin(II) 2‐ethylhexanoate as a catalyst in dimethyl sulfoxide. The relationship between the reaction conditions of the solution polymerization and the chemical structure of the graft copolymer was investigated. The degree of substitution (DS) and degree of polymerization (DP) of the PCL side chains were roughly controlled by varying the reaction periods and feed molar ratios of the monomer and the catalyst to the backbone. PVA‐g‐PCL with a PCL content of 97 wt.‐% (DP = 22.8, DS = 0.54) was obtained in 56 wt.‐% yield. The graft copolymer was soluble in a number of organic solvents, including toluene, tetrahydrofuran, chloroform, and acetonitrile, which are solvents of PCL. The molecular motion of the graft copolymer from ¹H NMR measurements appears to be restricted to some extent at 27–50°C, however the ¹H NMR signal intensities measured at temperatures higher than ca. 50°C reflect the actual chemical structure of the graft copolymer as determined by elemental analysis. The graft copolymer having a short PCL side chain (DP = 4.4, DS = 0.15) was amorphous. The melting temperature of a sample with relatively high PCL content (DP = 22.8, DS = 0.54) was observed at 39°C. Thermogravimetric analysis revealed that the thermal stability of PVA was improved by introducing PCL side chains. The surface free energies of the air‐side of a graft copolymer film, as calculated by Owens' equation using contact angles, were comparable to that of PCL homopolymer.     

Physically and Chemically Cross‐Linked Poly{[(maleic anhydride)‐alt‐styrene]‐co‐(2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid)}/Poly(ethylene glycol) Proton‐Exchange Membranes

Novel proton exchange membranes were solvent‐cast from DMF solutions of the terpolymers poly[(MA‐alt‐S)‐co‐AMPS], containing hydrophobic phenyl and reactive hydrophilic carboxylic and organo‐sulfonic acid fragments with different compositions, and PEGs with different molecular weights and amounts. These membranes were formed as a result of physical (via H‐bonding) and chemical (via PEG) cross‐linking. The structures of membranes were confirmed by FT‐IR and ¹H‐ and ¹³C NMR spectroscopy. Mechanical and thermal properties, swellability, and proton conductivity of these membranes were significantly affected both by the chemical composition of the terpolymers (mainly the AMPS content) and also the cross‐linker (PEG) molecular weight and content in the final form of the membranes. It was concluded that the membranes prepared by using the terpolymer with an AMPS content of 36.84 mol‐% and PEG with a molecular weight of 1 450 and with an initial PEG content of 30 wt.‐% are the most suitable ones for fuel cell applications.

     

New Complex Crystals of Chiral Poly(L‐lactic acid) and Different Tactic Poly(methyl methacrylate)

Based on evidence from differential scanning calorimetry (DSC), wide‐angle X‐ray diffraction (WAXD), and Fourier‐transform infrared (FTIR) spectroscopy, a new stereocomplex crystal (DSC T_m = 175 °C, with WAXD 2θ = 10.0° and 12.5°) is proven for the first time between structurally dissimilar chiral poly(L ‐lactic acid) (PLLA) and syndiotactic poly(methyl methacrylate) (sPMMA). There is a strong complexing capacity only between low molecular weight PLLA and sPMMA, in miscible state, at specific weight fractions (70:30). The complexing capacity is more significant when the mixtures are melt‐crystallized at T_c = 110 °C or lower, and the intensity of this complex can be further enhanced if it is annealed between 100 and 160 °C, below its T_m = 175 °C. The new complex crystal can be formed only between PLLA and sPMMA, but not with isotactic or atactic PMMA.     

Study of Uniaxially Stretched Isotactic Poly(propylene) by 1H Solid‐State NMR and IR Spectroscopy

Changes in the amount of the rigid, semi‐rigid and soft fractions, molecular mobility and domain thickness of uniaxially stretched iPP were investigated as a function of temperature, draw ratio, drawing temperature and drawing rate. Correlations are established between the thicknesses of rigid domains and the amount of the rigid fractions of uniaxially stretched iPP. Also established are correlations between the thickness of rigid domains and the molecular mobility of the rigid fraction of uniaxially stretched iPP. The drawing temperature has an important effect on the strain‐induced transformation of the spherulitic morphology of iPP to a fibrillar one.

     

Proton‐Conducting Zirconium Pyrophosphate/Poly(2,5‐benzimidazole) Composite Membranes Prepared by a PPA Direct Casting Method

Zirconium pyrophosphate (ZPP)/poly(2,5‐benzimidazole) composites were prepared by polymerization of 3,4‐diaminobenzoic acid with zirconium hydrogen phosphate in polyphosphoric acid. The composite membranes for polymer electrolyte membranes were prepared by casting the polymerization solutions directly onto stainless steel plates. Membranes doped in 60 wt.‐% phosphoric acid solution had high proton conductivity values of more than 0.12 S · cm^?1 (at 180 °C and 1% RH). Physical properties of the doped membranes, including the mechanical strength and dimensional stability, improved as ZPP content in the composites increased to 10–20 wt.‐%.

     

Crystallization of Poly(vinylidene fluoride) in Blends with Poly(methyl methacrylate‐co‐methacrylic acid) Copolymers

A series of poly(methyl methacrylate‐co‐methacrylic acid) (PMMA‐co‐MAA) random copolymers ranging in MAA content from 0–15 mol% is synthesized and blended with poly(vinylidene fluoride) (PVDF). Using infrared spectroscopy, it is observed that the absorption bands attributed to hydrogen‐bonded carbonyl groups increase in intensity as the amount of MAA in the copolymer increases. In DSC analysis, the crystallization temperature of the PVDF in the blend initially decreases by ca. 12 °C with MAA contents ranging from 0 to 5.5 mol%; however, a PVDF blend with a 15 mol% MAA copolymer has a crystallization temperature that is only ca. 3 °C below that of pure PVDF. Similarly, spherulitic growth rate analysis initially shows a decrease in radial growth rate for PVDF in blends with PMMA‐co‐MAA copolymers containing less than 5.5 mol% MAA. At higher MAA copolymer contents, the spherulitic growth rate approaches that of pure PVDF. It is concluded that the presence of the MAA comono­mer in the PMMA‐co‐MAA copolymer initially (<5.5 mol% MAA) increases the intermolecular interactions between the copoly­mer and the PVDF. However, as the MAA content of the copolymer rises above 5.5 mol%, intramolecular hydrogen bonding interactions within the PMMA‐co‐MAA copolymer cause the copoly­mer to be less compatible with PVDF.

     

Synthesis and Characterization of Comb‐Like Copolymers Based on Poly(ε‐caprolactone) and Poly(α‐olefin)

Comb‐like copolymers based on a polyolefin backbone of poly(10‐undecene‐1‐ol) (PUol) with poly(ε‐caprolactone) (PCL) side chains are synthesized in two steps. After synthesis of PUol by metallocene‐catalyzed polymerization, the side‐chain hydroxyl functionalities of this polar polyolefin are used as an initiator for the ring‐opening polymerization (ROP) of ε‐caprolactone (CL). In this context, copolymers with different lengths of PCL grafts are prepared. The chemical structure and the composition of the synthesized copolymers are characterized by ¹H and ¹³C NMR spectroscopy. It is shown that the hydroxyl end groups of PUol act effectively as initiating sites for the CL ROP. Size‐exclusion chromatography (SEC) measurements confirm the absence of non‐attached PCL and the expected increase in molar mass after grafting. The thermal and decomposition behaviors are investigated by DSC and thermogravimetric analysis (TGA). The effect of the length of the PCL grafts on the crystallization behavior of the comb‐like copolymers is investigated by DSC and wide‐angle X‐ray scattering (WAXS).

     

Effect of Tacticity on the Structure of Poly(1‐octadecene)

Summary: A sample of poly(1‐octadecene), synthesized with a highly active heterogeneous Ziegler‐Natta catalyst, has been fractioned with heptane, giving soluble and insoluble fractions. Both fractions and the original polymer have been characterized by size exclusion chromatography, solution and solid‐state ¹³C NMR, DSC and X‐ray diffraction. The results show that the fractionation occurs on the basis of both molecular mass and tacticity differences, with the atactic content concentrated in the lower molecular mass chains. Thus, the soluble fraction, having a lower average molecular mass than the original sample, consists predominantly of atactic chains, whereas the insoluble fraction is mainly isotactic. The analysis of the solid‐state structure reveals that both atactic and isotactic fractions are able to crystallize, although their crystalline structures are different. The NMR and X‐ray data together support the “most probable” structure for the isotactic polymer advanced by Turner‐Jones. That structure is characterized by an orthorhombic crystal form, where a) the backbone crystallizes in a quaternary helical conformation, b) the sidechains are packed in a way analogous to orthorhombic polyethylene, and c) successive sidechains are conformationally inequivalent. Support for points b) and c) are respectively found in the chemical shift of the sidechains and in the splittings observed for backbone carbons and for some sidechain carbons located near the points of attachment. In addition, there is evidence that the mobility of sidechain sites at points near both the bonded and free ends are not uniform from chain to chain. On the other hand, the crystal form for the atactic polymer shows only sidechain order with some support for the notion that this order approximates the disordered hexagonal rotator phase of the alkanes.

X‐ray diffractograms of the three poly(1‐octadecene) samples.     

Effect of Branched Side Chains on the Physicochemical and Photovoltaic Properties of Poly(3‐hexylthiophene) Isomers

Two P3HT isomers with branched alkyl side chains, P3EBT and P3MPT, are synthesized. The HOMO energy levels of P3EBT and P3MPT are ?5.35 and ?5.24 eV, respectively, which are significantly lower than that of P3HT with a linear side chain. The absorption edges of the two P3HT isomer films, especially those of P3EBT, are blue‐shifted in comparison with that of P3HT. A PSC based on P3EBT:IC₆₀BA (2:1 w/w) shows a high open‐circuit voltage of 0.98 V, which is the highest V_oc reported so far for polythiophene‐based PSCs. A PSC based on P3MPT:IC₇₀BA (2:1 w/w) exhibits a power conversion efficiency of 3.62% with a V_oc of 0.91 V. P3MPT is suitable for the application in tandem PSCs.     

Thermoresponsive UCST‐Type Behavior of Interpolymer Complexes of Poly(ethylene glycol) and Poly(poly(ethylene glycol) methacrylate) Brushes with Poly(acrylic acid) in Isopropanol

Upper critical solution temperature (UCST)‐type thermoresponsive behavior of poly(ethylene glycol)–poly(acrylic acid) (PEG–PAA) and poly(poly(ethylene glycol) methacrylate)–poly(acrylic acid) (PPEGMA–PAA) interpolymer complexes has been observed in isopropanol. For these investigations, PPEGMA and PAA with various average molecular weights have been synthesized by atom transfer radical polymerization. It has been found that both the PEG and PPEGMA have lower cloud point temperatures (T _cp) than its mixed polymer solutions with PAA, whereas PAA does not show such behavior in the investigated temperature range. These findings indicate the reversible formation of interpolymer complexes with variable structure and composition in the solutions of the polymer mixtures in isopropanol. Increasing the ethylene glycol/acrylic acid molar ratio or the molecular weight of either the PAA or the H‐acceptor PEG component of the interpolymer complexes increases the UCST‐type cloud point temperatures of these interpolymer systems. The polymer–polymer interactions by hydrogen bonds between PAA and PEG or PPEGMA and the correlations between T _cp and structural parameters of the components revealed in the course of these investigations may be utilized for exploring well‐defined UCST‐type material systems for various applications.

     

Immiscible Poly(L‐lactide)/Poly(ε‐caprolactone) Blends: Influence of the Addition of a Poly(L‐lactide)‐Poly(oxyethylene) Block Copolymer on Thermal Behavior and Morphology

Summary: A binary blend of poly (L ‐lactide) (PLLA) and poly(ε‐caprolactone) (PCL) of composition 70:30 by weight was prepared using a twin screw miniextruder and investigated by differential scanning calorimetry (DSC), optical microscopy and scanning electron microscopy (SEM). Ternary 70:30:2 blends were also obtained by adding either a diblock copolymer of PLLA and poly(oxyethylene) (PEO) or a triblock PLLA‐PCL‐PLLA copolymer as a third component. Optical microscopy revealed that the domain size of dispersed PCL domains is reduced by one order of magnitude in the presence of both copolymers. SEM confirmed the strong reduction in particle size upon the addition of the copolymers, with an indication of an enhanced emulsifying effect in the case of the PLLA‐PEO copolymer. These results are analyzed on the basis of solubility parameters of the blend components.

Optical micrograph of M3EG2 blend melt quenched at 125 °C.     

Molecular Motions in the Supramolecular Complexes between Poly(ε‐caprolactone)‐Poly(ethylene oxide)‐Poly(ε‐caprolactone) and α‐ and γ‐Cyclodextrins

The structure and molecular motions of the triblock copolymer PCL‐PEO‐PCL and its inclusion complexes with α‐ and γ‐cyclodextrins (α‐ and γ‐CDs) have been studied by solid‐state NMR. Different cross‐polarization dynamics have been observed for the guest polymer and host CDs. Guest–host magnetization exchange has been observed by proton spin lattice relaxation T₁, proton spin lattice frame relaxation T_1ρ and 2D heteronuclear correlation experiments. A homogeneous phase has been observed for these complexes. Conventional relaxation experiments and 2D wide‐line separation NMR with windowless isotropic mixing have been used to measure the chain dynamics. The results show that for localized molecular motion in the megahertz regime, the included PCL block chains are much more mobile than the crystalline PCL blocks in the bulk triblock copolymer. However, the mobility of the included PEO block chains is not very different from the amorphous PEO blocks of the bulk sample. The cooperative, long chain motions in the mid‐kilohertz regime for pairs of PCL‐PEO‐PCL chains in their γ‐CD channels seem more restricted than for the single PCL‐PEO‐PCL chains in the α‐CD channels, however, they are not influencing the more localized, higher frequency megahertz motions.