Rhythmic growth of ring‐banded spherulites in blends of liquid crystalline methoxy‐poly(aryl ether ketone) and poly(aryl ether ether ketone)

Rhythmic growth of ring‐banded spherulites in blends of liquid crystalline methoxy‐poly(aryl ether ketone) (M‐PAEK) and poly(aryl ether ether ketone) (PEEK) has been investigated by means of differential scanning calorimetry (DSC), polarized light microscopy (PLM), and scanning electron microscopy (SEM) techniques. The measurements reveal that the formation of the rhythmically grown ring‐banded spherulites in the M‐PAEK/PEEK blends is strongly dependent on the blend composition. In the M‐PAEK‐rich blends, upon cooling, an unusual ring‐banded spherulite is formed, which is ascribed to structural discontinuity caused by a rhythmic radial growth. For the 50:50 M‐PAEK/PEEK blend, ring‐banded spherulites and individual PEEK spherulites coexist in the system. In the blends with PEEK as the predominant component, M‐PAEK is rejected into the boundary of PEEK spherulites. The cooling rate and crystallization temperature have great effect on the phase behavior, especially the ring‐banded spherulite formation in the blends. In addition, the effects of M‐PAEK phase transition rate and phase separation rate on banded spherulite formation is discussed. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 3011–3024, 2007     

Thermal behavior and phase behavior in blends of liquid crystalline poly(aryl ether ketone) and poly(aryl ether ether ketone) containing thioether units

Thermal behavior and phase behavior in blends of liquid crystalline poly(aryl ether ketone) with lateral methoxy groups (M-PAEK) and poly(aryl ether ether ketone) containing thioether units (S-PEEK) have been investigated by differential scanning calorimetry (DSC) and polarized light microscopy (PLM) techniques. The results indicate that the composition of the blends has great effect on the phase behavior and morphology. Thin films of pure M-PAEK and S-PEEK crystallized from the melts exhibit typical mosaic and spherulitic structures, respectively. For the blends with higher M-PAEK contents (> 50%), an unusual ring-banded spherulite with structural discontinuity is formed. The bright core and rings of the ring-banded spherulites under PLM are composed of M-PAEK phase, while the dark rings consist mainly of S-PEEK phase. For the 50:50 M-PAEK/S-PEEK blend, the ring-banded spherulites and S-PEEK spherulites coexist, which implies that a partial phase separation between the two components takes place in the melting state. In S-PEEK-rich blends, a volume-filled spherulite is produced. In addition, the effect of isothermal crystallization temperature on the phase behavior, especially the ring-banded spherulite formation in the blends, is discussed.     

A Main‐Chain Liquid‐Crystalline Oligomer Prepared by in situ Photopolymerization of an LC Monomer Having Cinnamate Moieties

Summary: A liquid‐crystalline (LC) compound, having a cinnamate moiety on each end of the molecule, was synthesized and irradiated with UV light in its LC phase in the presence of a triplet sensitizer. Various measurements of the irradiated sample revealed that the linearly structured LC oligomers were formed by [2+2] cycloaddition of the cinnamate moieties, and that the resultant cyclobutane units dominantly assumed an anti head‐to‐head configuration.

Schematic structures of the LC oligomer obtained by photopolymerization.     

Studies on the thermotropic liquid crystalline polymer. VII. Synthesis and properties of photocrosslinkable poly(ether-ester) containing cinnamic group

A series of semi-aromatic poly(ether-ester)s containing cinnamic group was prepared from 4,4′-diacrylic acid-α,ω-phenoxyalkanes with diols in the presence of diphenylchlorophosphate (DPCP) and pyridine as a catalyst and solvent. The phase behavior of these polymers was studied by differential scanning calorimetry (DSC), optical polarizing microscopy equipped with a heating stage, and wide-angle x-ray diffraction (WAXD). All of the poly(ether-ester)s, except P3 , show nematic or smectic thermotropic liquid crystalline behaviour under optical polarizing microscopic observation. These polymers can undergo photocrosslinking reaction upon heating, as examined by IR, solubility, and DSC analysis. © 1993 John Wiley & Sons, Inc.     

Design,synthesis, and characterization of a combined main‐chain/side‐chain liquid crystalline polymer based on mesogen‐jacketed liquid crystal polymer via atom transfer radical polymerization

A novel combined main‐chain/side‐chain liquid crystalline polymer based on mesogen‐jacketed liquid crystal polymers (MJLCPs) containing two biphenyls per mesogenic core of MJLCPs main chain, poly(2,5‐bis{[6‐(4‐butoxy‐4′‐oxy‐biphenyl)hexyl]oxycarbonyl}styrene) (P1–P8) was successfully synthesized via atom transfer radical polymerization (ATRP). The chemical structure of the monomer was confirmed by elemental analysis, ¹H NMR, and ¹³C NMR. The molecular characterizations of the polymer with different molecular weights (P1–P8) were performed with ¹H NMR, gel permeation chromatography (GPC), and thermogravimetric analysis (TGA). Their phase transitions and liquid‐crystalline behaviors of the polymers were investigated by differential scanning calorimetry (DSC) and polarized optical microscope (POM). We found that the polymers P1–P8 exhibited similar behavior with three different liquid crystalline phases upon heating to or cooling in addition to isotropic state, which should be related to the complex liquid crystal property of the side‐chain and the main‐chain. Moreover, the transition temperatures of liquid crystalline phases of P1–P8 are found to be dependent on the molecular weight. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7310–7320, 2008     

Side chain liquid crystal poly(fumarate)s bearing tolane‐based mesogens

Cyanotolane or fluorotolane mesogens were for the first time introduced into the fumarate monomer under basic conditions. All fumarate monomers undergo radical polymerization in benzene in the presence of dimethyl 2,2′‐azobis(isobutyrate) as an initiator at 60 °C, affording the corresponding poly(fumarate)s with a molecular weight (M_n) of ～ 10⁴ and an exceptionally narrow polydispersity. The phase behaviors of the fumarate monomers and the correspoding poly(fumarate)s were comprehensively investigated by differential scanning calorimetry (DSC), polarized optical microscopy (POM), and X‐ray diffraction (XRD) analysis. For the fumarate monomers, fluorotolane derivatives were prone to form higher‐order liquid crystal phases such as a smectic phase, while cyanotolane derivatives tended to show a wide mesophase temperature range, depending on the alkyl chain spacer length. Very surprisingly, these features dramatically weakened when they were polymerized. The mesophase temperature ranges became narrow and completely disappeared for the poly(fumarate)s with a shorter alkyl chain spacer. A nematic phase representing lower‐order arrangements became a predominant liquid crystal phase for the poly(fumarate) carrying cyanotolane mesogens. Only the poly(fumarate) carrying fluorotolane mesogens with a longer alkyl chain spacer displayed the characteristic XRD patterns of the smectic B phase. The transient photocurrent measurements of the fumarate monomer with cyanotolane mesogens displayed a hole mobility of the order of 10^?4–10^?5 cm² V^?1 s^?1 at room temperature. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5101–5114, 2008     

Photoreactive main‐chain liquid‐crystalline polyesters: Synthesis,characterization, and photochemistry

Three series of semiflexible and rigid main‐chain polyesters containing photoreactive mesogenic units derived from p‐phenylenediacrylic acid (PDA) and cinnamic acid have been synthesized by high‐temperature polycondensation. The thermal and mesomorphic properties of the polymers have been determined. The photochemical behavior of polymer P‐[1]‐T, which contains a PDA unit, has been studied both in solution and in films. In solution, [2+2] photocycloaddition, E/Z photoisomerization, and photo‐Fries rearrangement can take place. In contrast, the dominant process in spin‐coated films is the [2+2] photocycloaddition reaction, which causes crosslinking of the polymer. In films, the photochemistry and induction of anisotropy are strongly influenced by the aggregation of the PDA phenylester unit. A dichroism of about 0.2 has been induced in films by irradiation with linearly polarized UV light, and thus the capability of these films to induce optical anisotropy and align liquid crystals has been demonstrated. Liquid‐crystalline cells have been made with polarized irradiated films of P‐[1]‐T as aligning layers. A commercial liquid‐crystalline mixture has been used for this study, and a similar liquid‐crystalline order determined by polarized Fourier transform infrared to a commercial cell with rubbed polyimide as an aligning layer has been detected. Because of crosslinking of the irradiated P‐[1]‐T photoaligning layer, the photoinduced anisotropy is stable at high temperatures, and the liquid‐crystalline molecules are insoluble in the irradiated polymer. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4907–4921, 2005     

Crystallization and melting behavior of liquid crystalline copolyesters based on poly(ethylene terephthalate)

A series of copolyesters were prepared by the incorporation of p‐hydroxybenzoic acid (HBA), hydroquinone (HQ), and terephthalic acid (TA) into poly(ethylene terephthalate) (PET). On the basis of viscosity measurements, high molar mass copolyesters were obtained in the syntheses, and ¹H‐NMR analyses indicated the total insertion of comonomers. They exhibit nematic phase above melting temperature, as observed by polarized light microscope (PLM). Their crystallization and melting behaviors were also studied by differential scanning calorimetry (DSC) and wide angle X‐ray diffraction (WAXD). It was found that these copolyesters are more crystalline than copolyesters prepared from PET and HBA. Introduction of HQ/TA disrupts longer rigid‐rod sequences formed by HBA, and thus enhances molecular motion and increases crystallization rate and crystallinity. Isothermal crystallization at solid phase polymerization conditions (up to 24 h at 200°C) resulted in increased copolymer randomness (by NMR) and higher melting point, the latter attributed to structural annealing. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 369–377, 1999     

Synthesis and characterization of hydrogen‐bonded thermotropic liquid crystalline aromatic‐aliphatic poly(ester–amide)s from amido diol

Fifteen highly regular hydrogen‐bonded, novel thermotropic, aromatic‐aliphatic poly(ester–amide)s (PEAs) were synthesized from aliphatic amido diols by melt polycondensation with dimethyl terephthalate and solution polycondensation with terephthaloyl chloride. Intermolecular hydrogen bonds more or less perpendicular to the main‐chain direction induce the formation and stabilization of liquid crystalline property for these PEAs. The structure of these polymers, even in the mesomorphic phase is dominated by hydrogen bonds between the amide–amide and amide–ester groups in adjacent chains. Aliphatic amido diols were synthesized by the aminolysis of γ‐butyrolactone, δ‐valerolactone and ε‐caprolactone with aliphatic diamines containing a number of methylene groups from two to six in isopropanol medium at room temperature. Effects of polarity of the solvent on solution polymerization and effect of catalyst on trans esterification were studied. These polymers were characterized by elemental analysis, FTIR, ¹H NMR, ¹³C NMR, solubility studies, inherent viscosity, DSC, X‐ray diffraction, polarized light microscopy, and TGA. All the melt/solution polycondensed PEAs showed multiple‐phase transitions on heating with second transitions identified as nematic/smectic/spherullitic texture. The mesomorphic properties were studied as a function of their chemical structure by changing alternatively m or n. Odd‐even effect on mesophase transition temperature, isotropization temperature, and crystallinity were studied. The effect of molecular weight and polydispersity on mesophase/isotropization temperature and thermal stability were investigated. It was observed that there exists a competition for crystallinity and liquid crystallinity in these PEAs © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2469–2486, 2000     

Nonisothermal crystallization kinetics of poly (phenylene sulphide) in composites with a liquid crystalline polymer

The article deals with the melting and nonisothermal crystallization behavior of neat poly (phenylene sulphide) (PPS) and its composites with a thermotropic liquid crystalline polymer (TLCP)—Vectra A950, prepared by melt mixing and probed by differential scanning calorimetry. The various macrokinetic models namely, the Ozawa, the modified Avrami, the Tobin, and the Mo models were applied to describe the crystallization kinetics under nonisothermal conditions. The kinetic crystallizabilty of PPS/TLCP composites calculated using the approach of Ziabicki varies depending on these two composite composition‐induced effects. Similarly Mo model predicts that to obtain a higher degree of crystallizabilty for PPS/TLCP composites, a higher cooling rate should be used. The effective energy barrier based on the differential isoconversional method of Friedman is found to be an increasing function of relative degree of melt conversion. The effect is explained in terms of nucleation theory proposed by Wunderlich to crystallization of polymers. The Lauritzen–Hoffman parameters are estimated using G = 1/t_0.5 effective activation energy equation proposed by Vyazovkin and Sbirrazzuoli. The K_g values estimated from latter equations are more comparable with values obtained using isothermal crystallization data than 1/t_0.5 method. Furthermore, the kinetic analysis using this equation shows a regime transition from regime II to regime III for 100/00, 90/10, 80/20 PPS/TLCP composites, basically attributed to reduced mobility of PPS chains in composites. This regime II to III transition is accompanied by a morphological transition from defective spherulitic sheaf‐like structures to ordered sheaf‐like structures. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1070–1100, 2010     

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 points (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°C. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 211–218, 1999     

Interfacial slip at the thermotropic liquid‐crystalline polymer/poly (ethylene naphthalate) interface

The unique rheological properties of a thermotropic liquid‐crystalline polymer (TLCP) were first studied. The thermal and shear history of the TLCP was found to play a critical role in its rheological properties. Crystallites were observed in the TLCP melt even above the melting temperature detected by differential scanning calorimetry. Because interfacial slip had long been suggested as an important reason for viscosity reduction in TLCP/thermoplastic blends, for the first time, interfacial slip at the TLCP/poly(ethylene naphthalate) (PEN) interface was investigated with an energy model. The model quantified the degree of interfacial slip at the TLCP/PEN interface by an energy factor. The calculated energy factors revealed a high degree of interfacial slip at the TLCP/PEN interface. It was proposed that the high rigidity of rodlike TLCP chains and their alignment parallel to the interface prevented mutual entanglements at the TLCP/PEN interface. The lack of mutual entanglements promoted the interfacial slip. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 302–315, 2004     

Study on the thermotropic liquid crystalline polycarbonates. IV. Synthesis and properties of liquid crystalline poly(imide-carbonate)s

Two series of novel thermotropic liquid crystalline poly(imide-carbonate)s were prepared by melt polycondensation from various arylene or alkylene bis(phenylcarbonate)s by using N,N′-bis(hydroxyethyl)pyromellitimide and N,N′-bis(hydroxypropyl)pyromellitimide as monomers. Thermotropic liquid crystalline properties were characterized by a polarizing microscope with a heating stage and a differential scanning calorimeter (DSC). Nematic melts were found for the synthesized aromatic poly(imide-carbonate)s. In order to investigate whether the pyromellitimide unit could be used as a mesogenic unit for preparing LC polymers, a series of aliphatic poly(imide-carbonate)s was prepared in this study. However, no significant LC textures were found under the observation by polarizing microscope. It was suggested that the aspect ratio of the pyromellitimide unit was too short to form liquid crystalline poly(imide-carbonate)s. In addition, it was interesting that the aliphatic poly(imide-carbonate)s with a longer spacer (n = 3) in the pyromellitimide unit showed better crystallinity. Thermostabilities of all synthesized poly(imide-carbonate)s were measured by thermogravimetric analysis (TGA). © 1994 John Wiley & Sons, Inc.     

Surface fixation of poly(ethylene glycol)via photodimerization of cinnamate group

This article reports a new fixation method for hydrophilic layers on substrates. The method is based on the photochemistry of the cinnamate group, which is capable of intermolecular dimerization upon ultraviolet (UV) light irradiation. The method used was as follows. First, two photoreactive polymers were sequentially coated on a polymeric surface: a polycinnamate as an adhesive layer and a cinnamated poly(ethylene glycol) (PEG) as a hydrophilic layer. Subsequently the surface was exposed to UV light. No delamination occurred upon washing with water and methanol; the photoreactive PEG was chemically bonded onto the surface via the polycinnamate. The higher the molecular weight of PEG, the higher the wettability of the surface was formed. Minimal cell adhesion was observed on such a surface. The biomedical applications of the method are discussed. © 1993 John Wiley & Sons, Inc.     

A novel phosphorus‐containing thermotropic liquid crystalline poly(ester‐imide) with high flame retardancy

A novel phosphorus–nitrogen thermotropic liquid crystalline poly(ester‐imide) (PN‐TLCP) derived from p‐acetoxybenzoic acid (ABA), terephthalic acid (TPA), acetylated 2‐(6‐oxide‐6H‐dibenz<c,e><1,2>oxa phosphorin‐ 6‐yl)‐1,4‐dihydroxy phenylene (DOPO‐AHQ) and N,N'‐hexane‐1,6‐diylbis(trimellitimide) was prepared by melt transesterification. The chemical structure, the mesophase behavior, and the thermal properties of the copolymer were investigated with Fourier transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance spectroscopy (¹H NMR), elemental analysis, wide‐angle X‐ray diffraction (WAXD), hot‐stage polarized light microscopy (PLM), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). PN‐TLCP exhibited a nematic mesophase with a strong birefringence at a low and broad mesomorphic temperature ranging from 220 to 350°C, an initial flow temperature as low as about 190°C and a glass transition temperature of about 160°C. PN‐TLCP has also good thermal stability, high char residues and excellent flame retardancy (limiting oxygen index, LOI = 71 and UL‐94 V‐0 rating). Copyright © 2009 John Wiley & Sons, Ltd.     

Synthesis and properties of segmented main‐chain liquid‐crystalline polyurethanes with a high aspect ratio mesogenic diol as a chain extender

Main‐chain liquid‐crystalline polyurethanes were synthesized based on a high aspect ratio mesogenic diol (4‐{[4‐(6‐hydroxyhexyloxy)‐phenylimino]‐methyl}‐benzoic acid 4‐{[4‐(6‐hydroxyhexyloxy)‐phenylimino]‐methyl}‐phenyl ester) as a chain extender; polycaprolactone (PCL) diol soft segments of different number‐average molecular weights (530, 1250, or 2000); and different diisocyanates, including 1,4‐hexamethylene diisocyanate (HMDI), 4,4′‐methylene bis(cyclohexyl isocyanate) (H₁₂MDI), and 4,4′‐methylene bis(phenyl isocyanate) (MDI). The structure of the polymers was confirmed with Fourier transform infrared spectroscopy, and differential scanning calorimetry and polarizing microscopy measurements were carried out to examine the liquid‐crystalline and thermal properties of the polyurethanes, respectively. The mesogenic diol was partially replaced with 20–50 mol % PCL. A 20 mol % mesogen content was sufficient to impart a liquid crystalline property to all the polymers. The partial replacement of the mesogenic diol with PCL of various molecular weights, as well as the various diisocyanates, influenced the phase transitions and the occurrence of mesophase textures. Characteristic liquid‐crystalline textures were observed when a sufficient content of the mesogenic diol was present. Depending on the flexible spacer length and the mesogenic content, grained and threadlike textures were obtained for the HMDI and H₁₂MDI series polymers, whereas the polyurethanes prepared from MDI showed only grained textures for all the compositions. The polymers formed brittle films and could not be subjected to tensile tests. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1527–1538, 2002     

Studies on thermotropic liquid crystalline polymers. XV. Synthesis and properties of liquid crystalline copoly(imide-ester)s

Three series of the thermotropic liquid crystalline copoly(imide-ester)s were prepared by direct polycondensation. The first two series of the copoly(imide-ester)s were synthesized from N-(4-carboxyphenyl) trimellitimide with N,N-di(hydroxypropyl) pyromellitic diimide and various aromatic diols. The third series of copoly(imide-ester)s were prepared by N-(4-carboxyphenyl) trimellitimide with various imide-diols (methylene spacer = 2–6) and phenyl hydroquinone. The structures and thermal properties of the synthesized poly(imide-ester)s were examined by FTIR spectrum, wide-angle x-ray diffraction (WAXD), differential scanning calorimetry (DSC), thermal optical polarized microscope, and thermogravimetric analysis (TGA). The effects of the structures of the aromatic diols on the thermal properties of the resulting copoly(imide-ester)s were investigated. It was found that most of the copoly(imide-ester)s possessed excellent mesophase stabilities and thermostabilities. The mesophase stabilities of poly(imide-ester)s decreased with the increase of the size of lateral group, and the mesophase range increased with the increase of the amount of PhHQ. No significant odd-even effects were observed between the methylene spacer lengths and transition temperatures. © 1996 John Wiley & Sons, Inc.     

Studies on thermotropic liquid crystalline polymers. XIV. Synthesis and properties of liquid crystalline poly(imide-ester)s by the direct polycondensation

A series of semi-aromatic poly(imide-ester)s were prepared by the direct polycondensation of N-(4-carboxyphenyl) trimellitimide or N-(3-carboxyphenyl) trimellitimide with various pyromellitic diimide diols containing methylene spacer = 2–6, respectively. The effect of the amount of LiCl, pyridine, and the kinds of condensation agents on the direct polycondensation were studied. The structures and thermal properties of the synthesized poly(imide-ester)s were examined by FTIR spectrum, wide-angle x-ray diffraction (WAXD), differential scanning calorimetry (DSC), thermal optical polarized microscopic observation, and thermogravimetric analysis (TGA). It is found that P1 series [derived from N-(4-carboxyphenyl) trimellitimide] with even number methylene spacer (n = 4, 6) exhibit smectic mesophase, but P2 series [derived from N-(3-carboxyphenyl) trimellitimide] do not show LC phase. © 1996 John Wiley & Sons, Inc.     

Synthesis and liquid crystalline properties of poly(1‐alkyne)s carrying triphenylene discogens

Triphenylene‐containing 1‐decynes with different alkyl chain lengths and their polymers are synthesized and the effects of the structural variables on their mesomorphic properties are investigated. The monomers [HC?C(CH₂)₈CO₂C₁₈H₆ (OC_mH_2m+1)₅; m = 4–9] are prepared by consecutive etherization, coupling, and esterification reactions. The monomers form columnar phases at room temperature. The polymerizations of the monomers are effected by [Rh(nbd)Cl]₂, producing soluble polymers in high yields (up to 84%). The structures and properties of the polymers are characterized and evaluated by IR, NMR, TGA, DSC, POM, and XRD analyses. All the polymers are thermally stable, losing little of their weights when heated to 300 °C. The isotropization temperature of the polymers increases initially with the length of alkyl chain but decreases on further extension. Although the polymers with shorter and longer alkyl chain lengths adopt a homogeneous hexagonal columnar structure, those with intermediate ones form mesophases with mixed structures. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2960–2974, 2008