Segmented polymer networks containing amino‐dendrimers

Polymer networks in which poly(propylene imine) dendrimers (Astramol?) are connected to each other by linear polytetrahydrofuran (polyTHF) segments, were prepared by two methods. The first method was a one‐step procedure in which bifunctionally living polyTHF, obtained by initiation of the THF polymerization with trifluoromethane sulfonic anhydride (triflic anhydride), was reacted with an amino‐dendrimer. This reaction was very fast but did not allow formation of the end products. The second method was a two‐step procedure. In a first step, living polyTHF, prepared with acryloyloxybutyl triflate as initiator, was grafted on an amino‐dendrimer, to form a star‐like, acrylate‐terminated polyTHF multi‐macromonomer with the dendrimer as core. In a second step, networks were obtained by Michael addition between the acrylate end‐groups and unreacted amino‐groups of the dendrimer. This cross‐linking reaction occurred spontaneously upon heating of the solution of the multi‐macromonomer with gelation times varying from a few minutes to a few hours, depending on the temperature and the composition of the prepolymers. With this method it was possible to prepare networks in the form of coatings or films. © 2003 Society of Chemical Industry     

The effect of segment length on some properties of thermoplastic poly(ester–siloxane)s

A series of novel thermoplastic elastomers, based on poly(dimethylsiloxane) (PDMS) as the soft segment and poly(butylene terephthalate) (PBT) as the hard segment, were synthesized by catalyzed two‐step, melt transesterification reactions of dimethyl terephthalate and methyl esters of carboxypropyl‐terminated poly(dimethylsiloxane)s (M?_n = 550–2170 g mol^?1) with 1,4‐butanediol. The lengths of both the hard and soft segments were varied while the weight ratio of the hard to soft segments in the reaction mixture was maintained constant (57/43). The molecular structure, composition and molecular weights of the poly(ester–siloxane)s were examined by ¹H NMR spectroscopy. The effectiveness of the incorporation of the methyl‐ester‐terminated poly(dimethylsiloxane)s into the copolymer chains was verified by chloroform extraction. The effect of the segment length on the transition temperatures (T_m and T_g) and the thermal and thermo‐oxidative degradation stability, as well as the degree of crystallinity and hardness properties of the synthesized TPESs, were studied. Copyright © 2003 Society of Chemical Industry     

Polymer networks based on α,ω-methacrylate-terminated poly(1,3-dioxolane)

α,ω-Methacrylate-terminated poly(1,3-dioxolane)s (polyDXL) were synthesized by cationic ring-opening polymerization of DXL in the presence of methylene-bis(oxyethylmethacrylate) as transfer agent. If the initiator concentration is small compared with the transfer agent concentration, the molecular weights of the polymers are governed by the ratio of the reacted monomer to the reacted transfer agent. The α,ω-methacrylate-terminated polyDXLs obtained undergo free radical polymerization with formation of polyacetal networks. The properties of the networks as function of the molecular weight of the corresponding prepolymers are reported.     

Synthesis and characterisation of copolyesters from poly(ethylene terephthalate) and poly(hexamethylene terephthalate)

Copolyesters containing poly(ethylene terephthalate) and poly(hexamethylene terephthalate) (PHT) were prepared by a melt condensation reaction. The copolymers were characterised by infrared spectroscopy and intrinsic viscosity measurements. The density of the copolyesters decreased with increasing percentage of PHT segments in the backbone. Glass transition temperatures (T_g). melting points (T_m) and crystallisation temperatures (T_c) were determined by differential scanning calorimetry. An increase in the percentage of PHT resulted in decrease in T_g, T_m and T_c. The as-prepared copolyesters were crystalline in nature and no exotherm indicative of cold crystallisation was observed. The relative thermal stability of the polymers was evaluated by dynamic thermogravimetry in a nitrogen atmosphere. An increase in percentage of PHT resulted in a decrease in initial decomposition temperature. The rate of crystallisation of the copolymers was studied by small angle light scattering. An increase in percentage of PHT resulted in an increase in the rate of crystallisation.     

Effects of hydrolysis on the physical properties of short glass-fibre reinforced poly(ethylene terephthalate)

The mechanical fracture strength and toughness of short-fibre composites, injection moulded from compounds of poly(ethylene terephthalate) (PET) containing 10 and 30% (by weight) (w/o) glass, have been investigated and the dependence upon matrix hydrolytic stability determined. Mouldings have been characterised by several physical techniques to evaluate molecular weight, degradation rates, crystallinity and morphology, whilst time-dependent gravimetric data were derived to quantify sorption kinetics and allow comparisons with theoretical reaction rates to be made. During melt processing, PET is hydrolysed extremely rapidly by traces of moisture (<0.02w/o). yet the inherent strength of moulded composites declines significantly only below an apparently critical molecular weight. However, on long-term humid ageing in hot water, impact behaviour especially is rendered more complex by simultaneous crystallisation, molecular reorder and losses of interfacial bond strength.     

Poly(butylene terephthalate)–clay nanocomposites prepared by melt intercalation: morphology and thermomechanical properties

Nanocomposites based on poly(butylene terephthalate) (PBT) and an organoclay (Cloisite 30B) were prepared by melt blending using a twin‐screw extruder. Two kinds of PBTs, ie PBT‐A and PBT‐B, with different inherent viscosities (η_inh), were used for this study (η_inh of PBT‐A and PBT‐B were 0.74 and 1.48, respectively). Dispersion of the clay layers in the PBT nanocomposites was characterized by using X‐ray diffraction (XRD) and transmission electron microscopy (TEM). Tensile and dynamic mechanical properties and non‐isothermal crystallization temperatures of the nanocomposites were also examined. Nanocomposites based on the higher‐viscosity PBT (PBT‐B) showed a higher degree of exfoliation of the clay and a higher reinforcing effect when compared to the composites based on the lower‐viscosity PBT (PBT‐A). The clay nanolayers dispersed in PBT matrices lead to increases in the non‐isothermal crystallization temperatures of the PBTs, with such increases being more significant for the PBT‐B nanocomposites than for the PBT‐A nanoocomposites. Copyright © 2004 Society of Chemical Industry     

Influence of the ethylene–(methacrylic acid)–Zn2+ ionomer on the thermal and mechanical properties of blends of poly(propylene) (PP)/ethylene–(vinyl alcohol) copolymer (EVOH)

The thermal and mechanical properties and the morphologies of blends of poly(propylene) (PP) and an ethylene–(vinyl alcohol) copolymer (EVOH) and of blends of PP/EVOH/ethylene–(methacrylic acid)–Zn²⁺ ionomer were studied to establish the influence of the ionomer addition on the compatibilization of PP/EVOH blends and on their properties. The oxygen transmission rate (O₂TR) values of the blends were measured as well. PP and EVOH are initially incompatible as was determined by tensile tests and scanning electronic microscopy. Addition of the ionomer Zn²⁺ led to good compatibility and mechanical behaviour was improved in all blends. The mechanical properties on extruded films were studied for 90/10 and 80/20 w/w PP/EVOH blends compatibilized with 10 % of ionomer Zn²⁺. These experiments have shown that the tensile properties are better than in the injection‐moulded samples. The stretching during the extrusion improved the compatibility of the blends, diminishing the size of EVOH domains and enhancing their distribution in the PP matrix. As was to be expected, the EVOH improved the oxygen permeation of the films, even in compatibilized blends. Copyright © 2004 Society of Chemical Industry     

Morphology and properties of poly[2‐methoxy‐5‐(2′‐ethyl‐hexyloxy)‐para‐phenylene vinylene]/silica nanoparticle hybrid films

Poly[2‐methoxy‐5‐(2′‐ethyl‐hexyloxy)‐para‐phenylene vinylene] (MEH‐PPV)/silica nanoparticle hybrid films were prepared and characterised. Three kinds of materials were compared: parent MEH‐PPV, MEH‐PPV/silica (hybrid A films), and MEH‐PPV/coupling agent MSMA/silica (hybrid B films), in which MSMA is 3‐(trimethoxysilyl) propyl methacrylate. It was found that the hybrid B films could significantly prevent macrophase separation, as evidenced by scanning electron and fluorescence microscopy. Furthermore, the thermal characteristics of the hybrid films were largely improved in comparison with the parent MEH‐PPV. The UV‐visible absorption spectra suggested that the incorporation of MSMA‐modified silica into MEH‐PPV could confine the polymer chain between nanoparticles and thus increase the conjugation length. The photoluminescence (PL) studies also indicated enhancement of the PL intensity and quantum efficiency by incorporating just 2 wt% of MSMA‐modified silica into MEH‐PPV. However, hybrid A films did not show such enhancement of optoelectronic properties as the hybrid B films. The present study suggests the importance of the interface between the luminescent organic polymers and the inorganic silica on morphology and optoelectronic properties. Copyright © 2004 Society of Chemical Industry     

Synthesis and characterization of new thermally stable poly(ester‐imide)s derived from 2,2′‐bis(4‐trimellitimidophenoxy)biphenyl and 2,2′‐bis(4‐trimellitimidophenoxy)‐1,1′‐binaphthyl and various aromatic dihydroxy compounds

A series of new alternating aromatic poly(ester‐imide)s were prepared by the polycondensation of the preformed imide ring‐containing diacids, 2,2′‐bis(4‐trimellitimidophenoxy)biphenyl (2a) and 2,2′‐bis(4‐trimellitimidophenoxy)‐1,1′‐binaphthyl (2b) with various aromatic dihydroxy compounds in the presence of pyridine and lithium chloride. A model compound (3) was also prepared by the reaction of 2b with phenol, its synthesis permitting an optimization of polymerization conditions. Poly(ester‐imides) were fully characterized by FTIR, UV‐vis and NMR spectroscopy. Both biphenylene‐ and binaphthylene‐based poly(ester‐imide)s exhibited excellent solubility in common organic solvents such as tetrahydrofuran, m‐cresol, pyridine and dichloromethane. However, binaphthylene‐based poly(ester‐imide)s were more soluble than those of biphenylene‐based polymers in highly polar organic solvents, including N‐methyl‐2‐pyrrolidone, N,N‐dimethylacetamide, N,N‐dimethylformamide and dimethyl sulfoxide. From differential scanning calorimetry thermograms, the polymers showed glass‐transition temperatures between 261 and 315 °C. Thermal behaviour of the polymers obtained was characterized by thermogravimetric analysis, and the 10 % weight loss temperatures of the poly(ester‐imide)s was in the range 449–491 °C in nitrogen. Furthermore, crystallinity of the polymers was estimated by means of wide‐angle X‐ray diffraction. The resultant poly(ester‐imide)s exhibited nearly an amorphous nature, except poly(ester‐imide)s derived from hydroquinone and 4,4′‐dihydroxybiphenyl. In general, polymers containing binaphthyl units showed higher thermal stability but lower crystallinity than polymers containing biphenyl units. Copyright © 2005 Society of Chemical Industry     

Synthesis and characterization of an interpenetrating polymer network composed of poly(methacrylic acid) and poly(vinyl alcohol)

Temperature and pH‐responsive interpenetrating polymer network (IPN) hydrogels, constructed with poly(methacrylic acid) (PMAA) and poly(vinyl alcohol) (PVA), by a sequential IPN method, were studied. The characterization of IPN hydrogels was investigated by Fourier‐transform infrared spectroscopy, differential scanning calorimetry (DSC) and swelling under various conditions. The IPN hydrogels exhibited relatively high swelling ratios, in the range 230–380 %, at 25 °C. The swelling ratios of the PMAA/PVA IPN hydrogels were pH and temperature dependent. DSC was used for the quantitative determination of the amounts of freezing and non‐freezing water. The amount of free water increased with increasing PMAA content in the IPN hydrogels. Copyright © 2004 Society of Chemical Industry