Abstract

Abstract

ABA-type amphiphilic triblock copolymers composed of poly(ethylene glycol)s (PEGs) with different number-average molecular weights as the hydrophilic blocks (B) and poly{6-[4-(4-ethoxyphenylazo)phenoxy]hexyl methacrylate} (PA6C) as the hydrophobic blocks (A) were prepared via atom transfer radical polymerization. These copolymers were prepared from bromo-terminated macroinitiators based on PEG6000, PEG2000, and PEG600, with CuBr/N,N,N′,N″,N″-pentamethyldiethylenetriamine as the catalytic system, at 85 °C in anisole. The block copolymers were characterized with ¹H NMR spectroscopy and gel permeation chromatography. Differential scanning calorimetry measurements were performed to reveal the phase segregation. In contrast to those polymers with similar compositions and structures in previous reports, these amphiphilic copolymers exhibited unusual liquid-crystalline properties over a wide temperature range, being stable even at room temperature. These copolymers showed photoresponsive isomerization under the irradiation of UV–vis light both in THF solutions and in solid films. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2225–2234, 2007

A series of novel comblike mesogen-jacketed liquid-crystalline graft copolymers, poly(p-phenylene)-g-poly{2,5-bis[(4-methoxyphenyl)oxycarbonyl]styrene} (PPP-g-PMPCS) copolymers, have been designed and successfully synthesized by a Yamamoto coupling reaction and subsequent atom transfer radical polymerization (ATRP). ¹H NMR spectroscopy, ultraviolet–visible spectra, and gel permeation chromatography (GPC) have been used to confirm the molecular structure of the macroinitiator and the copolymers. A study of the polymerization kinetics of ATRP has shown that the molecular weight of the copolymer increases linearly with the conversion of the monomer, whereas the polydispersity remains narrow (≤1.28), indicating that the ATRP of 2,5-bis[(4-methoxyphenyl)oxycarbonyl]styrene is well controlled. Thermogravimetric analysis and differential scanning calorimetry (DSC) measurements have indicated that the PPP-g-PMPCS copolymers have better thermal stabilities than the macroinitiator, and their thermal stabilities increase with increasing molecular weight. The liquid-crystalline behavior has been examined with polarized optical microscopy, DSC, one-dimensional wide-angle X-ray diffraction (1D WAXD), and two-dimensional wide-angle X-ray diffraction (2D WAXD). The results show that all the comblike copolymers exhibit obvious liquid-crystalline behaviors, even though the GPC molecular weight of the segments of poly{2,5-bis[(4-methoxyphenyl)oxycarbonyl]styrene} (PMPCS) have been determined to be far less than the critical value of linear PMPCS. Moreover, 1D WAXD measurements show that the temperature at which the comblike mesogen-jacketed liquid-crystalline copolymers can transform into a liquid-crystalline phase is low; about 20 °C in comparison with the linear ones. 2D WAXD analysis has revealed that these comblike copolymers should be assigned to a hexatic columnar nematic (Φ_HN) phase. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2543–2555, 2007

We have designed and synthesized rod–coil–rod triblock copolymers of controlled molecular weight by two-step nitroxide-mediated radical polymerization, where the rod part consists of “mesogen-jacketed liquid crystalline polymer” (MJLCP). The MJLCP segment examined in our studies is poly{2,5-bis[(4-methoxyphenyl)oxycarbonyl]styrene} (MPCS) while the coil part is polyisoprene (PI). Characterization of the triblock copolymers by GPC, ¹H and ¹³C NMR spectroscopies, TGA, DSC confirmed that the triblock copolymers were comprised of microphase-separated low T_g amorphous PI and high T_g PMPCS blocks. Analysis of POM and 1D, 2D-WAXD demonstrated that the triblock copolymers formed nematic liquid crystal phase. Morphological studies using TEM indicated the sample formed lamellar structure. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5949–5956, 2007

The effect of the terminal substituent of azobenzene on the properties of ABA triblock copolymers was investigated. For this study, three kinds of azobenzene-containing monomers with different terminal substituents—6-[4-(4-methoxyphenylazo)phenoxy] hexyl methacrylate, 6-[4-(4-ethoxyphenylazo)phenoxy]hexyl methacrylate, and 6-[4-(4-nitrophenylazo)phenoxy]hexyl methacrylate—were used to synthesize ABA triblock copolymers PMMAzo₂₅–PEG₁₃–PMMAzo₂₅/PMMAzo₁₂–PEG₁₃–PMMAzo₁₂, PEMAzo₁₄–PEG₁₃–PEMAzo₁₄, and PNMAzo₁₄–PEG₁₃–PNMAzo₁₄, respectively, by atom transfer radical polymerization (PMMAzo is poly{6-[4-(4-methoxyphenylazo)phenoxy]hexyl methacrylate}, PEMAzo is poly{6-[4-(4-ethoxyphenylazo)phenoxy]hexyl methacrylate}, and PNMAzo is poly{6-[4-(4-nitrophenylazo)phenoxy]hexyl methacrylate}). These copolymers were characterized with ¹H NMR spectroscopy and gel permeation chromatography and exhibited controlled molecular weights and narrow molecular weight distributions. Differential scanning calorimetry and polarizing optical microscopy showed that these copolymers had mesophases. PMMAzo₂₅–PEG₁₃–PMMAzo₂₅ and PMMAzo₁₂–PEG₁₃–PMMAzo₁₂ had a smectic mesophase and a nematic mesophase, whereas both PEMAzo₁₄–PEG₁₃–PEMAzo₁₄ and PNMAzo₁₄–PEG₁₃–PNMAzo₁₄ had a nematic mesophase. This demonstrated that the liquid-crystalline properties of these copolymers highly depended on the terminal substituent of azobenzene. The photoresponsive behavior of these copolymers was also investigated in tetrahydrofuran solutions, and the influence of the terminal substituents attached to azobenzene was studied. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5190–5198, 2007

A chiral azobenzene-containing N-propargylamide monomer, that is, (R)-2-(4-phenylazophenoxy)-n-prop-2-ynyl-propionamide, was prepared and polymerized in the presence of a rhodium catalyst to yield an optically active polyacetylene. The ¹H NMR analysis of the polymer indicated a predominant cis structure of the backbone (cis concentration = 80%); and the chiroptical property studies showed an enhanced optical rotatory power and a strong Cotton effect, indicating the formation of a secondary helical conformation. A reversible optical modulation of chiroptical properties of the polymer due to the reversible photoisomerization of the azobenzene was observed. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6047–6054, 2006

Copolymers of a liquid crystalline monomer, 2,5-bis[(4-methoxyphenyl)oxycarbonyl]styrene (MPCS), with St and MMA were prepared by free radical polymerization at low conversion in chlorobenzene with 2,2′-azobisisobutyronitrile (AIBN) as initiator. The copolymers of poly(MPCS-co-St) and poly(MPCS-co-MMA) were characterized by ¹H NMR and GPC. The monomer reactivity ratios were determined by using the extended Kelen–Tudos (EKT) method. Structural parameters of the copolymers were obtained from the possibility statistics and monomer reactivity ratios. The influence of MPCS content in copolymers on the glass transition temperatures of copolymers was investigated by DSC. The thermal stabilities of the two copolymer systems increased with an increase of the molar fraction of MPCS in the copolymers. The liquid crystalline behavior of the copolymers was also investigated using DSC and POM. The results revealed that the copolymers with high MPCS molar contents exhibited liquid crystalline behaviors. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2666–2674, 2005

A series of rod–coil diblock copolymers, consisting of poly{2,5-bis[(4-methoxyphenyl)oxycarbonyl]styrene} as a rigid segment and poly(n-butyl acrylate) as a flexible part, were successfully prepared through two inverse procedures by atom transfer radical polymerization. The copolymers were characterized by ¹H NMR and gel permeation chromatography and had high molecular weights and relatively narrow polydispersities (polydispersity index < 1.20). All the block copolymers synthesized had two distinct glass-transition temperatures according to differential scanning calorimetry. A polarizing optical microscopy investigation demonstrated the liquid crystallinity of the diblock copolymers. The self-assembly behaviors in dilute solutions was studied by transmission electron microscopy. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5935–5943, 2005

Liquid crystalline diblock copolymers with different molecular weights and low polydispersities were synthesized by atom transfer radical polymerization of methyl methacrylate (MMA) and 2,5-bis[(4-methoxyphenyl)oxycarbonyl]styrene (MPCS) monomers. The block architecture (coil-conformation of MMA segment and rigid-rod of MPCS segment) of the copolymer was experimentally confirmed by a combination of ¹H nuclear magnetic resonance and gel permeation chromatograph techniques. The liquid crystalline behaviour of the copolymer was studied using differential scanning calorimetry and polarized optical microscope. It was found that the liquid crystalline behaviour was dependent on the number average molecular weight of the rigid segment. Only those copolymers with M_n(GPC) of the rigid block above 9200 g mol⁻¹ could form liquid crystalline phases higher than the glass transition temperature of the rigid block. The random copolymers MPCS-co-MMA were also synthesized by conventional free radical polymerization. The molar content of MPCS in MPCS-co-MMA had to be higher than 71% to maintain liquid crystalline behaviour.

© 2003 Society of Chemical Industry

A series of novel rod–coil diblock copolymers on the basis of mesogen-jacketed liquid-crystalline polymer were successfully prepared by atom transfer radical polymerization from the flexible polydimethylsiloxane (PDMS) macroinitiator. The hybrid diblock copolymers, poly{2,5-bis[(4-methoxyphenyl)oxycarbonyl]styrene}-block-polydimethylsiloxane, had number-average molecular weights (M_n's) ranging from 9500 to 30,900 and relatively narrow polydispersities (≤1.34). The polymerization proceeded with first-order kinetics. Data from differential scanning calorimetry validated the microphase separation of the diblock copolymers. All block copolymers exhibited thermotropic liquid-crystalline behavior except for the one with M_n being 9500. Four liquid-crystalline diblock copolymers with PDMS weight fractions of more than 18% had two distinctive glass-transition temperatures. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1799–1806, 2003

Starting with 3,3′,4,4′-biphenyltetracarboxylic dianhydride and methyl aminobenzoate, we synthesized a novel rodlike imide-containing monomer, N,N′-bis[p-(methoxy carbonyl) phenyl]-biphenyl-3,3′,4,4′-tetracarboxydiimide (BMBI). The polycondensation of BMBI with dimethyl terephthalate and ethylene glycol yielded a series of copoly(ester imide)s based on the BMBI-modified poly(ethylene terephthalate) (PET) backbone. Compared with PET, these BMBI-modified polyesters had higher glass-transition temperatures and higher stiffness and strength. In particular, the poly(ethylene terephthalate imide) PETI-5, which contained 5 mol % of the imide moieties, had a glass-transition temperature of 89.9 °C (11 °C higher than the glass-transition temperature of PET), a tensile modulus of 869.4 MPa (20.2 % higher than that of PET), and a tensile strength of 80.8 MPa (38.8 % higher than that of PET). Therefore, a significant reinforcing effect was observed in these imide-modified polyesters, and a new approach to higher property polyesters was suggested. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 852–863, 2002; DOI 10.1002/pola.10169

Copoly(ethylene terephthalate-imide)s (PETIs) were synthesized by the melt copolycondensation of bis(2-hydroxyethyl)terephthalate with a new imide monomer, N,N′-bis[p-(2-hydroxyethoxycarbonyl)phenyl]-biphenyl-3,3′,4,4′-tetracarboxydiimide (BHEI). The copolymers were characterized by intrinsic viscosity, Fourier transform infrared, ¹H NMR, differential scanning calorimetry, and thermogravimetric analysis techniques. Although their crystallinities decreased as the content of BHEI units increased, the glass-transition temperatures (T_g) increased significantly. When 5 or 10 mol % BHEI units were incorporated into poly(ethylene terephthalate), T_g increased by 10 or 24 °C, respectively. The thermal stabilities of PETI copolymers were about the same as the thermal stability of PET, whereas the weight loss of PETIs decreased as the content of BHEI units increased. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 408–415, 2001

Cyclic oligomers of poly(1,4-cyclohexylenedimethylene terephthalate) (PCT) were prepared by reaction of 1,4-cyclohexanedimethanol (CHDM) with terephthaloyl chloride under diluted conditions and separated from the linear products by silica gel column at a yield of 23.7 wt %. Cyclic dimer, trimer, tetramer, pentamer, and hexamer were further separated by high performance liquid chromatography, and found to constitute 98% of the cyclics mixtures. The structures of PCT cyclics were confirmed by means of mass spectrometry, Fourier transform infrared, and ¹H NMR analysis. A series of experiments were carried out to study the effects of catalysts and cis/trans configuration of isomers of CHDM on the yield of cyclic oligomers. Ring opening polymerization of the cyclic oligomers was carried out by heating the sample mixtures at 310 °C for 30 min in the presence of antimony oxide. Polymerization was confirmed by inherent viscosity changes and infrared spectra of the resulting polyesters. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1828–1833, 2000

For the first time the flexible cyclopentyl ring is used to build mesogenic units, and thus a novel mesogen-jacketed liquid crystalline polymer (MJLCP) poly(dicyclopentyl vinylterephthalate) is synthesized. The polymer forms a stable mesophase which changes to an isotropic phase at 267°C. The formation of a stable mesophase may be attributed to the spatial interaction among flexible side groups which converts them into rigid mesogenic units.