A positive‐working photosensitive polyimide based on thermal cross‐linking and acidolytic cleavage

A novel positive‐working photosensitive polyimide (PSPI) based on a poly(hydroxyimide) (PHI), a crosslinking agent having vinyl ether groups, and a photoacid generator (PAG) was prepared. The PHI as a base resin of the three‐component PSPI was synthesized from 4,4′‐oxydiphthalic anhydride and 2,2′‐bis(3‐amino‐4‐hydroxyphenyl)hexafluoropropane through ring‐opening polymerization and subsequent thermal cyclization. 2,2′‐bis(4‐(2‐(vinyloxy)ethoxy)phenyl)propane (BPA‐DEVE) was used as a vinylether compound and diphenyliodonium 5‐hydroxynaphthalene‐1‐sulfonate was used as a PAG. The phenolic hydroxyl groups of the PHI and the vinyl ether groups of BPA‐DEVE are thermally crosslinked with acetal structures during prebake step, and the crosslinked PHI becomes completely insoluble in an aqueous basic solution. Upon exposure to UV light (365 nm) and subsequent postexposure bake (PEB), a strong acid generated from the PAG cleaves the crosslinked structures, and the exposed area is effectively solubilized in the alkaline developer. The dissolution behavior of the PSPI containing each 11.5 wt % of BPA‐DEVE and of the PAG was studied after UV exposure (365 nm) and PEB. It was found that the difference in dissolution rates between exposed and unexposed areas was enough to get high resolution. A fine positive pattern with a resolution of 5 μm in a 3.7‐μm‐thick film was obtained from the three‐component PSPI. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Visualization and quantification of the mechanical deformation induced by an electrical field in poly(ethylene naphthalene 2,6‐dicarboxylate) (PEN) films

An optical nondestructive strain measurement technique was performed to analyze the mechanical deformation induced by an electrical field within the insulating materials. Poly(ethylene naphthalene 2,6‐dicarboxylate) (PEN) films were then subjected to constant electrical fields right up to their electrical breakdown. The experimental technique made it possible to follow the various stages of the mechanical behavior of PEN in real time. The final breakdown occurred in the observation zone and the related mechanical deformation was captured. A “margarita” structure was observed with a hole at the center. The experimental results indicated that the level of the induced‐mechanical deformations depended on the local environment. We defined two different zones representing the inside and the outside of the damaged area. The induced‐deformations were larger in the damaged zone. It was also observed that deformations increased when the sample had a lower degree of crystallinity. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Organic‐acid‐catalyzed sol–gel route for preparing poly(methyl methacrylate)–silica hybrid materials

In this study, a series of organic–inorganic hybrid sol–gel materials consisting of a poly(methyl methacrylate) (PMMA) matrix and dispersed silica (SiO₂) particles were successfully prepared through an organic‐acid‐catalyzed sol–gel route with N‐methyl‐2‐pyrrolidone as the mixing solvent. The as‐synthesized PMMA–SiO₂ nanocomposites were subsequently characterized with Fourier transform infrared spectroscopy and transmission electron microscopy. The solid phase of organic camphor sulfonic acid was employed to catalyze the hydrolysis and condensation (i.e., sol–gel reactions) of tetraethyl orthosilicate in the PMMA matrix. The formation of the hybrid membranes was beneficial for the physical properties at low SiO₂ loadings, especially for enhanced mechanical strength and gas barrier properties, in comparison with the neat PMMA. The effects of material composition on the thermal stability, thermal conductivity, mechanical strength, molecular permeability, optical clarity, and surface morphology of the as‐prepared hybrid PMMA–SiO₂ nanocomposites in the form of membranes were investigated with thermogravimetric analysis, differential scanning calorimetry, dynamic mechanical analysis, gas permeability analysis, ultraviolet–visible transmission spectroscopy, and atomic force microscopy, respectively. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Polyurethane foams with 1,3‐pyrimidine ring

Attempts of obtaining of polyurethane foams using polyetherols with 1,3‐pyrimidine ring (obtained in reactions of 6‐aminouracil with oxiranes) are reported. Properties of the foams are investigated, especially their thermal stability. The foams show an improved thermal stability up to 200°C for a long time. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and aqueous solution behaviors of sodium sulfonate‐terminated dendritic poly(ester‐amine)

Sodium sulfonate‐terminated dendritic poly(ester‐amine) (SPEA) was synthesized by sulfonation of acrylic double bond‐terminated dendritic poly(ester‐amine) (APEA) with sodium hydrogen sulfite (NaHSO₃) in mixture of diglycol and 2‐butanone under normal pressure. The structure of SPEA was characterized by IR, ¹H‐NMR, and elemental analysis. SPEA was water‐soluble. 1.0–40.0% (mass) SPEA aqueous solutions appeared as dilatant fluid. When pH value varied from 1.5 to 12.0, the viscosity of 1–5% (mass) SPEA aqueous solutions changed very small, and the electric conductivity almost kept stable within pH 3.0–10.0. The relationship between the viscosity and the concentration of SPEA water solutions was similar to that of NaCl water solutions. The surface tension of SPEA water solutions was lower than that of polyethylene glycol 2000 water solutions with the same concentration. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Novel blood-compatible waterborne polyurethane using chitosan as an extender

A series of novel block polymers of polyurethane (PU) and chitosan have been prepared in two steps. The first step is the preparation of PU prepolymer, obtained from polytetramethylene oxide glycol (PTMO, M_n = 1000), isophrone diisocyanate (IPDI), and 2,2′-dimethylol propionic acid (DMPA), followed by ionizing PU prepolymer with triethylamine (TEA). The second step involves PU chain-extended by water-soluble chitosan of low molecular weight (M_n = 5000) by self-emulsion polymerization method. The sizes of the latex particles, morphology, and copolymer architecture have been characterized by dynamic light scattering (DLS), general tensile test, infrared spectroscopy (IR), surface contact angle measurement, and transmission electron microscopy (TEM). Furthermore, it shows that the addition of chitosan remarkably increases anticoagulative property of PU elastomers confirmed by the recalcification time. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Mechanical properties and antibacterial activity of peroxide‐cured silicone rubber foams

Silicone rubber (SR) foams were prepared by the peroxide curing of a silicone compound with 2,4‐dichlorobenzoyl peroxide (DCBP), di‐t‐butyl peroxide (DTBP), or 2,5‐dimethyl‐2,5‐di(t‐butylperoxy) hexane (DBPH) in the presence of 2,2′‐azobisisobutyronitrile (AIBN) as a blowing agent. The cells were formed in the foam as a result of nitrogen produced by the decomposition of AIBN during the foaming process. The cell size, hardness, and tensile properties of the SR foams were examined as a function of the peroxide concentration. When the peroxide concentration increased, the hardness and tensile strength of the SR foams increased, whereas the cell size and elongation at break decreased. The antibacterial activity of the prepared foams was also evaluated via their effects on Staphylococcus aureus and Escherichia coli. The peroxide‐cured SR foams had antibacterial activity because a toxic residue was generated by the peroxide decomposition. The foam prepared by the AIBN/DCBP system showed more antibacterial activity than the AIBN/DBPH and AIBN/DTBP ones. However, after postcuring at 250°C for 2 h, the antibacterial activity of the SR foams significantly decreased. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Entanglement network and relaxation temperature dependence of single‐site catalyzed ethylene/1‐hexene copolymers

In this work, we investigate the linear viscoelastic response of high molecular weight ethylene/1‐hexene copolymers, characterized by a narrow molecular weight distribution and comonomer content in the range from 0 to 10 mol %. A variation in the entanglement plateau modulus has been found in agreement with the recently developed packing length model. The packing model applied to viscoelastic data suggests decreased values of the characteristic ratio, accordingly with recent computer simulation results. The flow activation energy increases as the side chain content increases. This feature is thought to be related to the mobility of the molecules. The presence of side branches due to the comonomer hinders the mobility of the molecules, and increases the thermal barrier for the segmental motion. Then in the comonomer content range studied, the increase of the flow activation energy goes parallel with a decrease in the characteristic ratio. This result suggests that more parameters than only the stiffness of the chain modulate the thermal dependence of viscoelastic properties. A more refined study is necessary combining experiments with computer simulations in order to elucidate these aspects. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Restraining the associations of anthracene fluorophore by chemically linking to poly(methyl methacrylate)

Associations (dimer or aggregate) of anthracene (An) fluorophores tend to interrupt the monomer emission and reduce the quantum yield (Φ_PL); therefore, poly(methyl methacrylate) (PMMA) chain was used in this study to chemically link to anthracene and to block the mutual associations among the anthracene fluorophores. With this aim, the target polymers were prepared by anionic polymerizations with 9,10‐dibromoanthracene/s‐butyllithium as initiating system to proceed polymerizations of methyl methacrylate (MMA) directly or in the presence of 1,1‐diphenylethylene (DPE). Use of DPE before addition of MMA produces stable initiating anionic species and avoids potential side reactions during polymerization; however, it also introduces four β‐phenylene rings around the central anthracene ring, which interfere with the corresponding emission pattern and reduce the Φ_PL (32%) value due to potential interactions between phenylene rings and anthracene. On the contrast, polymerization without participation of DPE results in polymer with central anthracene ring directly connected to two PMMA chains, which gives clean vibronic emission pattern with limited association emissions and enhanced Φ_PL (52%) value. Physical blending of anthracene by PMMA is less efficient to restrain the associations and results in a film of lower Φ_PL (20%). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Development of a predictive model for polymer/solvent diffusion coefficient calculations

A new calculation procedure for free‐volume parameters is considered in this work by using viscosity prediction methods and the Levenberg‐Marquardt calculation scheme. All parameters used in the Vrentas–Duda free‐volume theory can be estimated from pure component properties. The prediction results are compared with experimental data for some polymer/solvent systems. The diffusion coefficient calculated by Vrentas–Duda theory can be used in the modeling of membrane separation processes. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008