Molecular composite films from polybenzoxazole and crosslinked polymer matrixes

Films consisting of a rigid-rod polymer and thermoset resin matrixes were prepared. Poly{(benzo[1,2-d : 5,4-d′]bis(oxazole-2,6-diyl))-1,4-phenylene} (PBO) in polyphosphoric acid (PPA) was blended with 2,6-bis(4-benzocyclobutene) benzo[1,2- d : 5,4-d′]bis(oxazole) ( 1 ), and films were extruded from these solutions. The coagulated films were soluble in methanesulfonic acid (MSA). After heat treatment at 300°C, the films became insoluble in MSA. Crosslinked films were homogeneous and did not show phase segregation between the two components. These were composite films at the molecular level. Transmission electron microscopy (TEM) showed enhanced interlayer integrity and reduced microfibril separation for the molecular composite films as compared to normal PBO film. These films had significantly better torsion and tension delamination resistance. The incorporation of a second component did not sacrifice the tensile properties of PBO film. Thermal stability of these composite films was only slightly lower than that of normal PBO film. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2157–2165, 1997     

Crosslinking of hyaluronic acid with glutaraldehyde

Hyaluronic acid (HA) was chemically crosslinked with glutaraldehyde (GA) to produce water-insoluble films having low water contents when brought into contact with water. The crosslinking reaction was performed using uncrosslinked HA films in acetone–water mixtures. This method could produce water-insoluble HA films with water contents as low as 60 wt % when subjected to swelling with phosphate-buffered saline of pH 7.4 at 37°C. This 60 wt % water content was lower than any values for HA ever reported. There was an optimal HCl concentration around 0.01N for the HA crosslinking with GA in acetone—water mixtures. To get information on the crosslinking mechanism, alginic acid, which possesses hydroxyl and carboxyl groups in one molecule, similar to HA, and poly(vinyl alcohol) (PVA) and amylopectin, which possess only hydroxyl groups, were subjected to crosslinking with GA. PVA and amylopectin were also found to become water-insoluble after reaction with GA. On the basis of the infrared spectra of these crosslinked films, it was concluded that intermolecular formation of hemiacetal bonds with GA between the hydroxyl groups belonging to different HA molecules led to crosslinking. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 3553–3559, 1997     

Novel green light-emitting diode with high efficiency; synthesis and electroluminescent property of poly(2-(2′-ethylhexylthio)-5-methoxy-1,4-phenylenevinylene) (PMEHTPV)

Poly(2-(2′-ethylhexylthio)-5-methoxy-1,4-phenylenevinylene) (PMEHTPV) was synthesized in thin films via a water-soluble precursor polymer and characterized with thermogravimetric analysis (TGA), FT–IR, and elemental analysis, etc. The PMEHTPV film could be stretched up to 10 times and showed conductivity of 0.13 Scm⁻¹ when doped with FeCl₃. The 2-ethylhexylthio group resulted in blue-shifted absorption and emission compared to those of poly(2-2′-ethylhexyloxy-5-methoxy-1,4-phenylenevinylene) (MEH-PPV). The relative quantum efficiency of the device made by PMEHTPV was 20 times higher than that of MEH-PPV. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2253–2258, 1997     

Layer‐by‐layer assembly of weak‐strong copolymer polyelectrolytes: A route to morphological control of thin films

Multilayer films were assembled from a strong polyelectrolyte (poly(diallyldimethylammonium chloride), PDADMAC) and a copolymer containing both strongly charged styrene sulfonate moieties and weakly charged maleic acid moieties (poly(4‐styrenesulfonic acid‐co‐maleic acid), PSSMA). Growth of PSSMA/PDADMAC multilayers was linear, as characterized by UV‐vis spectroscopy and quartz crystal microgravimetry. The influence of both the pH of the PSSMA adsorption solutions and the ratio of SS:MA in the PSSMA on multilayer properties was investigated. Fourier transform infrared spectroscopy results showed that the ionization of carboxylic acid groups in PSSMA/PDADMAC multilayers did not vary significantly with changes in the PSSMA assembly pH. However, the multilayers showed different thicknesses, surface morphologies, and stability to post‐assembly pH treatment. We also demonstrate that PSSMA/PDADMAC multilayers are significantly more stable than PSSMA/PAH multilayers after post‐assembly pH treatment (i.e. the films remain intact when exposed to pH extremes). In addition, the surface morphology of two films (PSSMA 1:1 assembled at pH 5.8, post‐treated at pH 2 and PSSMA 3:1 assembled at pH 5.8, post‐treated at pH 11) changed significantly when the films were exposed to solutions of different pH and, in the former case, this change in film morphology was reversible. The porous morphology after treatment at pH 2 could be reversed to give a significantly smoother film after subsequent exposure to water for 24 h. Our results demonstrate that by the rational choice of the assembly pH of PSSMA, stable and pH‐responsive films can be obtained via the sequential assembly of PSSMA and PDADMAC. These films have potential in controlled release applications where film stability and pH‐responsive behavior are essential. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4341‐4351, 2007     

Ferroelectric and piezoelectric properties of a quenched poly(vinylidene fluoride-trifluoroethylene) copolymer

The ferroelectric and piezoelectric properties of melt-quenched unoriented poly(vinylidene fluoride-trifluoroethylene) (73 : 27) copolymer films as a function of the number of poling cycles have been studied. The investigation revealed that quenched films exhibit a decrease in D-E hysteresis behavior as the number of poling cycles increases when the samples are poled at room temperature. Corresponding decreases in remanent polarization, Pr, as well as small increases in the coercive field, Ec, were observed as the material was subjected to successive poling cycles. The piezoelectric coefficients, d₃₁ and e₃₁, also decreased as the number of poling cycles increased. In addition, a clear reduction in the “apparent” Curie transition temperature between unpoled and poled material was observed. Preliminary evidence indicates that films quenched from the melt to below T_c do not form a stable ferroelectric crystal phase as previously believed. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2671–2679, 1997     

Surface stress of polydimethylsiloxane networks

For thin elastic films of crosslinked polydimethylsiloxane (PDMS), the tensile modulus was found to be an increasing function of reciprocal thickness over the whole range of elongations. PDMS films between 0.052 and 0.018 mm were investigated. With decreasing film thickness, surface properties may be expected to increasingly contribute to the measured modulus. For small elongations, surface tension is expected to have no effect or to decrease the measured modulus compared with that of a bulk sample. If a surface layer with a modulus greater than that of the bulk modulus is assumed to exist, then the observed increase in modulus with decreasing film thickness can be explained. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 2391–2396, 1997     

Synthesis and characterization of optically active polyamides derived from carbohydrate-based monomers

The synthesis of three new stereoregular AB-type polyamides based on D -ribono-1,4-lactone, L -arabinose, and D -xylose has been carried out by the active ester polycondensation method. These polyamides were characterized by elemental analysis, IR and NMR spectroscopies, and powder X-ray diffraction. They displayed optical activity and had a pronounced affinity to water, although they were not soluble in this solvent. The polyamide obtained from D -ribono-1,4-lactone was highly crystalline and yielded films with spherulitic texture. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3645–3653, 1997     

Thermo- and photooxidation of polyisobutylene. I. Evolutions at temperatures above 50°C

Polyisobutylene films (PIB) were submitted to a thermal oxidation at 100°C and to a photooxidation by exposure to long-wavelength radiations (λ ≥ 300 nm) at 60°C. The modifications of the chemical structure resulting from the oxidation were determined by FT-IR analysis of the polymer films, coupled to chemical treatments that converted specifically the oxidation products. Dissolution of oxidized samples permitted analysis of the polymer by ¹³C- and ¹H-NMR. The structure of the volatile products was determined by mass spectroscopy analysis of the gas phase. Identification of the numerous products formed permitted the proposal of a scheme that accounts for the oxidation of PIB. When the irradiations are carried out at a temperature above 50°C, the depolymerization is favored and the mechanism involves two main routes of oxidation. A direct oxidation starts with the oxidation of radicals obtained by homolysis of the C C bonds on the main chain, and an induced oxidation involves hydrogen abstraction on the methylene and methyl groups by radicals formed by the direct oxidation of the polymer. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 1689–1701, 1997     

Novel method for the preparation of poly(urethane–imide)s and their properties

A polymer blend consisting of polyimide (PI) and polyurethane (PU) was prepared by means of a novel approach. PU prepolymer was prepared by the reaction of polyester polyol and 2,4-tolylenediisocyanate (2,4-TDI) and then end-capped with phenol. Poly(amide acid) was prepared from pyromellitic dianhydride (PMDA) and oxydianiline (ODA). A series of oligo(amide acid)s were also prepared by controlling the molar ratio of PMDA and ODA. The PU prepolymer and poly(amide acid) or oligo(amide acid) solution were blended at room temperature in various weight ratios. The cast films were obtained from the blend solution and treated at various temperatures. With the increase of polyurethane component, the films changed from plastic to brittle and then to elastic. The poly(urethane–imide) elastomers showed excellent mechanical properties and moderate thermal stability. The elongation of films with elasticity was more than 300%. The elongation set after the breaking of films was small. From the dynamic mechanical analysis, all the samples showed a glass transition temperature (T_g) at ca. −15°C, corresponding to T_g of the urethane component, suggesting that phase separation occurred between the two polymer components, irrespective of polyimide content. TGA and DSC studies indicated that the thermal degradation of poly(urethane–imide) was in the temperature range 250–270°C. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3745–3753, 1997     

Surface modification of poly(tetrafluoroethylene) with benzophenone and sodium hydride by ultraviolet irradiation

Poly(tetrafluoroethylene) (PTFE) films were surface modified in a solution of benzophenone and sodium hydride in dry dimethylformamide by ultraviolet (UV) light irradiation. The extent of surface modification was characterized after durations of UV light irradiation from 5–20 min at temperatures from 19–60°C. The modified films were analyzed by electron spectroscopy for chemical analysis, diffuse reflectance ultraviolet-visible light spectroscopy, attenuated total reflection Fourier transform infrared spectroscopy, dynamic contact angle measurement, and low-voltage scanning electron microscopy. PTFE surfaces produced by this modification demonstrated extensive defluorination, oxygen incorporation, surface unsaturation, and reduction in both advancing and receding dynamic water contact angles in a manner that was more extensive at long durations of irradiation and at high temperatures. Morphological damage depended upon treatment conditions, but extensive surface modification could be obtained without substantial morphological damage to PTFE films. Control experiments indicated that the surface modification proceeded by photoexcitation of either diphenyl ketyl radical anion or benzhydrol anion, the products of reaction of benzophenone with sodium hydride. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1499–1514, 1997     

Synthesis and characterization of polyimides based on new fluorinated 3,3′-diaminobiphenyls

Two new fluorinated diamine monomers, 3,3′-diamino-5,5′-bis(trifluoromethyl)biphenyl and 3,3′-diamino-6,6′-bis(trifluoromethoxy)biphenyl, as well as a known nonfluorinated analog, 3,3′-diaminobiphenyl, were synthesized. Reaction of these diamines with rigid, highly rod-like dianhydrides produced poly(amic acid)s and polyimides, which were spin coated and thermally treated to produce polyimide films for evaluation in electronics applications. It was hoped that these polyimide films would exhibit an ideal combination of low thermal expansion, reduced water absorption, and low dielectric constant but with improved elongation due to the “crankshaft” nature of the 3,3′-biphenyl unit. Unlike polyimide films from analogous 4,4′-diaminobiphenyls, however, the 3,3′-diaminobiphenyl-based polyimides did not yield low in-plane thermal expansion coefficient in spin-coated films. In some cases high elongation was achieved, but with high thermal expansion. These new diamines may nevertheless find utility in polyimides and polyaramides for membrane, fiber, and other applications. Additionally, they may be useful in modifying the properties of polymer backbones via copolymerization. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2441–2451, 1997     

Structure and molecular conformation of tussah silk fibroin films: Effect of heat treatment

Structural changes of tussah (Antheraea pernyi) silk fibroin films induced by heat treatment were studied as a function of the treatment temperature in the range 200–250°C. The DSC curve of tussah films with α-helix molecular conformation displayed characteristic endo and exo peaks at 216 and 226°C, respectively. These peaks first weakened and then completely disappeared after heating at 230°C. Accordingly, the TMA thermal shrinkage at 206°C disappeared when the films were heated at 230°C. The onset of weight loss was monitored at 210°C by means of TG measurements. X-ray diffraction profiles gradually changed from α-helix to β-sheet crystalline structure as the treatment temperature increased from 200 to 250°C. On raising the heating temperature above 200°C, the intensity of IR and Raman bands characteristic of β-sheet conformation increased in the whole ranges of amide and skeletal modes. The sample treated at 200°C showed a spectral pattern intermediate between α-helix and β-sheet molecular conformation. The IR marker band for random coil structure, still detectable at 200°C, disappeared at higher treatment temperatures. Spectral changes attributable to the onset of thermal degradation appeared at 230°C. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 841–847, 1997     

Adhesion of silicon oxide layers on poly(ethylene terephthalate). II: Effect of coating thickness on adhesive and cohesive strengths

Fragmentation tests in the uniaxial mode were performed on poly (ethylene terephthalate) (PET) films coated with a silicon oxide layer of thickness ranging from 30 to 156 nm. The coating's fragmentation process was investigated to reveal the crack onset strain and the crack density at fragmentation saturation. Adhesive strength was modeled from the Kelly-Tyson approach, including a Weibull distribution of the coating strength. The prediction was found to be independent of coating thickness, and equal to the substrate shear stress at saturation. The cohesive strength of the coating was characterized from the crack onset strain. The measured decrease in crack onset strain with coating thickness increase was modeled by means of Weibull and fracture mechanics theories, the latter providing the best predictions. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 1463–1472, 1997     

The cooperative binding behavior of sodium dodecyl sulfate to crosslinked chitosan films

The binding behavior of sodium dodecyl sulfate (SDS) to cationic chitosan, in the form of a swollen crosslinked film is described. Chitosan films were crosslinked with epichlorohydrin. Binding isotherms were determined potentiometrically. The binding isotherms of the crosslinked chitosan was compared to the binding isotherms of chitosan in free solution. As expected, a more highly cooperative binding phenomena is observed, than for cationic chitosan in free solution. The collapse of the gel occurs at a binding fraction greater than 0.6. The collapsed cationic chitosan/SDS complex is described. The presence of hydrophobic regions within the chitosan-SDS complex was demonstrated with the oleophilic dyes C.I. Disperse Yellow 23 and C.I. Solvent Green 3. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3755–3765, 1997     

Interfacial structure and properties of polyurethane/poly(methylacrylate-co-styrene) coating to regenerated cellulose film

A semiinterpenetrating polymer network (IPN) containing 72 wt % polyurethane (PU) and 6 wt % poly(methylacrylate-co-styrene) [P(MA-St)] was coated onto surfaces of regenerated cellulose (RC) film, which was prepared by coagulating a cellulose cuoxam from bagasse pulp. The interfacial structures, bonding manner, and the strength of the coated film were studied by infrared (IR),¹³C nuclear magnetic resonance (NMR), differential thermal analysis (DTA), transmission electron microscopy (TEM), and electron probe microscopy analysis (EPMA). It was shown that the RC film coated with PU/P(MA-St) has strong interfacial interactions, where covalent and hydrogen bonds are formed across the interface between cellulose and the PU/P(MA-St) coating. The interfacial structure of the coated film is regarded as a shared PU network crosslinked simultaneously with P(MA-St) and cellulose film. The tensile strength, water resistivity, and optical transmission of the coated films were considerably higher than that of the uncoated films. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 2495–2501, 1997     

Blends of polyester having amino sulfonic acid moieties with poly(vinyl alcohol) and their metal complex formation

Polyester having amino sulfonic acid moieties (TBES) was prepared by a liquid/solid biphase polycondensation of terephthaloyl chloride (TPC) and N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid (BES) in trimethyl phosphate (TMP) using triethylamine (TEA) as an acid acceptor. Blends of TBES with PVA and their metal complexes with Ni²⁺ and Co²⁺ ions were prepared. A strong interaction was observed between TBES and PVA. An electric conductivity of 10⁻⁶ S cm⁻¹ was attained for the blend films containing about 5 wt % water. A coordination structure with two chelate rings is proposed for the metal complex with Ni²⁺ and Co²⁺ ions when the molar ratio of amino sulfonic acid groups in TBES to metal ions is larger than 2. Polymer blends complexed with Ni²⁺ or Co²⁺ ions result in semi-interpenetrating polymer networks from chelate formation. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 3561–3569, 1997     

Film-forming ability and mechanical properties of coalesced latex blends

The film-forming ability of latex blends (hard latex + soft latex) and the mechanical behavior at finite strain of latex blend films (soft matrix with tough inclusions) has been investigated. The maximum weight fraction of hard latex particles (ϕ_max) which still gives rise to transparent and crack-free films has been used as film-forming ability criterion. It was shown that when the T_g of the soft latex is low (T_g(soft) < 0°C), ϕ_max is constant and equal to 0.55 because the film-forming ability is controlled by contacts between hard particles. Nevertheless, the expected effect of T_g(soft) on film-forming ability is observed (i.e., ϕ_max decreases when T_g(soft) increases) when T_g(soft) is above 0°C. From the mechanical behavior point of view, it was shown that the two main parameters controlling the mechanical behavior of latex blend films are: the mechanical properties of the soft polymer because it represents the continuous matrix and the weight fraction of hard latex particles since they enhance the local deformation of matrix under load. However, it was also proven that debounding between the T_g latex particles and low T_g matrix occurs rapidly (at an elongation ratio ≈ 30%) during uniaxial strain experiments and has to be taken into account in order to gain a thorough understanding of the mechanical behavior of these biphasic films. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2093–2101, 1997     

Controlled co‐solvent vapor annealing and the importance of quenching conditions in thin‐film block copolymer self‐assembly

A controlled co‐solvent vapor annealing system was designed and constructed to investigate the effects of solvent vapor activity during the rapid ambient quenching process on the morphology of a cylinder‐forming poly(styrene)‐b‐poly (ethylene oxide) (PS‐PEO) annealed in toluene and water vapor. A phase transformation from cylinders in the bulk to close‐packed spheres in swollen thin films occurred, which was reversed upon quenching with dry nitrogen. Quenching with humidified nitrogen preserved the spherical morphology but could significantly alter domain spacing and reduce long‐range order in the dried films under some circumstances. Specifically, long‐range order in the quenched films was found to decrease as the quenching humidity decreased from the humidity used during annealing, and the best long‐range order was obtained when the humidity remained consistent throughout both annealing and quenching. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1125–1130     

Synthesis of degradable crosslinked polymers based on 1,5-dioxepan-2-one and crosslinker of bis-ϵ-caprolactone type

Poly(lactones) may be crosslinked by ring-opening polymerization of the corresponding cyclic esters in the presence of tetrafunctional bis(ϵ-caprolactone). The homopolymer of 1.5-dioxepan-2-one (DXO) has poor mechanical properties but also some very good properties, such as biocompatibility and degradability. Crosslinking of degradable polymer based on the poly(ether-ester) DXO was performed with crosslinkers having the same reactivity as the monomer. 2,2-Bis(ϵ-caprolactone-4-yl)propane (BCP) and bis(ϵ-caprolactone-4-yl) (BCY) with tetrafunctionalities were synthesized from the corresponding diols and then used as comonomers during the polymerization of DXO. The comonomers showed the same reactivity to the initiator, stanneous 2-ethylhexanoic acid, as DXO and perfectly random crosslinked films were obtained. The crosslinked films showed a high degree of swelling already at 2–3 mol % BCP or BCY. The BCP crosslinker was somewhat less soluble in DXO at lower temperatures, but all BCP was soluble at 180°C. These polymeric films were elastic with no crystallinity and the T_g values increased from −39°C for pure DXO to −35°C for BCP crosslinked films and −21°C for BCY crosslinked ones. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 1635–1649, 1997     

Synthesis and properties of polyimide-clay hybrid films

Polyimide-clay hybrid films with four different sizes of clay minerals have been synthesized to investigate the effect of the size of clay minerals to the properties of the hybrids. Hectrite, saponite, montmorillonite, and synthetic mica were used as clay minerals. Those clays consist of stacked silicate sheets about 460 Å (hectrite), 1650 Å (saponite), 2180 Å (montmorillonite), and 12300 Å (synthetic mica) in length, 10 Å in thickness. The longer the length of clay mineral was, the more effectively properties of polyimide were improved. In the case of polyimide-mica hybrid, only 2 wt % addition of synthetic mica brought permeability coefficients of water vapor to value less than one-tenth of that of ordinary unfilled polyimide, and thermal expansion coefficient was lowered at the level of 60% of the original one. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2289–2294, 1997