Miscibility of poly(methoxymethyl methacrylate) and poly(methylthiomethyl methacrylate) with poly(styrene-co-acrylonitrile) and poly(p-methylstyrene-co-acrylonitrile)

The miscibility of poly(methoxymethyl methacrylate) (PMOMA) and poly(methylthiomethyl methacrylate) (PMTMA) with poly(styrene-co-acrylonitrile) (SAN) and poly(p-methylstyrene-co-acrylonitrile) (pMSAN) was studied by differential scanning calorimetry. PMOMA is miscible with SAN having an acrylonitrile (AN) content around 30 wt %. However, PMOMA is immiscible with any of the pMSAN having AN contents between 9 and 36 wt % and with pMSAN having AN contents between 19 and 34 wt %. The miscibility of the blends enables the evaluation of various segmental interaction parameters.     

Miscibility of poly(methoxymethyl methacrylate) and poly(methylthiomethyl methacrylate) with poly(vinylidene fluoride)

Summary The miscibility behaviour of poly(methoxymethyl methacrylate) (PMOMA) and poly(methylthiomethyl methacrylate) (PMTMA) with poly(vinylidene fluoride) (PVDF) was examined by differential scanning calorimetry. PMOMA/PVDF blend system was judged to be miscible on the bases of the presence of a single, composition-dependent glass transition for the blend and a pronounced melting point depression of the PVDF component. Furthermore, lower critical solution temperature (LCST) behaviour was observed for all PMOMA/PVDF blends. PMTMA/PVDF blends were found to be immiscible. Based on the melting point depression of PVDF in PMOMA/PVDF blends, the interaction parameter B was found to be -14.5 J/cm³.     

Synergetic toughening of poly(phenylene sulfide) by poly(phenylsulfone) and poly(ethylene-ran-methacrylate-ran-glycidyl methacrylate)

Poly(phenylene sulfide) (PPS) is a high-performance super-engineering plastic, but is brittle. In this study, super-tough PPS-based blends were successfully generated by melt blending PPS with poly(ethylene-ran-methacrylate-ran-glycidyl methacrylate) (EGMA) and poly(phenylsulfone) (PPSU) at (56/14/30) PPS/EGMA/PPSU composition, and their toughening mechanisms were investigated in detail. It was demonstrated the interfacial reaction between PPS and EGMA and partial miscibility between PPS and PPSU, both play important synergistic roles on the toughening. The interfacial reaction between PPS and EGMA contributes to the reduction of the PPSU domain size by the increased viscosity of the PPS matrix containing EGMA, and the increased mobility of EGMA chains by negative pressure effect. The partial miscibility between PPS and PPSU contributes to the increased interfacial adhesion between PPS and PPSU, resulting in effective propagation of the impact to the domains, and the increased mobility of not only PPSU chains but also PPS chains, causing a reduction in crystallization.     

Miscibility of poly(methoxymethyl methacrylate) and poly(methylthiomethyl methacrylate) with poly(methyl methacrylate)

Summary Poly(n-propyl methacrylate) is known to be immiscible with poly(methyl methacrylate) (PMMA). However, we have found that poly(methoxymethyl methacrylate) is miscible with PMMA, indicating the importance of ether oxygen atoms in achieving miscibility. On the other hand, poly(methylthiomethyl methacrylate) is immiscible with PMMA.     

Short poly(phenylene vinylene) chains grafted poly(organophosphazene)

Brominated poly(bis(4-methylphenoxyphosphazene) was allowed to react with 1,4-bischloromethylbenzene or 1,4-bischloromethyl-2,5-dimethoxybenzene in solution using phase transfer catalyst or potassium t-butoxide. Poly(p-phenylene vinylene) or poly(2,5-methoxy-1,4-phenylene vinylene) grafted organophosphazene copolymers were obtained. The UV-Vis absorption, photoluminescent, and thermal properties of the copolymers were measured. The copolymers are complete soluble in common organic solvents and fluoresce in the blue color range. The copolymers were used to build a series of organic light emitting diode (OLED). Only weak to nominated intensities with emission color from blue to red were obtained. The photoluminescent and electroluminescent (EL) spectra indicated there is a distribution in the PPV conjugated length. The compositions of the copolymers before and after the graft reaction were analyzed using NMR.     

Novel branched poly(l-lactide) with poly(glycerol-co-sebacate) core

A series of biodegradable poly (glycerol-sebacate-l-lactide) (PGSLA) copolymers, with variable PLLA length, were synthesized and characterized. The copolymers comprised PGS backbone chain with a nominal molecular weight of 2,800 g/mol. The length of each PLLA side chain covered the 800–14,000 range, while the length of the PLLA was easily controlled by the feed molar ratio of the l-lactide to the PGS. The structure of the copolymer was studied by nuclear magnetic resonance spectroscopy and gel permeation chromatography. Differential scanning calorimetric measurements and thermal gravimetric analysis had been performed to indicate the glass transition temperature (T _g), melting point (T _m), and the degree of crystallinity (χ _c). It was also found that the onset decomposition temperature (T _d) of the copolymers was lower than those of the linear polylactide (LPLLA). After solution casting and solvent evaporation, porous structures were found in the copolymer films by scanning electron microscope (SEM). Water contact angle results showed that the hydrophilicity of the copolymers was much higher than that of linear PLLA. In vivo, PGSLA copolymer demonstrated a favorable tissue response profile compared to PGS/LPLLA blend. There was also significantly less inflammation and fibrosis during degradation. PGSLA might therefore serve as an excellent candidate material for medical applications, given its minimal in vivo tissue response.     

Complexation between poly(methacrylic acid) and poly(vinylpyrrolidone)

The complexation between poly(methacrylic acid) (PMAA) and poly(vinylpyrrolidone) (PVP) in aqueous phase was studied by various fluorescence techniques, including fluorescence anisotropy measurements, fluorescence probe studies, and nonradiation energy transfer. It was demonstrated that the complexation of PMAA with PVP occurs within a pH range of 1 to 5 and along with complexation, the conformation of PMAA changed from a hypercoiled to a loosely coiled form. The complex ratio between the two polymers is 2:1 (PMAA/PVP, in monomer unit). Salt effect studies showed that the complexation occurred due to formation of hydrogen bonds between the two polymers. Based on these conclusions and the “connected cluster model” for PMAA at low pH, a “ladder with connected cluster” model was proposed for the structure of PMAA/PVP complex formed at low pH. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 620–627, 2001     

Victrex® poly(ethersulfone) (PES) and Victrex® poly(etheretherketone) (PEEK)

Properties of two high performance engineering thermoplastics, amorphous polyethersulfone (PES) and semicrystalline polyetheretherketone (PEEK), are discussed. Both resins can be processed by conventional techniques, compounded with high performance fibers, and have high service temperature (up to 300°C). Due to the amorphous character PES can be dissolved and spray coated into metals.     

Chemical cross-linking of conducting poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) using poly(ethylene oxide) (PEO)

Hybrid films of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) were prepared with different molecular weights of poly(ethylene oxide) (PEO). The cross-linking reaction between PEO and PEDOT:PSS was performed at high temperature and confirmed by using differential scanning calorimeter (DSC), contact angle measurement, and solid-state ¹H NMR. The effect of chemical reaction on the conductivity and morphology of these hybrid films was studied by using 4-point probe and atomic force microscope (AFM), respectively. As-spun PEO/PEDOT:PSS films have lower electric conductivity due to the addition of nonconductive PEO, and exhibits no molecular weight dependence on conductivity. After chemical cross-linking reaction at high temperature, only PEDOT:PSS films with lowest molecular weight PEO additives show enhanced conductivity with increasing reaction time. AFM result indicates that the heat-treated PEO/PEDOT:PSS hybrid films show grain-like morphology compared to ethylene glycol treated PEDOT:PSS films which shows continuous PEDOT domain. In the present work we demonstrate that the cross-linking reaction can be used to improve the wet stability of PEDOT:PSS nanofiber, showing good water resistance and excellent dimensional stability.     

Biodegradability of poly(ethylene terephthalate) copolymers with poly(ethylene glycol)s and poly(tetramethylene glycol)

Poly(ethylene terephthalate) copolymers were prepared by melt polycondensation of dimethyl terephthalate and excess ethylene glycol with 10–40mol% (in feed) of poly(ethylene glycol) (E) and poly(tetramethylene glycol) (B), with molecular weight (MW) of E and B 200–7500 and 1000, respectively. The reduced specific viscosity of copolymers increased with increasing MW and content of polyglycol comonomer. The temperature of melting (T_m), cold crystallization and glass transition (T_g) decreased with the copolymerization. T_m depression of copolymers suggested that the E series copolymers are the block type at higher content of the comonomer. T_g was decreased below room temperature by the copolymerization, which affected the crystallinity and the density of copolymer films. Water absorption increased with increasing content of comonomer, and the increase was much higher for E1000 series films than B1000 series films. The biodegradability was estimated by weight loss of copolymer films in buffer solution with and without a lipase at 37°C. The weight loss was enhanced a little by the presence of a lipase, and increased abruptly at higher comonomer content, which was correlated to the water absorption and the concentration of ester linkages between PET and PEG segments. The weight loss of B series films was much lower than that of E series films. The abrupt increase of the weight loss by alkaline hydrolysis is almost consistent with that by biodegradation.     

Miscibility of poly (etherimide) and poly (butylene naphthalate) blends

Summary Differential scanning calorimeter (DSC), optical microscopy (OM) and scanning electron microscopy (SEM) were performed to characterize the miscibility of a blend system comprising poly (butylene naphthalate) (PBN) and poly (ether imide) (PEI). DSC scans showed there was only one single Tg for each blend and the glass transitions increase monotonously with the increase of PEI content. The glass transition temperatures of the blends fitted the Fox equation well implying that the blends exhibited fine segmental scale of mixing. No lower critical solution temperature (LCST) was observed by OM for the blends. SEM micrographs showed the fracture surface of quenched sample exhibited a homogeneous structure. No obvious IR peak shift of C=O absorption at 1780 cm⁻¹ was observed suggesting a relatively low level of specific interaction between two molecules. It was concluded that these blends were miscible with non-specific intermolecular interactions. Received: 5 January 2001/Accepted: 27 February 2001     

Phase behavior of poly(methylmethacrylate) and poly(styrene-co-acrylonitrile) blends

Summary Laser light scattering was used to study the miscibility behavior of PMMA/SAN blends. These systems tend to phase separation at elevated temperatures, Above the lower critical solution temperature (LCST) a regular highly interconnected two-phase morphology is displayed. The region of stability of this structure is determined. Finally, the binary interactional parameter is estimated. It is negative due to the sufficiently repulsive intramolecular interactions relative to the repulsive intermolecular interactions.     

Synthesis of poly(phenylene acetylene) from poly(phenylene vinylene)

Summary The objective of this work was to prepare films of poly(phenylene acetylene) from films of a precursor polymer, namely poly(a, a-dibromoxylylene). This polymer was obtained by selective bromination of the vinylene groups of poly(phenylene vinylene) films in bromine/CHCl₃. Pyrolytic dehydrobromination of the brominated films under argon atmosphere gave dark yellow films which showed about 65 wt% of desired phenylene acetylene units.     

Configurational statistics of poly(L-lactide) and poly(DL-lactide) chains

Conformational characteristics of poly(lactide)s have been investigated by density functional theory and ab initio molecular orbital (MO) calculations and NMR experiments on model compounds. Characteristic ratios, configurational entropies, and internal energies of poly(L-lactide) and poly(DL-lactide), whose stereosequences were generated by Bernoulli and Markov stochastic processes, were calculated under the refined rotational isomeric state scheme with conformational energies and geometrical parameters derived from the MO calculations. In terms of the conformational characteristics thus revealed, we have elucidated the reason why unperturbed chain dimensions determined experimentally for poly(L-lactide) are scattered considerably and, furthermore, discussed crystallization and crystal structures of poly(L-lactide) and molecular characteristics of poly(DL-lactide) synthesized from rac-lactide with stereospecific polymerization catalysts.     

Solubility characteristics of poly(etheretherketone) and poly(phenylene sulfide)

The crystalline high-performance polymers poly(etheretherketone) (PEEK) and poly(phenylene sulfide) (PPS) are generally considered to be highly resistant to dissolution in most common solvents. This article reveals numerous compounds that dissolve in excess of 25 wt % of each polymer at elevated temperatures. Typical binary-phase diagrams depicting the minimum solubility temperature vs. concentration are also presented for several representative polymer–solvent mixtures for both PEEK and PPS. The phenomenon of the solvent-induced crystallization of PEEK is presented. The importance of these polymer–solvent systems for the preparation of permselective membranes is discussed.     

Mechanical properties in torsion for poly(butylene terephthalate) and a poly(ether ester) based on poly(ethylene glycol) and poly(butylene terephthalate)

The torsional behavior of poly(ether ester) (PEE) thermoplastic elastomer, based on poly(ethylene glycol) (PEG) and poly(butylene terephthalate) (PBT) was studied and compared with that of PBT itself. Two types of experiments were performed: (1) stress relaxation in torsion, and (2) measurement of intermittent couple-twist responses. It was shown that the relaxation of the torsional couple M could be represented as a sum of several exponential terms in the time, rather than as a simple exponential function. This sum might be called a Prony series on the analogy of the usual stress relaxation which occurs after stretching a sample to a certain deformation and holding it constant. The intermittent couple-twist experiments were carried out by analogy with similar experiments in elongation. For PEE the couple rises steadily with the twist, whereas for PBT it rises abruptly and remains constant within the experimental error for high twists. The residual twist, however, showed a similar trend for both PEE and PBT. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 495–502, 1998     

Interpolymer complexes of poly(acrylamide) and poly(N-isopropylacrylamide) with poly(acrylic acid): a comparative study

The interpolymer complexation, through successive hydrogen bonding, between poly(acrylamide) (PAAm) and poly(N-isopropylacrylamide) (PNiPAAm) with poly(acrylic acid) (PAA) in aqueous solution has been viscometrically and potentiometrically investigated. The stoichiometry of the complexes formed was determined. By comparing the strength of the two complexes the very important contribution of the hydrophobic interaction in their formation has been indicated.     

Thermal characteristics of poly(ethylene terephthalate) fiber grafted with poly(vinyl acetate) and poly(vinyl alcohol)

Poly(ethylene terephthalate) (PET) fibers were grafted with poly(vinyl acetate) (PVAc) and poly(vinyl alcohol) (PVA). The effects of graft copolymers PVAc and PVA on morphological properties of PET were evaluated by differential thermal analysis, differential scanning calorimetry, and thermogravimetric analysis. Melting temperature, heat of fusion, and mass fractional crystallinity of PET was not affected by graft PVAc and PVA. No individual glass transition and melting points corresponding to the graft PVAc and PVA were observed, indicating thereby that graft copolymer mainly exists in the form of free chains inside the PET matrix. Poly(vinyl alcohol) graft copolymer degraded at much lower temperatures than poly(vinyl alcohol) in powder form. Thermal stability of PET fiber was not affected by graft PVAc, where as PET–g–PVA showed an additional degradation point at 360°C.