Preparation and photochromism of poly(methyl methacrylate) microspheres containing spirooxazine

Photochromic poly(methyl methacrylate) (PMMA)/spirooxazine microspheres were prepared by in situ suspension polymerization and those photochromic behaviors were investigated. When UV irradiation was subjected to the PMMA/spirooxazine microspheres, the reflection spectra generated by photochromic reaction was clearly observed and its reversible decoloration behaviors responded rapidly in the dark. Photochromic microspheres prepared in this work, could be used to photochromic fabrics such as microcapsules for fragrant finishing of fabrics, as well as those are could be applied in sensing materials.     

Low temperature suspension polymerization of methyl methacrylate for the preparation of high molecular weight poly(methyl methacrylate)/silver nanocomposite microspheres

In order to prepare high molecular weight poly(methyl methacrylate) (PMMA)/silver nanocomposite microspheres, methyl methacrylate was suspension-polymerized in the presence of silver nanoparticles at low temperature with 2,2′-azobis(2,4-dimethylvaleronitrile) as an initiator. The rate of conversion was increased by increasing the initiator concentration. When silver nanoparticles were added, the rate of polymerization decreased slightly. High monomer conversion (about 85 %) was obtained in spite of low polymerization temperature of 30°C. Under controlled conditions, PMMA/silver microspheres with various number-average degrees of polymerization (6,000–37,000) were prepared. Morphology studies revealed that except for normal suspension microspheres with a smooth surface, a golf ball-like appearance of the microspheres was observed, due to the migration and aggregation of the hydrophilic silver nanoparticles at the sublayer beneath the microsphere’s surface.     

Miscibility and crystallization behaviors of poly(trimethylene terephthalate)/poly(ethylene naphthalate) blends

Poly(trimethylene terephthalate) (PTT)/poly(ethylene naphthalate) (PEN) blends of various compositions were prepared by the solution-blending and melt-blending methods. The changes in miscibility and crystallization behaviors of the blends upon thermal treatment above the melting temperature of the blends at 280°C were investigated by using DSC, DMA,¹H NMR, and SAXS analyses. Without any thermal treatment, the blend systems were not miscible, and the thermal transitions, such as glass transition, cold crystallization, and crystal melting of the individual components were observed in the DSC and DMA analyses. With thermal treatment, though, they became miscible as the thermal transitions of each component disappeared and single glass transition peaks were observed in the thermal analysis. The chain randomness determined using¹H NMR spectroscopy revealed that thermal treatment at 280°C for more than 30 min brought about transesterification reactions between the PTT and PEN segments resulting in an increase in their miscibility. These results were confirmed by the small angle X-ray analysis conducted to determine the long period (L), the thickness of the crystalline lamella stack (l _c ), and the thickness of the amorphous region (l _a ). After short thermal treatment, the melt-blended sample followed the values for the individual components. However, with extended thermal treatment, the blend became homogeneous, possessing different crystalline morphologies which resulted in different values ofL, l _c , andl _a .     

Preparation of high molecular weight poly(methyl methacrylate) with high yield by room temperature suspension polymerization of methyl methacrylate

To obtain high molecular weight (HMW) poly(methyl methacrylate) (PMMA) with high conversion, methyl methacrylate (MMA) was polymerized in suspension using a room temperature initiator, 2,2′-azobis(2,4-dimethylvaleronitrile) (ADMVN), and the effects of polymerization conditions on the polymerization behavior of MMA and the molecular parameters of PMMA were investigated. On the whole, the experimental results well corresponded to the theoretically predicted tendencies. These effects could be explained by a kinetic order of ADMVN concentration calculated by an initial rate method and an activation energy difference of polymerization obtained from the Arrhenius plot. Suspension polymerization at 25 °C by adopting ADMVN proved to be successful in obtaining PMMA of HMW (number-average degree of polymerization (P_n): 30,900–36,100) and of high yield (ultimate conversion of MMA into PMMA: 83–93 %) with diminishing heat generated during polymerization. The P_n and lightness were higher and polydispersity index was lower with PMMA polymerized at lower temperatures.     

Synthesis and hydrophilicity of poly(trimethylene 2,6-naphthalate)/poly(ethylene glycol) copolymers

Poly(trimethylene 2,6-naphthalate) (PTN)/poly(ethylene glycol) (PEG) copolymers were synthesized by the two-step melt copolymerization process of dimethyl-2,6-naphthalenedicarboxylate (2,6-NDC) with 1,3-propanediol (PD) and PEG. The copolymers produced had different PEG molecular weights and contents. The structure, thermal property, and hydrophilicity of these copolymers were studied by proton nuclear magnetic resonance (¹H-NMR) analysis, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and by contact angle, moisture content, and instantaneous elastic recovery measurements. The intrinsic viscosity and the instantaneous elastic recovery of the PTN/PEG copolymers increased with increasing PEG molecular weight and content, whereas the glass transition, melting, and cold crystallization temperatures, and the heat of fusion of the PTN/PEG copolymers all decreased with increasing PEG molecular weight or content. The thermal stability of the copolymers was not affected by PEG molecular weight or content. The hydrophilicity, as determined by contact angle and moisture content measurements of the copolymer films, was significantly improved with increasing PEG molecular weight and content.     

Thermal degradation studies of poly(o-anisidine) doped with 5-sulfosalicylic acid

Thermal decomposition of the solid state of poly(o-anisidine) (POAN) base (POAN-EB) and salt [doped with 5-sulfosalicylic (SSA) acid] (SSA-doped POAN) forms has been studied by thermogravimetric analysis (TGA) and differential thermal analysis (DTA) under non-isothermal conditions. The potential (PE) and optimum molecular geometric (OMG) energies of the repeating unit (tetramer form) of investigated matrix were calculated using molecular mechanics (MM+) calculations. These calculations (PE= −3.48×10⁹ and OMG=−122.72 kJ mol⁻¹) indicate that the optimum molecular geometric structure of this matrix is highly stable. The empirical formula of the doped polymer is best represented by [POAN-2SSA.n/6H₂O] and substantiate by elemental analysis and MM+ calculations. The full polymer decomposition and degradation were found to occur in three stages during the temperature increase. The decomposition activation energy (E _d) of both POAN base (POAN-EB) and its doped (SSA-doped POAN) were calculated by employing different approximations. The heating rate of decomposition and the frequency factor (k _o ) as well as kinetic parameters were calculated for doped or base form of this matrix. A remarkable heating rate dependence of the decomposition rate of the SSA-doped POAN matrix was observed.     

Thermal degradation and cyclodepolymerization of poly(ethylene terephthalate-co-isophthalate)s

The thermal degradation of poly(ethylene terephthalate-co-isophthalate)s (PETIs) is investigated by using isothermal thermogravimetric analysis at the temperature range of 280–310°C. The degradation rate of PETIs is increased as the mole ratio of ethylene isophthaloyl (EI) units in PETIs increases. The activation energies for the thermal degradation of poly(ethylene terephthalate), PETI(5/5), and poly(ethylene isophthalate) are 33.4, 16.6, and 8.9 kcal/mole, respectively. The degradation rate of PETIs is influenced by their volatile cyclic oligomer components formed during the polymerization and the thermal degradation. It is simulated by the rotational isomeric state model that the content of cyclic dimer in PETIs, which is the most volatile cyclic oligomer component, increases with the EI units in PETIs.     

Compatibilization of immiscible poly(<Emphasis Type="Italic">l</Emphasis>-lactide) and low density polyethylene blends

Blends of poly(l-lactide) (PLA) and low density polyethylene (LDPE) were prepared by melt mixing in order to improve the brittleness of PLA. A reactive compatibilizer with glycidyl methacrylate (GMA), PE-GMA, was required as a compatibilizer due to the immiscibility between PLA and LDPE. It contributes to reduce the domain size of dispersed phase and enhance the tensile properties of PLA/LDPE blends, especially for PLA matrix blends. A reaction product between PLA and PE-GMA, which was formed during melt-mixing and considered to act as a reactive compatibilizer, was characterized using¹H-NMR spectroscopy.     

Synthesis and hydrophilicities of Poly(ethylene 2,6-naphthalate)/Poly(ethylene glycol) copolymers

Poly(ethylene 2,6-naphthalate) (PEN)/Poly(ethylene glycol) (PEG) copolymers were synthesized by two step reaction during the melt copolymerization process. The first step was the esterification reaction of dimethyl-2,6-naphthalenedicarboxylate (2,6-NDC) and ethylene glycol (EG). The second step was the condensation polymerization of bishydroxyethylnaphthalate (BHEN) and PEG. The copolymers contained 10 mol% of PEG units with different molecular weights. Structures and thermal properties of the copolymers were studied by using¹H-NMR, DSC, TGA, etc. Especially, while the intrinsic viscosities of PEN/PEG copolymers increased with increasing molecular weights of PEG, but the glass transition temperature, the cold crystallization temperature, and the weight loss temperature of the copolymers decreased with increasing molecular weights of PEG. Consequently, the hydrophilicities by means of contact angle measurement and moisture content of the copolymer films were found to be significantly improved with increasing molecular weights of PEG.     

Improvement of mechanical and electrical properties of poly(ethylene glycol) and cyanoresin based polymer electrolytes

Ionic conductivity and mechanical properties of a mixed polymer matrix consisting of poly(ethylene glycol) (PEG) and cyanoresin type M (CRM) with various lithium salts and plasticizer were examined. The CRM used was a copolymer of cyanoethyl pullulan and cyanoethyl poly(vinyl alcohol) with a molar ratio of 1:1, mixed plasticizer was ethylene carbonate (EC) and propylene carbonate (PC) at a volume ratio of 1:1. The conductive behavior of polymer electrolytes in the temperature range of 298∼338 K was investigated. The PEG/LiClO₄ complexes exhibited the highest ionic conductivity of ∼10⁻⁵ S/cm at 25°C with the salt concentration of 1.5 M. In addition, the plasticized PEG/LiClO₄ complexes exhibited improvement of ionic conductivity. However, their complexes showed decreased mechanical properties. The improvement of ionic conductivity and mechanical properties could be obtained from the polymer electrolytes by using CRM. The highest ionic conductivity of PEG/CRM/LiClO₄/(EC-PC) was 5.33×10⁻⁴ S/cm at 25°C.     

Mechanical properties of semi-interpenetrating polymer network hydrogels based on poly(2-hydroxyethyl methacrylate) copolymer and chitosan

Semi-interpenetrating polymeric network (semi-IPN) hydrogels based on poly(2-hydroxyethyl methacrylate) (PHEMA) and poly(2-hydroxyethyl methacrylate-co-sodium methacrylate) [P(HEMA-co-SMA)], and chitosan with different molecular weights were prepared by crosslinking with ethylene glycol dimethacrylate (EGDMA) and poly(ethylene glycol) diacrylate (PEGDA) and their gelation time, water content, mechanical properties, and morphology were investigated. In consideration of the influence of the molecular weight of chitosan, there is no big difference in the water content, while tensile properties and compressive modulus increased as the molecular weight of chitosan increased. The water content increased and tensile properties and compressive modulus decreased with increasing SMA concentration. Considering the effect of the crosslinking agent, PEGDA had higher water content and lower tensile and compressive moduli than EGDMA. It is suggested that PHEMA/chitosan and P(HEMA-co-SMA)/chitosan semi-IPN hydrogels with different structures and physical properties can be prepared depending on the molecular weight of chitosan, the copolymerization with SMA, and the crosslinking agent type.     

Crystallization of poly(vinylidene fluoride)-SiO2 hybrid composites prepared by a Sol-gel process

Organic-inorganic hybrid composites consisting of poly(vinylidene fluoride) (PVDF) and SiO₂ were prepared through a sol-gel process and the crystallization behavior of PVDF in the presence of SiO₂ networks was investigated by spectroscopic, thermal and x-ray diffraction measurements. The hybrid composites obtained were relatively transparent, and brittleness increased with increasing content of tetraethoxysilane (TEOS). It was regarded from FT-IR and DSC thermal analyses that at least a certain interaction existed between PVDF molecules and the SiO₂ networks. X-ray diffraction measurements showed that all of the hybrid samples had a crystal structure of PVDFγ-phase. Fresh gel prepared from the sol-gel reaction showed a very weak x-ray diffraction peak near 2θ=21° due to PVDF crystallization, and intensity increased gradually with time after gelation. The crystallization behavior of PVDF was strongly affected by the amount of SiO₂ networks. That is, SiO₂ content directly influenced preference and disturbance for crystallization. In polymer-rich hybrids, SiO₂ networks had a favorable effect on the extent of PVDF crystallization. In particular, the maximum percent crystallinity of PVDF occurred at the content of 3.7 wt% SiO₂ and was higher than that of pure PVDF. However, beyond about 10 wt% SiO₂, the crystallization of PVDF was strongly confined.     

Poly(vinylidene fluoride)/poly(ethylene-co-vinyl acetate) (20/80) blend. I. Miscibility and crystallization behavior

The miscibility and crystallization behavior of the blends of poly(vinylidene fluoride) (PVDF) and ethylene/vinyl acetate(20/80) copolymer (EVAc80) have been studied using a differential scanning calorimeter and a polarizing microscope equipped with a heating stage. From the melting point depression, the values of interaction energy densityB were calculated to be −1.3004 (cal/cm³) and the Flory-Huggins interaction parameterχ ₁₂ was found to be −0.0818 at 445.6 K. With increasing concentration of EVAc80, the radial growth rate of spherulite was reduced drastically. The FT-IR analysis of samples quenched from the melt to various temperatures showed increasing content ofβ-phase with increasing amount of blended EVA80 along with lower quenching temperature.     

Thermal decomposition kinetics of copolymers derived from<Emphasis Type="Italic">p</Emphasis>-dioxanone,L-lactide and poly(ethylene glycol)

The kinetic parameters, including the activation energyE, the reaction ordern, and the pre-exponential factorZ, of the degradation of the copolymers based on the poly(L-lactide) (PLLA) or poly(p-dioxanone-co-L-lactide) (PDO/PLLA) and diol-terminated poly(ethylene glycol) (PEG) segments have been evaluated by the single heating methods of Friedman and Freeman-Carroll. The experimental results showed that copolymers exhibited two degradation steps under nitrogen that can be ascribed to PLLA or PDO/PLLA and PEG segments, respectively. However, copolymers exhibited almost single degradation step in air. Although the values of initial decomposition temperature were scattered, copolymers showed the lower maximum weight loss rate and degradation-activation energy in air than in nitrogen whereas the higher value of temperature at the maximum rate of weight loss was observed in air.     

Surface modification of poly(lactic acid) by UV/Ozone irradiation

Hydrophobic poly(lactic acid), PLA, was modified to give hydrophilicity and dyeability to cationic dyes via UV/O₃ irradiation. The UV irradiation treatment caused ester linkage of PLA surface to break down resulting in reduced molecular weight and generation of new photooxidized products as indicated in subtracted ATR spectra and ESCA analysis. It was found that water contact angle decreased from 61 ° to 39 ° and surface energy slightly increased with increasing UV energy, which was attributed to significant contribution of polar component rather than nonpolar component resulting from the surface photooxidation of PLA. Also the surface treatment increased dyeability of PLA to C.I. Basic Blue 41 in terms of both K/S and %E. The increased dyeability may be due to photochemically introduced anionic and dipolar dyeing sites which electrostatically interact with the cationic dye as ascertained by the decreased zeta potential and its pH dependence of the modified PLA.     

Preparation and characterization of nanoscaled poly(vinyl alcohol) fibers via electrospinning

Nanoscaled PVA fibers were prepared by electrospinning. This paper described the electrospinning process, the processing conditions, fiber morphology, and some potential applications of the PVA nano-fibers. PVA fibers with various diameters (50–250 nm) were obtained by changing solution concentration, voltage and tip to collector distance (TCD). The major factor was the concentration of PVA solution which affected the fiber diameter evidently. Increasing the concentration, the fiber diameter was increased, and the amount of beads was reduced even to 0%. The fibers were found be efficiently crosslinked by glyoxal during the curing process. Phosphoric acid was used as a catalyst activator to reduce strength losses during crosslinking. Scanning electron micrograph (SEM) and differential scanning calorimetric (DSC) techniques were employed to characterize the morphology and crosslinking of PVA fibers. It was found that the primary factor which affected the crosslinking density was the content of chemical crosslinking agent.     

Spinodal phase separation and isothermal crystallization behavior in blends of VDF/TrFE(75/25) copolymer and poly(1,4-butylene adipate) (I)

Phase behavior and spinodal phase separation kinetics in binary blends of a random copolymer of vinylidene fluoride and trifluoroethylene (75/25) [P(VDF/TrFE)] and poly(1,4-butylene adipate) (PBA) have been investigated by means of optical microscopic observation and time-resolved light scattering. The blends exhibited a typical lower critical solution temperature (LCST)∼34 °C above the melting temperature of the P(VDF/TrFE) crystals over the entire blend composition range. P(VDF/TrFE) and PBA were totally miscible in the temperature gap between the melting point of P(VDF/TrFE) and the LCST. Temperature jump experiments of the 3/7 P(VDF/TrFE)/PBA blend were carried out on a light-scattering apparatus from a single-phase melt state (180 °C) to a two-phase region (205∼215 °C). Since the late stage of spinodal decomposition (SD) is prevalent in the 3/7 blend, SD was analyzed using a power law scheme. Self-similarity was preserved well in the late stage of SD in the 3/7 blend.     

Synthesis,structure, and thermal property of poly(trimethylene terephthalate-<Emphasis Type="Italic">co</Emphasis>-trimethylene 2,6-naphthalate) copolymers

Poly(trimethylene terephthalate-co-trimethylene 2,6-naphthalate)s (P(TT-co-TN)s) with various copolymer composition were synthesized, and their chain structure, thermal property and crystalline structure were investigated by using¹H-NMR spectroscopy, differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD), respectively. It was found from sequence analysis that all the P(TT-co-TN) copolymers synthesized have a statistical random distribution of TT and TN units. It was also observed from DSC thermograms that the glass transition temperature increases linearly with increasing the TN comonomer content, whereas the melting temperature of copolymer decreases with increasing the corresponding comonomer content in respective PTT- and PTN-based copolymer, showing pseudo-eutectic melting behavior. All the samples melt-crystallized isothermally except for P(TT-co-66 mol % TN) exhibit multiple melting endotherms and clear X-ray diffraction patterns. The multiple melting behavior originates from the dual lamellar population and/or the melting-recrystallization-remelting. The X-ray diffraction patterns are largely divided into two classes depending on the copolymer composition, i.e., PTT and PTNβ-form diffraction patterns, without exhibiting cocrystallization.     

Copper metallization of poly(ethylene terephthalate) fabrics via intermediate polyaniline layers

Poly(ethylene terephthalate) fabrics were metallized through electroless plating of copper. The copper plating was performed on palladium-decorated polyaniline surfaces, and polyaniline was present as an intermediate layer on fabrics to facilitate palladium formation. Different oxidation states of polyaniline were tested in their efficacy in Pd (II) reduction and subsequent Cu plating. X-ray photoelectron spectroscopy was used to monitor the surface changes along the metallization procedure, and surface resistance was measure to probe the electrical properties of the metallized fabrics.     

Syntheses of new film-forming aromatic poly(amide-imide)s containing isoindoloquinazolinedione unit in the backbone: Poly(biphenylphthalicdianhydride-oxydianiline-4,4′-diamino-3′-carbamoyl-benzanilide) (poly(BPDA-ODA-DACB))

New film forming aromatic poly(amide-imide)s containing isoindoloquinazolinedione (IQ) unit in the backbone chain (polymerXIV) have been successfully synthesized by preparing prepolymers of poly(amic acid-carbonamide), followed by subsequent thermal cyclization of the prepolymers. 4,4′-Diamino-3′-carbamoylbenzanilide (DACB)V has been synthesized by reduction of 3′-carbamoyl-4′-amino-4-nitrobenzanilideIV. The prepolymers of poly(amic-acid-carbonamide) (polymersVII andVIII) which exhibit viscosities ranging from 1.4 to 1.7 dl/g have been prepared by a condensation polymerization of monomers such as BPDA, ODA, and DACB. PolymerXIV has been obtained by thermal cyclization of the polymersVII andVIII. During the thermal cyclization reaction, imide ring structure was first introduced and then transformed to the structure of IQ unit. The thermal degradation rate of the resultant polymers were influenced by the cleavage of amide bond but the final char yield was comparable to that of poly(BPDA-ODA).