Confined crystallization behavior of PEO in organic networks

Poly (ethylene oxide) (PEO) and poly (trimethopropane trimethacrylate) (PTMPTMA) interpenetrate networks have been synthesized. The confined crystallization behavior of PEO in the PTMTYTMA networks has been investigated by a differential scanning calorimeter and scanning electron microscope. The degree of PEO crystallinity in PEO/PTMPTMA interpenetrate networks reduces with the increase of PTMPTMA. PEO is in an amorphous state when the concentration of PEO is lower than 50% in the interpenetrate networks system. The melting points of crystalline PEO in the networks are lower than that of pure PEG, and the melting point of PEO in the networks is higher and increases with the increase of PEO in the interpenetrate networks. Wide-angle X-ray diffraction results show that the PEO crystallite size perpendicular to the (120) plane is not affected as much as PEO in silica networks. (C) 2001 Elsevier Science Ltd. All rights reserved.

Syntheses and properties of thermotropic copolyesters of p-hydroxybenzoic acid

Two series of thermotropic copolyesters of p-hydroxybenzoic acid (HBA) were synthesized by direct thermal polycondensation. One comprised aromatic copolyesters from HBA, terephthalic acid, bis(4-hydroxyphenyl) ketone (BHP) and resorcinol. The other comprised semi-aromatic copolyesters from HBA, terephthalic acid, BHP and alpha,-diols with carbon atom number of 4, 6, 8, 10. The properties of the two series were characterized by polarized light microscopy, differential scanning calorimetry and wide angle X-ray diffraction. Most of the resulting copolyesters could form a nematic phase over a wide temperature range above their melting points. The effects of Variation in composition and monomer structure on the properties of copolyesters were discussed. (C) 2001 Elsevier Science Ltd. All rights reserved.

Phase identification in a series of liquid crystalline TPP polyethers and copolyethers having highly ordered mesophase structures. 7. Phase structures in a series of copolyethers containing odd and even numbers of methylene units of different compositions

A series of liquid crystalline copolyethers have been synthesized from 1-(4-hydroxy-4'-biphenyl)-2-(4-hydroxyphenyl)propane with 1,7-dibromoheptane and 1,12-dibromododecene [coTPPs(7/12)], which represents copolyethers containing both odd and even numbers of methylene units. The molar ratio of odd to even methylene units in this series ranges from 1/9 to 9/1. The coTPPs(7/12) exhibit multiple phase transitions during cooling and heating in differential scanning calorimetry experiments. For all these thermal transitions, a small undercooling and superheating dependence is observed upon cooling and heating at different rates. Three types of phase behaviors can be classified in coTPPs(7/12) on the basis of the structural analyses by wide-angle X-ray diffraction on powder and fiber samples and by electron diffraction experiments in transmission electron microscopy. At room temperature, highly ordered smectic and smectic crystal (SC) phases are identified in coTPPs(7/12: 1/9 and 2/8), which is similar to the homopolymer TPP(m = 12). The coTPPs(7/12: 3/7, 4/6, and 5/5) possess a hexagonal columnar (Phi(H)) phase in which the molecular and columnar axes are parallel to the fiber direction and perpendicular to the hexagonal lateral packing. The coTPPs(7/12: 6/4, 7/3, and 8/2) possess a tilted hexagonal columnar (Phi(TH)) phase with a single tilt angle which increases with the increasing composition of the seven-numbered methylene units. However, in coTPP(7/12: 9/1), a Phi(TH) phase with multiple tilt angles is found. Upon heating, phase structures in most coTPPs(7/12) involving the columnar phases enter directly into the nematic (N) phase, while the coTPP(7/12: 1/9) exhibits a highly ordered smectic F (S-F) phase before it reaches the N phase. One exception is found in coTPP(7/12: 2/8), wherein the transformation from the S-F to Phi(H) occurs prior to the N phase. Combining the copolymer phase behaviors observed with the corresponding homopolymers TPP(n = 7) and TPP(m = 12), a phase diagram describing transition temperatures with respect to the composition can be constructed.

Synthesis of a novel graft-like copolymer of syndiotactic polystyrene with polybutadiene

A novel graft-like copolymer of syndiotactic polystyrene (sPS) with polybutadiene (PB) was synthesized by polymerization of styrene in a toluene solution of PB using the cyclopentadiene titanium trichloride (CpTiCl3)/methylaluminoxane (MAO) catalytic system. The effect of PB on the crystallization behavior of the copolymer was investigated by differential scanning calorimetry and wide angle X-ray diffraction. Hydrogenation of the sPS/PB copolymer with p-toluenesulfonyl hydrazide afforded a PE-like copolymer.

Phase identification in a series of liquid crystalline TPP polyethers and copolyethers having highly ordered mesophase structures. 6. Structure changes from smectic to columnar phases in a series of copolyethers containing odd and even numbers of methylene units in equal molar composition

A series of liquid crystalline copolyethers has been synthesized from 1-(4-hydroxy-4'-biphenyl)-2-(4-hydroxyphenyl)propane and different alpha,omega-dibromoalkanes [coTPP(n/m)]. In this report, coTPPs having n = 5, 7, 9, 11 and m = 12 are studied, which represent copolyethers having both varying odd number and a fixed even number of methylene units. The compositions were fixed at an equal molar ratio (50/50). These coTPPs(nlm) show multiple phase transitions during cooling and heating in differential scanning calorimetry experiments. The undercooling dependence of these transitions is found to be small, indicating that these transitions are close to equilibrium, Although the coTPPs possess a high-temperature nematic (N) phase, the periodicity order along the chain direction is increasingly disturbed when the length of the odd-numbered methylene units decreases from n 11 to 5. in the coTPPs(5/12, 7/12, and 9/12), wide-angle X-ray diffraction experiments at different temperatures show that, shortly after the N phase formation during cooling, the lateral molecular packing improves toward a hexagonal lattice, as evidenced by a gradual narrowing of the scattering halo. This process represents the possible existence of an exotic N phase, which serves as a precursor to the columnar (Phi(H)) phase. A further decrease in temperature leads to a (PH phase having a long-range ordered, two-dimensional hexagonal lattice. In coTPP(11/12), the phase structures are categorized as highly ordered and tilted, smectic and smectic crystal phases, similar to homoTPPs, such as the smectic F (S-F) and smectic crystal G (SCG) phases. An interesting observation is found for coTPP(9/12), wherein a structural change from the high-temperature Phi(H) phase to the low-temperature S-F phase occurs. It can be proven that, upon heating, the well-defined layer structure disappears and the lateral packing remains hexagonal. The overall structural differences in this series of coTPPs between those of the columnar and highly ordered smectic phases are related to the disorders introduced into the layer structure by the dissimilarity of the methylene unit lengths in the comonomers.

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.

Enzymatic degradation of poly(epsilon-caprolactone)/poly(DL-lactide) blends in phosphate buffer solution

Blend films of poly(epsilon-caprolactone) (PCL) and poly(DL-lactide) (PDLLA) with 0.5 weight fraction of PCL were prepared by means of solution casting and their degradation behavior was studied in phosphate buffer solution containing Pseudomonas (PS) lipase. Enzymatic degradation of the blend films occurred continuously within the first 6 days and finally stopped when the film weight loss reached 50%, showing that only PCL in the blends degraded under the action of PS lipase in the buffer solution. These results indicate the selectivity of PS lipase on the promotion of degradation for PCL and PDLLA. The thermal properties and morphology of the blend films were investigated by differential scanning calorimetry, wide-angle X-ray diffraction and scanning electron microscopy (SEM). The morphology resulting from aggregate structures of PCL in the blends was destroyed in the enzymatic degradation process, as observed by SEM. These results confirm again the enzymatic degradation of PCL in the blends in the presence of PS lipase. (C) 1999 Published by Elsevier Science Ltd. All rights reserved.

Synthesis and characterization of thermotropic liquid crystalline poly(ester imide)s

Two closely series of poly(ester imide)s had been synthesized by solution polycondensation of p-phenylenebis(trimellitate) dianhydride with aliphatic diamines. The differential scanning calorimetry (DSC) traces of the most poly(ester imide)s exhibited two endotherms representing the solid state to anisotropic phase transition (T-m1) and the anisotropic to isotropic melt transition (T-m2), respectively. Observation under polarizing microscope and wide-angle X-ray diffraction (WAXD) measurements suggested that the anisotropic phase formed above the melting paints (T-m1) had a smectic character. The thermogravimetric analyses (TGA) revealed that the thermal stabilities of the poly(ester imide)s were up to 350 degrees C. (C) 1999 John Wiley & Sons, Inc.

Studies on blends of LLDPE and ethylene-methacrylic acid random copolymer

Blends of linear low-density polyethylene (LLDPE) and poly(ethylene-co-methacrylic acid) (EMA) random copolymer were studied by differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), and excimer fluorescence. In binary blends, crystallization of EMA was studied, and no modification of crystal structure was detected. In excimer fluorescence measurements, emission intensities of blends of EMA and naphthalene-labeled LLDPE were measured. The ratio of the excimer emission intensity (I-D) to the emission intensity of the isolated "monomer" (I-M) decreases upon addition of EMA, indicating that PE segments of EMA interpenetrate into the amorphous phase of LLDPE. (C) 1998 Published by Elsevier Science Ltd,. All rights reserved.

Crystallization kinetics of poly(ether ether ketone) (PEEK) from its metastable melt

After isothermal crystallization of the amorphous poly(ether ether ketone), double endothermic behaviour can be found through differential scanning calorimetry experiments. During the heating scan of semicrystalline PEEK, a metastable melt, which comes from the melt of the thinner lamellar crystal populations, can be obtained between these two endotherms. The metastable melt can recrystallize immediately just above the lower melting temperature and form slightly thicker lamellae than the original ones. The thickness and the perfection depend upon the crystallization time and the crystallization temperature. By comparing the TEM morphological observations of the samples before and after partial melting, it can be shown that lamellar crystals, having different thermodynamic stability, form during isothermal crystallization. After partial melting, only the type of lamellar crystal exhibiting the higher thermodynamic stability remains. Wide angle X-ray diffraction measurements shows a slightly change in the crystallinity of the samples before and after the partial melting. Small angle X-ray scattering results exhibit a change in the long period of the lamellar crystals before and after the partial melting process. The crystallization kinetics of the metastable melt can be determined by means of differential scanning calorimetry. The kinetic analysis showed that the isothermal crystallization of the metastable PEEK melt proceeds with an Avrami exponent of n = 1.0 similar to 1.4, reflecting that probably one-dimensional or an irregular line growth of the crystal occurred between the existing main lamellae with heterogeneous nucleation. (C) 1998 Elsevier Science Ltd. All rights reserved.

Blends of linear low-density polyethylene and a diblock copolymer of hydrogenated polybutadiene and methyl methacrylate

Blends of linear low-density polyethylene (LLDPE) and a diblock copolymer of hydrogenated polybutadiene and methyl methacrylate [P(HB-b-MMA)] were studied by transimission electron microscope (TEM), differential scanning calorimetry (DSC), and wide angle X-ray diffraction (WAXD). At 10 wt% block copolymer content, block copolymer chains exist as spherical micelles and cylindrical micelles in LLDPE matrix. At 50 wt% block copolymer content, block copolymer chains mainly form cylindrical micelles. The core and corona of micelles consist of PMMA and PHB blocks, respectively. DSC results show that the total enthalpy of crystallization of the blends varies linearly with LLDPE weight percent, indicating no interactions in the crystalline phase. In the blends, no distortion of the unit cell is observed in WAXD tests.

Synthesis and properties of two series of H-bonded and non-H-bonded thermotropic liquid crystal monomers

Two series of monomers, namely n-1-bromo-(4-(4-nitrophenylazo)phenyloxy]alkanes (Bn, n = 2, 3, 4, 5, 6, 8, 10) and N-n-[4-(4-nitrophenylazo)phenyloxy]alkyl diethanolamines (Cn, n = 3, 5, 6, 10), were synthesized and characterized. Their thermal behaviour was studied by differential scanning calorimetry (DSC), wide angle X-ray diffractometry (WAXD) and polarizing optical microscopy (POM) equipped with a hot stage. The results showed that the Bns (n greater than or equal to 6) exhibit monotropic nematic liquid crystalline behaviour; no liquid crystalline phase was found for the Bns (n < 6), while for the Cns, enantiotropic smectic liquid crystallinity for n = 5, 6, 10 was seen, and for n = 3 monotropic smectic phases were found. This different phase behaviour between Bn and Cn compounds is attributed to their different end groups. The FTIR analysis of Cn indicated that there exists an intermolecular hydrogen bond between hydroxy groups, so that more stable liquid crystalline phase are formed. The effect of the length of the flexible chain on the thermal behaviour is also discussed.

Heterogeneous nucleation effects of neodymium oxide on polyamide-1010

In this paper microcrystalline structures of polyamide-1010 (PA1010) mixed with neodymium oxide (Nd2O3) were studied by Wide Angle X-ray Diffraction (WAXD) and Small Angle X-ray Scattering (SAXS). Crystallization behavior was investigated by DSC. The transition and relaxation of macromolecules in the crystalline phase were explored by Differential Scanning Calorimetry (DSC). It was revealed that neodymium oxide plays an important role in PA1010 crystallization as a heterogeneous nucleating agent. It can improve the crystallization rate, reduce crystallite size and introduce crystal imperfections. The microcrystalline structure was imposed by the addition of Nd2O3 However, the heterogeneous nucleation effect obviously does not exert its influence on the transition and relaxation of macromolecules in the crystalline phase.

The multiple melting behaviour of immiscible poly(ether ether ketone) poly(ether diphenyl ether ketone) blend

Poly(ether ether ketone)/poly(ether diphenyl ether ketone) blend containing 30 wt% PEDEK was used to investigate the melting behaviour of immiscible PEEK/PEDEK blends. The results measured from differential scanning calorimetry (d.s.c.) and wide-angle X-ray diffraction (WAXD) showed that immiscible PEEK/PEDEK blends isothermally crystallized at a temperature between Tg and Tm-2 (PEEK's normal melting point) from the glassy state also exhibited the multi-melting behaviour like poly(aryl ether ketones) homopolymers. In addition, the low-temperature melting peak was independent of composition of poly(aryl ether ketones) blends and only associated with the thermal history. (C) 1997 Elsevier Science Ltd.