Syntheses of novel macrocyclic polyarylate oligomers based on phenolphthalein and m-phthaloyl-dichloride

Novel macrocyclic oligomers were synthesized through the condensation of phenolphthalein and m-phthaloyl-dichloride with triethylamine as catalyst in the mixed solution of methylene chloride and THF via pseudo-high-dilution technique. The oligomers were characterized by IR, H-1 NMR, MS, WAXD, TGA and DSC. It was found that the 3 : 3 adduct (molar ratio of phenolphthalein to m-phthaloyl-dichloride) and the 4 : 4 adduct were the main products and there was a small amount of crystalline in the macrocyclic mixtures. When the mixtures were heated to 360 degrees C, the crystalline disappeared.

Controlled synthesis of L-lactide-b-epsilon-caprolactone block copolymers using a rare earth complex as catalyst

Well-defined block copolymers of L-lactide-b-epsilon-caprolactone were synthesized by sequential polymerization using a rare earth complex, Y(CF3COO)(3)/Al(iso-Bu)(3), as catalyst system. The compositions of the block copolymers could be adjusted by manipulating the feeding ratio of comonomers. The characterizations by GPC, H-1 NMR, C-13 NMR, and DSC displayed that the block copolymer, poly(epsilon-caprolactone-b-L-lactide) [P(CL-b-LLA)], had a narrow molecular weight distribution and well-controlled sequences without random placement.

Influence of interface on radiation effects of crystalline polymer - radiation effects on polyamide-1010 containing BMI

Aimed at saving the radiation dose required to crosslinking the polyamid-1010, BMI/PA1010 systems containing different amounts of difunctional crosslinking agent N,N'-bis-maleimide-4,4'-biphenyl methane (BMI) were prepared and the structure changes at the crystallographic and supermolecular levels before and after irradiation were studied by using WAXD, SAXS, and DSC techniques. It was found that by incorporation of BMI the microcrystal size L-100 is lowered due to the formation of hydrogen bond between the carbonyl oxygen of BMI and the amide hydrogen of PA1010 in the hydrogen bonded plane, and the overall crystallinity W-c is also decreased. The presence of BMI causes the crystal lamella thickness d(c) to decrease and greatly thickens the transition zone d(tr) between the crystalline and amorphous regions. As for the irradiated specimen, the maximum increments in the L-100 and W-c against dose curves decrease with BMI content, and the interception point D-i, at which the L-100 and W-c curves intercept their respective horizontal line of L-100/L-100(0) and W-c/W-c(0)=1, shift to lower dose with an increase in BMI concentration. In addition. the mechanism of the radiation chemical reactions in the three different phases under the action of BMI are discussed with special focus on the interface region. (C) 1999 Published by Elsevier Science Ltd. All rights reserved.

Mixing enthalpy and phase behavior of PEO/PVAc blends

Phase behaviors and heats of mixing of the miscible blends of poly(ethylene oxide) (PEO) and poly(vinyl acetate) (PVAc) with different molecular weights were investigated by DSC. A method proposed by Natasohn and Ebert et al. was adopted to estimate the binodal temperatures and the enthalpies of mixing from onset temperatures and values of areas of a series of endothermic peaks (corresponding to heats of demixing), respectively, in their heating scanning thermograms obtained with different heating rates. Phase diagrams and heats of mixing of this blending system were also predicted by using Sanchez-Lacombe lattice fluid theory. A very good agreement was obtained for both. phase behaviors and heats of mixing obtained with two different methods.

Miscibility and crystallization behavior of poly(beta-hydroxybutyrate)/poly(ethylene oxide) blends

The miscibility and crystallization behavior of poly(beta-hydroxybutyrate) (PHB)/poly(ethylene oxide) (PEO) blends were studied by differential scanning calorimetry(DSC) and polarizing microscopy (POM). It is found that the miscibility is related to the composition of the blends. When the PEO content is over 20 percent, the miscible blends turn into partially miscible and the phase separation can be observed with POM. The addition of the PEO influences not only the morphology of PHB crystals and the radial growth rate of spherulites, but also the cold crystallization temperature.

Crystallization behevior of poly(3-dodecylthiophene)

The crystallization behavior of poly (3-dodecylthiophene) (P3DDT) is studied bq differential scanning calorimetry (DSC) under different cooling rates. When the methods of Jeziorny., Ozawa and a new one proposed by our laboratory are applied to describe its nonisothermal crystallization behavior, the new one is confirmed to be the best and convenient. By determining kinetic parameters, the analysis of the nonisothermal crystallization behavior is performed. According to Kissinger method, the crystallization activation energy of P3DDT is also evaluated.

Study of the effect of hydrogen bonding on the phase behaviour of p-nitro azobenzene derivatives with hydrophilic tails

The infrared spect ra of N-n-(4-nitrophenyl)azophenyloxyalkyldiethanolamines (Cn) are examined in the range of 4000-400 cm(-1) at different temperatures and the assignment of the fundamental vibrations given. Based on (1) the localization of the broad absorption band at 3456 cm(-1), and (2) attribution of the associated OH bands centred at 1410-1390, 1100, and 650-634 cm(-1) to, respectively delta OH deformation, nu C-O stretching and gamma OH out-of-plane bending, intermolecular hydrogen bonding between OH groups in the crystalline, liquid crystalline and isotropic states is proposed. By considering the results of FTIR, WAXD and DSC measurements, the molecular arrangement of C10 in its smectic A phase as consisting of hydrogen bonding and strong interaction between dipolar groups (NO,) is proposed. This may explain the high stability and high orientational ordering property of Cn compounds in the liquid crystalline state compared with that of n-bromo-1-[4-(4-nitrophenyl)azophenyl]oxyalkanes (Bn).

Conformation transformation of syndiotactic polypropylene induced by stretching and annealing

Conformation transformation of syndiotactic polypropylene(sPP) induced by stretching and annealing processes has been investigated by WAXD, IR and DSC, The results indicate that not only the quenched samples but also the isothermally crystallized samples can form the crystals with all-trans conformation by means of uniaxially stretching at room temperature. The all-trans conformation crystals are of metastability, which can transform to stable crystals with (TTGG)(2) helical conformation at higher annealing temperatures.

Isothermal and non-isothermal crystallization kinetics of syndiotactic polypropelene

Isothermal and non-isothermal crystallization kinetics of a syndiotactic polypropylene(sPP) sample synthesized by new metallocene catalyst at different annealing temperatures and different cooling rates have been investigated by using differential scanning calorimetry(DSC) and density analysis. The equilibrium melting temperature( T-m(0)) is 158 degrees C by Hoffman-Weeks method. The equilibrium heat of fusion(Delta H-m(0)) is 88J/g in terms of the density analysis and DSC methods. The lateral and end surface free energies derived from the Lauritzen-Hoffman spherulitic growth rate equation are sigma = 5.2erg/cm(2) and sigma(e) = 69erg/cm(2), respectively. The work of chain folding is determined to be q = 33.75kJ/mol. Modified Avrami equation and Ozawa equation can be used to describe the non-isothermal crystallization behavior. And a new and convenient approach by combining the Avrami equation and Ozawa equation in a same crystallinity is used to describe the non-isothermal behavior as well. The crystallization activation energies are evaluated to be 73.7kJ/mol and 73.1kJ/mol for isothermal crystallization and non-isothermal crystallization, respectively. The Avrami exponent n is 1.5 similar to 1.6 for isothermal crystallization procedure, while the Avrami exponent n,is 2.5 similar to 3.5 for non-isothermal crystallization procedure. This indicated the difference of nucleation and growth between the two procedures.

Synthesis and properties of optically active poly(amide-imide)s containing axially dissymmetric 1,1 '-binaphthyl moieties

Novel optically active aromatic poly(amide-imide)s (PAIs) containing 1,1'-binaphthyl-2,2'-diyl units in the main chain were prepared by polycondensation reactions of newly synthesized dianhydride, 2,2'-bis(3,4-dicarboxylzenzamido)-1,1'-binaphthyl dianhydride[(S)-BN-DADA and (+/-)-BNDADA], with diamines, The properties of the resulted PAIs were fully characterized by a combination of investigations on inherent viscosity, thermal properties(DSC and TGA), specific rotation, CD and UV-Vis absorbance. These PAIs showed good solubilities, thermal properties and optical stabilities. Interesting UV-Vis absorption behavior of films casted from these PAIs was observed and analyzed.

Synthesis and characterization of novel crosslinkable side-chain liquid crystalline polyesters

Crosslinkable side-chain liquid crystalline polyesters PCn from N-[n-(4-(4-nitrophenylazo)phenyloxy)alkyl]diethanolamine (Cn, n = 3, 5, 6, 10) as mesogenic monomers and maleic anhydride were synthesized and characterized. The thermal properties of PCn's were studied by means of DSC, polarized optical microscopy (POM) and wide angle X-ray diffraction (WAXD), and the results showed that all the polymers studied exhibit enantiotropic liquid crystallinity. In the molar mass independent region, the relatively high content of cis -CH=CH- groups in the polymer backbone of PC3 causes an increase of the melting temperature (T-m) and a decrease of T-g and isotropisation temperature (T-i). The crosslinking of PCn in the radical polymerization with styrene was confirmed by FTIR spectroscopy. The absorption band at 1300 cm(-1) attributed to the in-plane C-H-bending vibration of trans -CH=CH- in the polymer backbone disappeared after crosslinking, indicating that the trans -CH=CH- functions are consumed in the crosslinking polymerization of styrene.

Synthesis and properties of thermotropic copoly(ester imide)s

A dicarboxylic acid, N,N'-hexane-1,6-diylbis(trimellitimide), was prepared by the reaction of trimellitic anhydride with 1,6-hexane diamine. From the diacid, a series of copoly(ester imide)s had been synthesized by thermal condensation with p-hydroxybenzoic acid and diphenols with different structures. Properties of the resulting copoly(ester imide)s were characterized by polarized light microscopy, differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD). Most of the copoly(ester imide)s formed a nematic phase over a wide temperature range above their melt. The effects of the copoly(ester imide)s composition and the structures of diphenols on the temperature related to liquid crystalline transition were investigated.

Syndiotactic polystyrene/thermoplastic polyurethane blends using poly(styrene-b-4-vinylpyridine) diblock copolymer as a compatibilizer

The effect of adding diblock copolymer poly(styrene-b-4-vinylpyridine) (P(S-b-4VPy), to immiscible blends of syndiotactic polystyrene (sPS)/thermoplastic polyurethane (TPU) on the morphology, thermal transition, crystalline structure, and rheological and mechanical properties of the blends has been investigated. The diblock copolymer was synthesized by sequential anionic copolymerization and was melt-blended with sPS and TPU. Scanning electron microscopy (SEM) showed that the added block copolymer reduced the domain size of the dispersed phase in the blends. Differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) revealed that the extent of compatibility between sPS and TPU affected the crystallization of the sPS in the blends. Tensile strength and elongation at break increased, while the dynamic modulus and complex viscosity decreased with the amount of P(S-b-4VPy) in the blend. The compatibilizing effect of the diblock copolymer is the result of its location at the interface between the sPS and the TPU phases and penetration of the blocks into the: corresponding phases, i.e. the polystyrene block enters the noncrystalline regions of the sPS, and the poly(4-vinylpyridine) block interacts with TPU through intermolecular hydrogen bonding. (C) 1999 Elsevier Science Ltd. All rights reserved.

Rheological, thermal, and morphological properties of ABS-PA1010 blends

Noncompatibilized and compatibilized ABS-nylon1010 blends were prepared by melt mixing. Polystyrene and glycidyl methacrylate (SG) copolymer was used as a compatibilizer to enhance the interfacial adhesion and to control the morphology. This SG copolymer contains reactive glycidyl groups that are able to react with PA1010 end groups (-NH2 or -COOH) under melt conditions to form SG-g-Nylon copolymer. Effects of the compatibilizer SG on the rheological, thermal, and morphological properties were investigated by capillary rheometer, DSC, and SEM techniques. The compatibilized ABS-PA1010 blend has higher viscosity, lower crystallinity, and smaller phase domain compared to the corresponding noncompatibilized blend. (C) 1999 John Wiley & Sons, Inc.

Nonisothermal crystallization and melting behavior of poly(beta-hydroxybutyrate)-poly(vinyl-acetate) blends

Nonisothermal crystallization and melting behavior of poly(P-hydroxybutyrate) (PHB)-poly(vinyl acetate) (PVAc) blends from the melt were investigated by differential scanning calorimetry using various cooling rates. The results show that crystallization of PHB from the melt in the PHB-PVAc blends depends greatly upon cooling rates and blend compositions. For a given composition, the crystallization process begins at higher temperatures when slower scanning rates are used. At a given cooling rate, the presence of PVAc reduces the overall PHB crystallization rate. The Avrami analysis modified by Jeziorny and a new method were used to describe the nonisothermal crystallization process of PHB-PVAc blends very well. The double-melting phenomenon is found to be caused by crystallization during heating in DSC. (C) 1999 John Wiley & Sons, Inc.