Thermal properties and morphology of α-methylstyrene-butadiene-α-methylstyrene triblock copolymer

Poly(α-methylstyrene-butadiene-α-methylstyrene) (mSBmS) was synthesized by two stages living anionic polymerization. Sodium naphthalene was used as initiator and HMPT as promoter to accelerate cross-over reactions. The microstructure and composition of mSBmS were identified by infrared and nuclear magnetic resonance spectroscopes. The domain size was roughly calculated from TEM observation. It was observed that the morphology changed with the composition. The mSBmS exhibited two T_g^s, ?4 and 172°C, that associated with polybutadiene and poly-α-methylstyrene, respectively. Comparing stress relaxation behaviors of mSBmS and styrene-butadienestyrene (SBS) at various temperatures, mSBmS showed a better thermal stability and degradation resistance than SBS. From the thermal gravimetric analysis, at 200°C, mSBmS gave a weight loss less than 1%, which provided a further evidence of better thermal stability of this material than of SBS.     

Tetrahydrofuran and 3,3-bis(chloromethyl) oxetane triblock copolymers synthesized by two-end living cationic polymerization

Triblock copolymers based on tetrahydrofuran (THF) and 3,3-bis(chloromethyl) oxetane (BCMO), BCMO-block-THF-block-BCMO and poly(BCMO-co-THF)-THF-(BCMO-co-THF), have been synthesized by two-end living cationic polymerization with a bifunctional initiator, trifluoromethanesulfonic anhydride [(CF₃SO₂)₂O]. The polymers are obtained by using the two end propagating species of poly(THF) to initiate the sequential BCMO polymerization. The resulting polymers are characterized by infrared (IR), nuclear magnetic resonance (NMR), and differential scanning calorimetry (DSC), confirming that the polymers are ABA-type block copolymers. The identities of the molecular weights predetermined and which determined by GPC show the success of predetermining molecular weights of the polymers and preparing well-defined polymers. The narrow polydispersities, 1.1–1.3, indicate that the chains are propagating by a living mechanism. © 1993 John Wiley & Sons, Inc.     

Polymeric complexed membranes used as oxygen carrier: Axial and in-plane ligand effects

The complex formation reaction of modified styrene–butadiene–styrene block copolymer (SBS-g-VP and ESBS) with cobalt Schiff base (CoS) in chloroform solution is studied. The coordination number and formation constant are determined by the Miller method. The polymeric complexed membranes (SBS-g-VP–CoS and ESBS–CoS and ESBS–CoS) are made by solution casting method. The kinetics of oxygen binding to polymeric complexed membranes (SBS-g-VP–CoS and ESBS–CoS) is studied and the equilibrium, association, and dissociation constants are determined. The effects of polymeric axial ligand and of the equatorial chelate group are discussed. © 1993 John Wiley & Sons, Inc.     

Organic/Inorganic NLO materials based on reactive polyimides and a bulky alkoxysilane dye via sol/Gel process

A series of the organic–inorganic materials based on reactive polyimides and a bulky alkoxysilane dye (ASD) for second‐order nonlinear optics have been developed. Sol‐gel reaction of ASDs is utilized to grow a network in polymer matrices (composite) or to create inter‐polymer network among polyimide chains (hybrid). Moreover, a full interpenetrating polymer network (IPN) was formed through simultaneous free radical polymerization of a methacryloyl group containing polyimide, and sol‐gel process of ASDs. Scanning electron microscopy (SEM) results indicate that the inorganic networks are distributed uniformly throughout the polymer matrices on the molecular scale. The silica particle sizes are well under 1 µm based on AFM study. Second harmonic coefficients, d₃₃ of 4.5 to 48.5 pm/V have been obtained for the optically clear poled/cured polyimide/ASD samples. Excellent temporal stability was obtained for these NLO materials at 100 °C. The dynamic thermal and temporal stabilities of the IPN system were much better than those of composite and hybrid systems. Copyright ­© 2003 John Wiley & Sons, Ltd.     

Synthesis and characterization of hydrophilic thermotropic block copolyetheresters

The block copolyetheresters with a hard segment of poly (hexamethylene p,p′-bibenzoate) and a soft segment of poly (ethylene oxide) were prepared by melt polycondensation of dimethyl-p,p′-bibenzoate, 1,6-hexanediol, and polyethylene glycol (PEG) with molecular weights of 400, 1000, 2000, or 4000. These block copolyetheresters were characterized by intrinsic viscosity, GPC, FT-IR, ¹H-NMR, and water absorption. The thermotropic liquid crystalline properties were investigated by DSC, polarized microscope, and x-ray diffraction. The block copolyetheresters exhibit smectic liquid crystallinity due to the polyester segment. The transitions are dependent on the molar content and the molecular weight of PEG used. The block copolyetheresters show high water absorption due to the hydrophilic nature of the poly (ethylene oxide) segment. The water absorption increases with increasing PEG content. As the molecular weight of PEG increases, the water absorption increases significantly. The results indicate that the water absorption of the poly (ethylene oxide) segment in the block copolymers is affected by the presence of polyester segments. © 1995 John Wiley & Sons, Inc.     

Dielectric study of ferroelectric side-chain liquid crystalline polysiloxanes with broad temperature ranges of the chiral smectic C phase 1. Structure dependence of dielectric relaxation

The dielectric behavior of a series of ferroelectric side-chain liquid crystalline polysiloxanes containing 1–3 oligooxyethylene units as spacers, and 4-(S)-2-methyl-1-butyl[[[(4-hydroxy-biphenyl-4′-yl)]carbonyl]oxy] benzoate or 4-(S)-2-methyl-1-butyl[[(4-hydroxy-biphenyl-4′-yl)carbonyl]oxy]-3-fluoro benzoate side groups was studied by broadband dielectric spectroscopy. The increase of the spacer length, and incorporation of a strong dipole moment fluoro-substituent into the mesogenic group, resulted in a decrease of the relaxation activation energy and an increase in the intensity of the relaxation. Moreover, the relaxation peak of the Goldstone mode has only been observed for the FLCP with a lateral fluoro-substituent. The relationship between the thermal dynamic behavior and chemical structure is discussed in detail. Furthermore, analysis of the dielectric relaxation behavior of these FLCPs showed that the molecular relaxations could be described by the Cole-Cole equation. © 1996 John Wiley & Sons, Inc.     

Enhanced Temporal Stability of an NLO Polyurethane via a Two‐Dimensional Chromophore

A new NLO‐active polyurethane (T_g = 145°C) based on a two‐dimensional NLO chromophore has been investigated. Two ends of this lambda‐shaped chromophore can be directly bound to the main chain of polyurethane. After poling, fast relaxation of the effective second harmonic (SH) coefficient was observed at temperatures higher than 122°C. Moreover, excellent temporal stability at 100°C was obtained despite the operating temperature being very close to the fast relaxation temperature. This is due to the fact that embedding the rigid lambda‐shaped chromophores into the polymer backbone effectively restricts molecular motion at temperatures close to T_g.     

Organic sol-gel materials for second-order nonlinear optics based on melamines

A series of all organic nonlinear optical (NLO) sol-gel materials based on melamines and an azobenzene dye (Disperse Orange 3; DO3) have been investigated. Different contents of DO3 were covalently bonded with the melamine-based organic network via condensation of amino and methylol groups. The optically clear samples exhibited second-order optical nonlinearity (second-harmonic coefficient d₃₃) = 35.4 and 11.5 pm/V at 1064 and 1542 nm, respectively) after poling and curing at 220°C for 1 h. Thermal behavior of these organic NLO sol-gel systems was studied by temperature-dependent dielectric relaxation. The results indicate that the incorporation of rigid NLO-active chromophore into the melamine-based matrix leads to high rigidity and dense packing of the organic network. Subsequently, higher glass transition temperatures were obtained for the organic NLO sol-gel material with higher DO3 content. The influence of composition on the temporal stability at 100°C was also investigated. Temporal stability at 100°C was studied as a function of system composition. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2503–2510, 1999     

Synthesis,characterization, thermal,and flame retardant properties of phosphate-based epoxy resins

A new phosphorus-containing oxirane bis-glycidyl phenylphosphate (BGPP), and a diamine, bis(4-aminophenyl)phenylphosphate (BAPP), were synthesized. Both of these two phosphorus-containing compounds lead to phosphate-containing epoxy resin via curing reaction. The kinetics of the curing reaction of BGPP with various curing agents, including BAPP, were studied. The introduction of electron-withdrawing group into the compounds increases the BGPP and decreases the BAPP reactivity in the curing reaction. The thermal and the weight loss behavior of the cured epoxy resins were studied by TGA. High char yields (32–52%) as well as high limiting oxygen index (LOI) values (34–49) of these phosphorylated resins were found, confirming the usefulness of these phosphorus-containing epoxy resins as flame retardants. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 565–574, 1997.