Amorphous-smectic glassy main chain LCPs. II. Dielectric study of the glass transition

The analysis of the dielectric relaxations of two main chain liquid crystalline polymers, derived from hydroxybibenzoic acid and (R,S)- and (R)-2-methyl-1,3-propanediol, is reported. These polymers can be obtained in their glassy amorphous, glassy liquid crystalline or in the crystalline state depending on their thermal history. The effect of the morphology of the sample on the dielectric spectra is analyzed. Particular interest has been paid to the characteristics of the dynamic glass transition of the different glassy states. It has been observed that the glass transition of the liquid crystalline SmC_alt phase occurs at lower temperatures and involves a smaller free volume than the glass transition of the amorphous fraction. The glass transition of the semicrystalline material follows the classical tendency of semicrystalline polymers.     

液晶热性能的研究

讨论了液晶聚合物及相应的液晶单体的热性能,指出液晶聚合物的液晶温度区间总量宽于液晶单体。通常在侧链液晶聚合物中第二种单体的引 导致液晶温度区间变宽。     

胆甾液晶高分子的研究及信息领域的潜在应用

胆甾液晶高分子兼具胆甾相液晶的独特光学性质及高分子的特点从而具有广泛的应用前景。本文在介绍胆甾相液晶独特的螺旋状分子结构和光学性能的基础上,概括了热致侧链胆甾高分子(ChSLCP)的结构及其对性能的影响,并介绍其在光信息记录方面的研究进展。     

Raman spectroscopic study of a substituted poly(phosphazene)

Summary Polyphosphazenes present a range of unique and fascinating physical properties, including thermotropic behaviour, which are highly dependent both on the type of substitution at the P atom in the inorganic backbone, and the thermal history of the material. Recent technological advances have allowed us to study this group of polymers using vibrational spectroscopy. Fourier transform (FT) Raman spectra have been recorded from samples of poly[bis(4-methoxy-phenoxy)phosphazene] with different thermal histories. With the aid of spectral subtraction methods, differences observed between the spectra have been related to the crystalline and mesophase content of the materials.     

Synthesis and characterization of chiral side‐chain liquid‐crystalline polymer containing menthol ester

The synthesis of new chiral side‐chain liquid‐crystalline polysiloxanes containing p‐(allyoxy)benzoxy‐p‐chlorophenyl (ABCH) as mesogenic units and undecylenic acid menthol ester (UM) as chiral nonmesogenic units is presented. The chemical structures of monomers and polymers are confirmed by IR spectroscopy. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) are used to measure thermal properties of those polymers. Mesogenic properties are characterized by polarized optical microscope (POM), DSC, and small‐angle X‐ray diffraction. Analytic results revealed that polymers P₀–P₆ are thermotropic liquid‐crystalline polymers with low glass transition; Polymers P₂–P₆ exhibit chiral smectic liquid‐crystalline properties with marble texture, optical rotation, and a sharp reflection at low angles in X‐ray diffraction; polymers P₀, P₁ only exhibit smectic liquid‐crystalline properties without chirality; and P₇ only exhibits chirality without liquid‐crystalline properties. All the polymers exhibit good thermal stability with temperature of 5% mass loss over 297°C. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2845–2851, 2003     

Thermotropic liquid‐crystalline polymers: Synthesis,characterization, and properties of poly(azomethine esters)

A series of poly(azomethine ester) copolymers were synthesized by the solution polycondensation method with different diamines. The synthesized polymers were characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry (DSC), hot‐stage polarized microscopy, wide‐angle X‐ray diffraction, and solution viscosity. All polymers showed good thermal stability. The thermotropic liquid‐crystalline properties were examined by DSC and by microscopic observations. Except for one, all of the polymers showed nematic liquid‐crystalline behavior. The effects of temperature on crystallinity and the substituent on solubility, thermal stability, melting temperature, and viscosity were also studied. The voluminosity and shape factor were also computed from the viscosity data. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 153–160, 2003     

Influence of shearing history on the rheological properties and processability of branched polymers. III. An amorphous long-chain branched polymer

Viscoelastic properties of branched polymers vary with their shearing history; notwithstanding, their primary molecular parameters do not change. According to a recent study, such viscoelastic variation was believed to be observed only with crystalline long-chain branched polymers such as low-density polyethylene or polyacetal. That is, the origin of the viscoelastic variation was attributed to the presence of specific entanglements at the branching points, which was formed during the crystallization process. However, the viscoelastic variation of the long-chain branched polymers is the phenomenon at temperatures well above their melting points, namely, it is considered that whether the long-chain branched polymers are crystalline or not is not essential for the occurrence of the viscoelastic variation. Thus, the influence of the shearing history on the rheological properties of an amorphous long-chain branched polymer was investigated in this paper, and it was found that, irrespective of their crystallinity, the viscoelastic properties of long-chain branched polymers vary according to their shearing history.     

Crystalline characteristics of ethylene/propylene/1,4-hexadiene terpolymers and related ethylene copolymers

An improved differential thermal analytical technique which permits the rapid, convenient characterization of the thermal behavior of crystalline polymers free of any influence of prior thermal history is presented. Characterization of both crystallization and fusion phenomena is described for ethylene/propylene copolymers subjected to well-controlled thermal scanning techniques. Parameters describing these phenomena are derived. While they are nonequilibrium parameters, they are reproducible and capable of correlation with polymer composition. the crystallization onset temperature determined by this cooling technique was found to relate to the molar ethylene content of the copolymers by an equation similar to the one derived by Flory⁵ based on equilibrium melting point. The relationship was found to hold true for a number of ethylene copolymers, including samples of linear and branched polyethylene, commercial EPDM, and ethylene/vinyl acetate copolymers.     

Synthesis, thermal and optical properties of liquid crystalline terpolymers containing azobenzene and dye moieties

The synthesis, thermal properties and photochemical and photophysical studies of new azopolymers are described. These polymers contain three different types of monomer, each of which is mainly responsible for a particular function: A mesogenic benzanilide, a photochromic azobenzene and a dye unit (a benzoxazole, an anthracene or a stilbene derivative). This approach provides liquid crystalline terpolymers with different spectral properties and with the potential ability to be photoaligned by irradiation and thermotropic self-organization. The polymers have been prepared by random radical polymerisation of the corresponding methacrylate-fucntionalised units. All of the materials show good thermal stability and liquid crystalline behaviour, displaying smectic A or nematic mesophases. Optical properties of the polymers in solution display additive bands in the absorbance spectrum and luminescent properties in the emission region of the individual dye monomers. However, films of these polymers are not luminescent. A study of the absorption and redox properties of the dyes has been performed in order to evaluate the quenching process in the polymers.     

Precipitation from glassy polymer solutions

Solid solutions of general-purpose polystyrene containing crystalline tetrabromoxylene, tetrachloroxylene, or tetrachlorobenzene were prepared. The effects of the low molecular weight crystalline additive concentration and the thermal history on the thermal properties of the system have been studied. The system solubility, rejection of solute, etc., were characterized by such techniques as rheology, thermal analysis (DSC), and Vicat softening point.     

液晶高分子材料的研究与开发进展

简述液晶高分子的发展历史,综述1990年以来液晶高分子在合成技术、新产品开发及应用开发诸方面的最新研究成果,并展望其研究开发方向。     

Comparative Mechanical and Dielectric Relaxational Study of Low-Density Polyethylene

Some polymers show varying dynamic responses according to the technique employed to measure them. The polyethylenes are a good example, with a wide range of circumstances complicating the analysis of mechanical and dielectric relaxation spectra. First, the polyethylenes are nonpolar polymers that require oxidation or chlorination to obtain consistent dielectric activity; second, the relaxation spectrum is highly complicated in each of the three characteristic zones (γ, β, and α); and finally, the response to an alternative stimulus differs according to its physical origin. Thus it is well known that differences arise between dynamic mechanical and dielectric spectra when they are compared (McCrum et al., 1967; Morozuni et al., 1970; Ribes-Greus, 1986). Moreover, to obtain reasonable conclusions, it is necessary to use the same type of polymer in all cases; and to control the crystalline morphology of the specimen, a constant thermal history is needed.     

Synthesis and characterisation of a nematic homo-polyurethane

The presence of hydrogen bonds in the chemical structure of polymers promotes and stabilises the crystalline phase. For liquid crystalline (LC) polymers, the side insertion of aliphatic units to the mesogenic unit is a suitable artifice to decrease the crystalline stability, without significantly affecting the stability of the LC phases. Here, we report on the synthesis of a LC homo-polyurethane with high hydrogen bond concentration along the chain and bearing an n-pentyl side-chain. Rheological behaviour, thermal analysis, and X-ray diffraction show that the stable LC phase is the nematic.     

Reorganization and improvement of bulk polymers by processing with their cyclodextrin inclusion compounds

The formation of polymer-cyclodextrin inclusion compounds of polycarbonate (PC), poly(methylmethacrylate) (PMMA) and poly(vinylacetate) (PVAc) guests with host γ-cyclodextrin (γ-CD) have been successfully achieved. Coalesced bulk polymer samples were obtained by removal of γ-CD from their inclusion compounds (ICs). The chemical and crystalline structures of ICs and coalesced PC, PMMA and PVAc were studied by Fourier transform infrared spectroscopy (FTIR) and wide-angle X-ray diffraction (WAXD). The thermal transitions, thermal stability, and degradation mechanisms of the samples were investigated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and direct insertion probe pyrolysis mass spectrometry (DIP-MS). FTIR findings indicated that the chain conformations of the bulk polymers were altered when they were included inside the CD channels and extended chain conformations were retained when coalesced from their ICs. Significant improvements were observed in the thermal transitions observed for the coalesced polymers, with glass transitions shifted to higher temperatures. The TGA results reveal that the thermal stabilities of coalesced polymers increased slightly compared to the corresponding as-received polymers. The DIP-MS observations indicated that the thermal stability and degradation products of the polymers are affected once the polymers chains are included inside the γ-CD-IC cavities.     

Aromatic thermotropic polyesters based on 2,5-furandicarboxylic acid and vanillic acid

This paper addresses a route to synthesize bio-based polymers with an aromatic backbone having a liquid crystalline (LC) phase in the molten state. The LC phase is employed to achieve uniaxial orientation during processing required in e.g. fiber spinning. For this purpose 2,5-furandicarboxylic acid (2,5-FDCA) and O-acetylvanillic acid (AVA), obtained from natural resources, are used as monomers. Similar to the 2,6-hydroxynapthoic acid used to perturb the crystalline packing of poly(oxybenzoate) in the Vectran^® series, these bio-based monomers are used to lower the crystal to liquid crystal transition temperature. Considering that the poly(oxybenzoate) can also be obtained from natural resources, the adopted route provides the unique possibility to synthesize bio-based polymers that can be used for high performance applications. To obtain the desired polymers, a synthetic route is developed to overcome the thermal instability of the 2,5-FDCA monomer. Experimental techniques, such as optical microscopy, FTIR spectroscopy, DSC, and TGA are employed to follow the polymerization, phase transitions and evaluate thermal stability of the synthesized polymers.     

Regulating the Interface in Graphite/Thermoplastic Composites

Among the many engineering thermoplastics available today, there exists a large subgroup of difficult-to-crystallize or amorphous polymers which possess a rather unique micronodular morphology in their normally produced solid state. When these polymers are processed in the unfilled state, changes in process thermal history have little effect on mechanical properties; but when reinforcement such as graphite is added, pronounced effects of thermal treatment arise which are relatable to the nodular polymer morphology. These effects will be documented and explained for graphite fiber-filled polycarbonate and poly(phenylene oxide). The practical application of these results to hot-forming techniques will also be described. Finally, extension of these techniques to the more easily crystallized thermoplastics such as polypropylene will be considered.     

Solidification of poly(ethylene terephthalate) with incomplete crystallization

Cooling is a critical step in any crystalline polymer molding or extrusion process. A simulation is proposed which will predict the transient temperature and crystallinity profiles developed when a finite polymeric slab comes in contact with a cooling fluid. A generalized, phenomenological model of the crystallization kinetics of polymers is incorporated to account for the effect of the latent heat of crystallization on the thermal history as well as on the crystalline structure at any point in the slab. The model assumes heterogeneous nucleation and temperature-dependent radial growth of spherulites. DSC cooling thermograms for the polymer are used to verify the kinetic model for comparing experimental measurements against simulated results. Observed spherulite sizes should also be matched by the simulation. Kinetic data have been obtained for two grades of poly(ethylene terephthalate) which have the same growth rate expression but different nucleation characteristics. Crystallinity of these two polymers decreases rapidly as either quench temperatures or nucleation densities are decreased independently. Calculations have been carried out for 1/16 in. thick sheets of polymer exposed to a cooling medium with a heat transfer coefficient of 100 Btu/hr/ft²/°F. Temperature gradients are also presented. The simulation can be used for optimizing quench conditions in polyester film extrusion.     

Side‐chain liquid‐crystalline polymers with a limonene‐co‐methyl methacrylate main chain: Synthesis and characterization of polymers with phenyl benzoate mesogenic groups

A new series of liquid‐crystalline polymers with a polymer backbone of limonene‐co‐methyl methacrylate were synthesized and characterized, and the spacer length was taken to be nine methylene units. The chemical structures of the obtained olefinic compound and polymers were confirmed with elemental analysis and proton nuclear magnetic resonance spectroscopy. The thermal behavior and liquid crystallinity of the polymers were characterized with differential scanning calorimetry and polarized optical microscopy. The polymers exhibited thermotropic liquid‐crystalline behavior and displayed a glass‐transition temperature at 48°C. The appearance of the characteristic schlieren texture confirmed the presence of a nematic phase, which was observed under polarized optical microscopy. These liquid‐crystalline polymers exhibited optical activity. A comparison was also made with polyacrylates and polymethacrylate‐based materials. This revealed that the nature of the polymer backbone had a major effect on the liquid‐crystalline properties. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4595–4600, 2006     

Crystaline polymers as heat storage materials in passive thermal protection systems

Previous studies have evaluated low molecular weight crystalline materials as latent heat sinks for passive thermal protection systems. This study evaluated crystalline polymers as heat storage materials. Differential scanning calorimetry and Instron thermomechanical analysis are applied in dynamic studies of cumulative histories of melting and recrystallization. Commercially available crystalline polymers with melting temperatures T_m ≥ 100°C can provide fully reversible heats of fusion ΔH_m ≥ 35 cal/gm under programmed heating-cooling cycles. A linear polyethylene (Marlex 6050) is modified by radiation crosslinking to retain shape stability above T_m with-out loss of heat storage capability. The essentially zero vapor pressure and inherent shape stability of crosslinked crystalline polymers may provide unique advantages as uncontained, non-expendable, heat storage materials.     

Synthesis, characterization and liquid crystalline behavior of poly(monomethyl itaconate)s with new pendant cholesterol moieties

In order to investigate the effects of cholesteryl pendant groups on inducing liquid crystalline (LC) phase formation, a new series of cholesteryl-modified poly(monomethyl itaconate) (PMMI-Chol-C₆) have been synthesized from poly(monomethyl itaconate) (PMMI) and 6-(cholesteryloxycarbonyloxy) hexanol (Chol-C₆) with different degrees of substitution (DS_chol). All the obtained compounds were characterized by conventional spectroscopic methods. The DS_chol values of the modified PMMI were obtained by ¹H NMR spectroscopy and conductometric titration. The inherent viscosities of polymers were determined by an Ubbelohde viscometer at 35 °C in DMSO solution. The resulting products of modified PMMA polymers were soluble in a variety of organic solvents, and the solubility improved by increasing the DS_chol. Thermal behavior and optical properties of Chol-C₆ and PMMI-Chol-C₆ polymers were investigated by thermal gravimetric analysis, differential scanning calorimetry and hot-stage polarizing optical microscopy. The glass transitions of the modified PMMI polymers occurred at lower temperatures than the parent PMMI. It was found that among the synthesized polymers with different molar ratios of the substitution, only the PMMI-Chol-C₆ (1) polymer bearing 77 mol% of the side chains, with reduced melting point and increased thermal stability, formed thermotropic liquid crystalline smectic phases. This polymer exhibited wider mesophase than the mesogenic side chain Chol-C₆ and amorphous morphology. The results of a comparative study on the structure and properties of the polymers showed that liquid crystalline polymers may be achieved through the attachment of mesogenic cholesterol side chain onto the main chain via methylene chains of side branches.