Poly‐Schiff bases. V. Synthesis and characterization of novel soluble fluorine‐containing polyether azomethines

A new dialdehyde monomer, 4,4′‐(hexafluoroisopropylidine) bis(p‐phenoxy) benzaldehyde, was prepared; it led to a number of novel poly‐Schiff bases in reactions with different diamines, such as 4,4′‐diaminidiphenyl ether, 4,4′‐(isopropylidine) bis(p‐phenoxy) dianiline, 4,4′‐(hexafluoroisopropylidine) bis(p‐phenoxy) dianiline, and benzidine. The polymers were characterized with viscosity measurements, nitrogen analyses, and IR and ¹H NMR spectroscopy. These poly‐Schiff bases showed good thermal stability up to 491 °C for 10% weight loss in thermogravimetric analysis under air and high glass‐transition temperatures up to 215 °C in differential scanning calorimetry. These polymers were soluble in a wide range of organic solvents, such as CHCl₃, dimethylformamide (DMF), dimethyl sulfoxide, and 1‐methyl‐2‐pyrrolidon (NMP), and were insoluble in toluene and acetone. Thin films of these polymers cast from DMF exhibited tensile strengths up to 38 MPa. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 383–388, 2001     

New polymer syntheses. LXI. Synthesis and alkylation of aromatic poly(pyrazine-ether)s

Three poly(pyrazine-ether)s were prepared from 2,6-dichloropyrazine, silylated bisphenol-A and, in two cases, 4,4′-dichlorodiphenylsulfone. The alkylation of these poly(pyrazine-ether) with methyl triflate, dimethyl sulfate, methyl 4-nitrobenzenesulfonate, or γ-propanesultone was studied by ¹H-NMR spectroscopy in nitrobenzene. Several N-methylated poly(pyrazine-ether)s were also isolated and characterized by elemental analyses, inherent viscosities, ¹H-NMR spectra, ¹⁵N-NMR spectra, and DSC measurements. Furthermore, their solubilities in six different solvents were determined. Complete methylation raises the glass transition temperatures, reduces the solubility in aprotic solvents, and favors dissolution in methanol or ethanol.     

Preparation and physical properties of poly(4,4′‐diamino‐3′‐carbamoylbenzanilide terephthalamide) and poly(4,4′‐diamino‐3′‐carbamoylbenzanilide isophthalamide) films

To prepare thermally stable and high‐performance polymeric films, new solvent‐soluble aromatic polyamides with a carbamoyl pendant group, namely poly(4,4′‐diamino‐3′‐carbamoylbenzanilide terephthalamide) (p‐PDCBTA) and poly(4,4′‐diamino‐3′‐carbamoylbenzanilide isophthalamide) (m‐PDCBTA), were synthesized. The polymers were cyclized at around 200 to 350 °C to form quinazolone and benzoxazinone units along the polymer backbone. The decomposition onset temperatures of the cyclized m‐ and p‐PDCBTAs were 457 and 524 °C, respectively, lower than that of poly(p‐phenylene terephthalamide) (566 °C). For the p‐PDCBTA film drawn by 40% and heat‐treated, the tensile strength and Young's modulus were 421 MPa and 16.4 GPa, respectively. The film cyclized at 350 °C showed a storage modulus (E′) of 1 × 10¹¹ dyne/cm² (10 GPa) over the temperature range of room temperature to 400 °C. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 775–780, 2000     

Gas separation properties of ultra-thin films based on fully cyclized polyimides

Fully cyclized polyimides based on octadecyl- or hexadecyl 3,5-diaminobenzoate and 4,4′-(hexafluoroisopropylidene)diphthalic anhydride or 4,4′-oxydiphthalic anhydride were synthesized and deposited by the Langmuir-Schaefer technique onto a poly(1-trimethylsilylprop-1-yne) support. Composite membranes thus prepared show selective gas permeation for N₂, O₂, CO₂, H₂ with permeation rates in the range of 10⁻⁵ to 10⁻⁷ cm³ (STP)/(cm² · s · cmHg).     

Synthesis and absorption/emission properties of novel poly(silylenearylenevinylene)s

Polymerization of p-(dimethylsilyl)phenylacetylene in toluene at 25 and 80 °C with RhI(PPh₃)₃ catalyst afforded highly regio- and stereoregular poly(dimethylsilylene-1,4-phenylenevinylene)s [cis- and trans-poly( 1a )s] containing 98% cis- and 99% trans-vinylene moieties, respectively. The trans-type polymers exhibited redshifts and hyperchromic effects in the ultraviolet–visible spectrum as compared with the cis-type counterparts. Photoirradiation of cis- and trans-poly( 1a )s gave cis-rich mixtures at equilibrium states. The trans and cis polymers exhibited different emission properties, for example—trans polymer, emissn λ_max = 400 nm, quantum yield: 3.4 × 10⁻³ and cis polymer, emissn λ_max = 380 nm, quantum yield: 1.5 × 10⁻³. Besides poly( 1a ), poly(dimethylsilylenearylenevinylene)s containing biphenylene and phenylenesilylenephenylene units [poly( 3 )] were prepared. The extent of conjugation in these polymers decreased in the orders of biphenylene > phenylene > phenylenesilylenephenylene as well as trans-vinylene > cis-vinylene. The quantum yield of the trans-rich polymer with biphenylene moiety was fairly large and 0.15. Polyaddition of 1,4-bis(dimethylsilyl)benzene and three types of diethynylarenes (4,4′-diethynylbiphenyl, 2,7-diethynylfluorene, and 2,6-diethynylnaphthalene) catalyzed by RhI(PPh₃)₃ provided novel regio- and stereoregular polymers [poly( 6 )]. These polymers displayed blue light emission with high quantum yields (4–81%). © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3615–3624, 2003     

Scalings of fluorine‐containing polyimides in cyclopentanone

Eight 2,2′‐bis(3,4‐dicarboxyphenyl) hexafluoropropane dianhydride‐4,4′‐diamino‐3,3′‐dimethylbiphenyl (6FDA‐OTOL) fractions and seven 2,2′‐bis[4‐(3,4‐dicarboxyphenoxy) phenyl] propane dianhydride‐4,4′‐diamino‐3,3′‐dimethylbiphenyl (BISADA‐OTOL) fractions in cyclopentanone at 30 °C were characterized by a combination of viscometry and static and dynamic laser light scattering (LLS). In static LLS, the angular dependence of the absolute scattered intensity led to the weight‐average molar mass (M_w), the z‐average root mean square radius of gyration, and the second virial coefficient. In dynamic LLS, the Laplace inversion of each measured intensity–intensity time correlation function resulted in a corresponding translational diffusion coefficient distribution [G(D)]. The scalings of 〈D〉 (cm²/s) = 8.13 × 10⁻⁵ M_w^−0.47 and [η] (dL/g) = 2.36 × 10⁻³ M_w^0.54 for 6FDA‐OTOL and 〈D〉 (cm²/s) = 3.02 × 10⁻⁴ M_w^−0.60 and [η] (dL/g) = 2.32 × 10⁻³ M_w^0.53 for BISADA‐OTOL were established. With these scalings, we successfully converted each G(D) value into a corresponding molar mass distribution. At 30 °C, cyclopentanone is a good solvent for BISADA‐OTOL but a poor solvent for 6FDA‐OTOL; this can be attributed to an ether linkage in BISADA‐OTOL. Therefore, BISADA‐OTOL has a more extended chain conformation than 6FDA‐OTOL in cyclopentanone. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2077–2080, 2000     

Aromatic polybenzoxazoles containing ether–sulfone linkages

A series of poly(o‐hydroxy amide)s having both ether and sulfone linkages in the main chain were synthesized via the low‐temperature solution polycondensation of 4,4′‐[sulfonylbis(1,4‐phenylene)dioxy]dibenzoyl chloride and 4,4′‐[sulfonylbis(2,6‐dimethyl‐1,4‐phenylene)dioxy]dibenzoyl chloride with three bis(o‐aminophenol)s including 4,4′‐diamino‐3,3′‐dihydroxybiphenyl, 3,3′‐diamino‐4,4′‐dihydroxybiphenyl, and 2,2‐bis(3‐diamino‐4‐hydroxyphenyl)hexafluoropropane. Subsequent thermal cyclodehydration of the poly(o‐hydroxy amide)s afforded polyethersulfone benzoxazoles. Most of the poly(o‐hydroxy amide)s were soluble in polar organic solvents such as N‐methyl‐2‐pyrrolidone; however, the polybenzoxazoles without the hexafluoroisopropylidene group were organic‐insoluble. The polybenzoxazoles exhibited glass‐transition temperatures (T_g) in the range of 219–282 °C by DSC and softening temperatures (T_s) of 242–320 °C by thermomechanical analysis. Thermogravimetric analyses indicated that most polybenzoxazoles were stable up to 450 °C in air or nitrogen. The 10% weight loss temperatures were recorded in the ranges of 474–593 °C in air and 478–643 °C in nitrogen. The methyl‐substituted polybenzoxazoles had higher T_g's but lower T_s's and initial decomposition temperatures compared with the corresponding unsubstituted polybenzoxazoles. For a comparative purpose, the synthesis and characterization of a series of sulfonyl polybenzoxazoles without the ether group that derived from 4,4′‐sulfonyldibenzoyl chloride and bis(o‐aminophenol)s were also reported. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2262–2270, 2001     

Synthesis of Poly(ether ether ketone)s with High Content of Sodium Sulfonate Groups as Gas Dehumidification Membrane Materials

Sodium sulfonate‐functionalized poly‐(ether ether ketone)s derived from Bisphenol A with a degree of sulfonation up to 2.0 were synthesized by aromatic nucleophilic polycondensation of various amounts of 5,5′‐carbonylbis(2‐fluorobenzenesulfonate) ( 1 ), 4,4′‐difluorobenzophenone ( 2 ) and Bisphenol A ( 3 ). Copolymers showed excellent thermal stability and good mechanical properties. The selectivity of water vapor over nitrogen of membranes prepared from copolymers 3a and 3b was determined to be 3.43×10⁶ and 1.05×10⁷, respectively.     

Preparation and characterization of branched and linear sulfonated poly(ether ketone sulfone) proton exchange membranes for fuel cell applications

Branched sulfonated poly(ether ketone sulfone)s (Br‐SPEKS) were prepared with bisphenol A, bis(4‐fluorophenyl)sulfone, 3,3′‐disodiumsulfonyl‐4,4′‐difluorobenzophenone, and THPE (1,1,1‐tris‐p‐hydroxyphenylethane), respectively, at 180 °C using potassium carbonate in NMP (N‐methylpyrrolidinone). THPE, as a branching agent, was used with 0.4 mol % of bisphenol A to synthesize branched copolymers. Copolymers containing 10–50 mol % disulfonated units were cast from dimethylsulfoxide solutions to form films. Linear sulfonated poly(ether ketone sulfone)s (SPEKS) were also synthesized without THPE. The films were converted from the salt to acid forms with dilute hydrochloric acid. A series of copolymers were studied by Fourier transform infrared, ¹H‐NMR spectroscopy, differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). Sorption experiments were conducted to observe the interaction of sulfonated polymers with water and methanol. The ion‐exchange capacity (IEC), a measure of proton conductivity, was evaluated. The synthesized Br‐SPEKS and SPEKS membranes exhibit conductivities (25 °C) from 1.04 × 10^?3 to 4.32 × 10^?3 S/cm, water swell from 20.18 to 62.35%, IEC from 0.24 to 0.83 mequiv/g, and methanol diffusion coefficients from 3.2 × 10^?7 to 4.7 × 10^?7 cm²/S at 25 °C. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1792–1799, 2008     

Preparation and characterization of new thermally stable and optically active poly(ester‐imide)s by direct polycondensation with thionyl chloride in pyridine

4,4′‐hexafluoroisopropylidene‐2,2‐bis‐(phthalic acid anhydride) (1) was reacted with L ‐methionine (2) in acetic acid and the resulting N,N′–(4,4′‐hexafluoroisopropylidenediphthaloyl)‐bis‐L ‐methionine (4) was obtained in high yield. The direct polycondensation reaction of this diacid with several aromatic diols such as bisphenol A (5a), phenolphthalein (5b), 1,4‐dihydroxybenzene (5c), 4,4′‐dihydroxydiphenyl sulfide (5d), 4,6‐dihydroxypyrimidine (5e), 4,4′‐dihydroxydiphenyl sulfone (5f) and 2,4′‐dihydroxyacetophenone (5g) was carried out in a system of thionyl chloride and pyridine. Expecting that the reaction with thionyl chloride in pyridine might involve alternative intermediates different from an acyl chloride, the polycondensation at a higher temperature favorable for the reaction of the expected intermediate with nucleophiles was attempted, and a highly thermally stable poly(ester‐imide) was obtained by carrying out the reaction at 80°C. All of the above polymers were fully characterized by ¹H‐NMR, ¹⁹F‐NMR FT‐IR spectroscopy, elemental analysis and specific rotation. Some structural characterization and physical properties of these optically active poly(ester‐ imide)s are reported. Copyright © 2006 John Wiley & Sons, Ltd.     

Tridentate Schiff base and 4,4′-bipyridine coordinated di/polynuclear Cu (II) complexes: Synthesis,crystal structure,DNA/protein binding and catecholase activity

4,4′-bipyridine bridged two Cu (II) complexes, [Cu₂L¹₂(4,4′-bipy)(H₂O)₂](ClO₄)₂ ( 1 ) and [Cu₂L²₂(4,4′-bipy)]_n·(2H₂O)_n ( 2 ) (where, HL¹ = 2-[(3-methylamino-propylimino)-methyl]-phenol, H₂L² = 3-[(2-hydroxy-3-methoxy-benzylidene)-amino]-propionic acid, and 4,4′-bipy = 4,4′-bipyridine) have been synthesized and characterized by single crystal structure determination, mass spectrometry, FT-IR, electronic absorption, and emission spectroscopy. Complex 1 is dinuclear cationic compound and counter balanced by perchlorate anion, whereas complex 2 possesses 1D poly-nuclear structure. Both the complexes crystallize in monoclinic system with P2₁/c space group and the copper centers possess square pyramidal geometry. H-bonding, C-H···π, π···π interactions results the formation of two dimentional supramolecular structure for both the complexes. Interactions of complexes with bovine serum albumins (BSA) and human serum albumins (HSA) have been studied by using electronic absorption and emission spectroscopic technique. The calculated values of binding constants (K_b) are (9.22 ± 0.26) × 10⁵ L mol⁻¹ ( 1 -BSA), (7.19 ± 0.16) × 10⁵ L mol⁻¹ ( 1 -HSA), (5.05 ± 0.20) × 10⁵ L mol⁻¹ ( 2 -BSA) and (3.56 ± 0.25) × 10⁵ L mol⁻¹ ( 2 -HSA). The mechanism of serum albumins-complex interactions have been investigated by fluorescence lifetime measurement. Fluorescence spectroscopic studies indicate that both the complexes interact with calf thymas-DNA. Catecholase activity of the complexes has been studied in methanol using 3,5-di-tert-butylcatechol (3,5-DTBC) as substrate and the result show that both the complexes are active for catalytic oxidation of 3,5-DTBC to 3,5-di-tert-butylquinone (3,5-DTBQ) in presence of molecular oxygen. Calculated values of turnover numbers are 71.81 ± 1.04 h⁻¹ and 69.45 ± 0.74 h⁻¹ for 1 and 2 , respectively.     

Synthesis and characterization of new selenophene‐based conjugated polymers for organic photovoltaic cells

Three new polymers poly(3,4′′′‐didodecyl) hexaselenophene) (P6S), poly(5,5′‐bis(4,4′‐didodecyl‐2,2′‐biselenophene‐5‐yl)‐2,2′‐biselenophene) (HHP6S), and poly(5,5′‐bis(3′,4‐didodecyl‐2,2′‐biselenophene‐5‐yl)‐2,2′‐biselenophene) (TTP6S) that have the same selenophene‐based polymer backbone but different side chain patterns were designed and synthesized. The weight‐averaged molecular weights (M_w) of P6S, HHP6S, and TTP6S were found to be 19,100, 24,100, and 19,700 with polydispersity indices of 2.77, 1.48, and 1.41, respectively. The UV–visible absorption maxima of P6S, HHP6S, and TTP6S are at 524, 489, and 513 nm, respectively, in solution and at 569, 517, and 606 nm, respectively, in the film state. The polymers P6S, HHP6S, and TTP6S exhibit low band gaps of 1.74, 1.95, and 1.58 eV, respectively. The field‐effect mobilities of P6S, HHP6S, and TTP6S were measured to be 1.3 × 10^?4, 3.9 × 10^?6, and 3.2 × 10^?4 cm² V^?1 s^?1, respectively. A photovoltaic device with a TTP6S/[6,6]‐phenyl C₇₁‐butyric acid methyl ester (1:3, w/w) blend film active layer was found to exhibit an open circuit voltage (V_OC) of 0.71 V, a short circuit current (J_SC) of 5.72 mA cm^?2, a fill factor of 0.41, and a power conversion efficiency (PCE) of 1.67% under AM 1.5 G (100 mW cm^?2) illumination. TTP6S has the most planar backbone of the tested polymers, which results in strong π–π interchain interactions and strong aggregation, leading to broad absorption, high mobility, a low band gap, and the highest PCE. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Electrical,Mechanical, and Thermal Properties of Poly(4,4′-Cyclohexylidene Diphenylene-m-Benzene/Toluene-2,4-Disulfonate)

Abstract

The films of poly(4,4′-cyclohexylidene diphenylene-m-benzene disulfonate) (PSBB, 0.610 mm thick) and poly(4,4′-cyclohexylidene diphenylene-toluene-2,4-disulfonate) (PSBT, 0.537 mm thick) showed 8.23 ± 0.25 and 9.6 ± 0.245 kV, respectively, as the dielectric breakdown voltage (ac) in air at room temperature. The same films have 8.8 × 10¹¹ and 7.2 × 10¹⁴ ω°Cm volume resistivity. PSBB (40 μm thick) and PSBT (50 μm thick) films have tensile strengths of 1971 and 1677 kg/cm² and percent elongations of 1.3 and 1.2, respectively. The static hardnesses of PSBB (0.178 mm thick) and PSBT (0.190 mm thick) at three different loads (15–60 g) are 12.8–15.5 and 14.5–16.5 kg/mm², respectively. PSBB and PSBT are thermally stable up to about 355°C in an N₂ atmosphere and involve two-step degradation. DSC and DTA showed T _g at about 125–127 and 138–142°C, respectively, for PSBB and PSBT in N₂. PSBB and PSBT have comparable breakdown voltages and volume resistivity with some useful plastics whereas they have superior T _g and thermal stability with retention of excellent solubility in common solvents over polysulfonates without a cardo group. Thus, the cardo (cyclo-hexyl) group has enhanced thermal and mechanical properties with excellent solubility and easy processing.     

Synthesis and Characterization of Sulfonated Polyimides Containing Trifluoromethyl Groups as Proton Exchange Membranes

A novel sulfonated diamine, 4,4′‐bis(4‐amino‐3‐trifluoromethylphenoxy) biphenyl 3,3′‐disulfonic acid (F‐BAPBDS), was successfully synthesized by nucleophilic aromatic substitution of 4,4′‐dihydroxybiphenyl with 2‐chloro‐5‐nitrobenzotrifluoride, followed by reduction and sulfonation. A series of sulfonated polyimides of high molecular weight (SPI‐x, x represents the molar percentage of the sulfonated monomer) were prepared by copolymerization of 1,4,5,8‐naphathlenetetracarboxylic dianhydride (NTDA) with F‐BAPBDS and nonsulfonated diamine. Flexible and tough membranes of high mechanical strength were obtained by solution casting and the electrolyte properties of the polymers were intensively investigated. The copolymer membranes exhibited excellent oxidative stability due to the introducing of the CF₃ groups. The SPI membranes displayed desirable proton conductivity (0.52×10⁻¹–0.97×10⁻¹ S·cm⁻¹) and low methanol permeability (less than 2.8×10⁻⁷ cm²·s⁻¹). The highest proton conductivity (1.89×10⁻¹ S·cm⁻¹) was obtained for the SPI‐90 membrane at 80°C, with an IEC of 2.12 mequiv/g. This value is higher than that of Nafion 117 (1.7×10⁻¹ S·cm⁻¹). Furthermore, the hydrolytic stability of the obtained SPIs is better than the BDSA and ODADS based SPIs due to the hydrophobic CF₃ groups which protect the imide ring from being attacked by water molecules, in spite of its strong electron‐withdrawing behaviors.     

Enhanced third‐order nonlinear optical properties determined in thin films using the Z‐scan technique: bis(μ‐4,4′‐oxydibenzoato)bis[(4′‐phenyl‐2,2′:6′,2′′‐terpyridine)cobalt(II)]

π‐Conjugated organic materials exhibit high and tunable nonlinear optical (NLO) properties, and fast response times. 4′‐Phenyl‐2,2′:6′,2′′‐terpyridine (PTP) is an important N‐heterocyclic ligand involving π‐conjugated systems, however, studies concerning the third‐order NLO properties of terpyridine transition metal complexes are limited. The title binuclear terpyridine Co^II complex, bis(μ‐4,4′‐oxydibenzoato)‐κ³O,O′:O′′;κ³O′′:O,O′‐bis[(4′‐phenyl‐2,2′:6′,2′′‐terpyridine‐κ³N,N′,N′′)cobalt(II)], [Co₂(C₁₄H₈O₅)₂(C₂₁H₁₅N₃)₂], (1), has been synthesized under hydrothermal conditions. In the crystal structure, each Co^II cation is surrounded by three N atoms of a PTP ligand and three O atoms, two from a bidentate and one from a symmetry‐related monodentate 4,4′‐oxydibenzoate (ODA²⁻) ligand, completing a distorted octahedral coordination geometry. Neighbouring [Co(PTP)]²⁺ units are bridged by ODA²⁻ ligands to form a ring‐like structure. The third‐order nonlinear optical (NLO) properties of (1) and PTP were determined in thin films using the Z‐scan technique. The title compound shows a strong third‐order NLO saturable absorption (SA), while PTP exhibits a third‐order NLO reverse saturable absorption (RSA). The absorptive coefficient β of (1) is −37.3 × 10⁻⁷ m W⁻¹, which is larger than that (8.96 × 10⁻⁷ m W⁻¹) of PTP. The third‐order NLO susceptibility χ⁽³⁾ values are calculated as 6.01 × 10⁻⁸ e.s.u. for (1) and 1.44 × 10⁻⁸ e.s.u. for PTP.     

Thermoplastic urethane elastomers. VI. Dilute solution properties in various solvents

A thermoplastic urethane elastomer prepared from a polycaprolactone diol, 4,4′-diphenylmethane diisocyanate, and 1,5-pentanediol was fractionated and the solution properties of the fractions were characterized in terms of viscosity and sedimentation. Mark-Houwink relations were established for data obtained at 30° in various solvents: In dimethylacetamide, tetramethylurea, and N-methyl pyrrolidone, the value of K_θ increased systematically in the range (1.7 to 2.0) × 10^?3. Lower values of K_θ were obtained in dimethylformamide (0.8 × 10^?3) and meta-cresol (0.9 × 10^?3). The molecular expansion coefficients in the various solvents were approximated from the experimental viscosity data. Short-range interactions between the solvent molecules and polymer chains are suggested as possible causes for differences in the hydrodynamic parameters.     

LC-Polyimides. XIX. Chiral and thermotropic poly(esterimide)s based on N-(4′-caboxyphenyl)trimellitimide and novel chiral spacers

Starting from commercial S- or R-3-bromo-2-methylpropanol, several new spacer diols were prepared. These spacers were polycondensed with the acid chloride of N-(4′-carboxyphenyl)trimellitimide. The resulting poly(ester-imide)s were characterized by elemental analyses, viscosity measurements, ¹H-NMR spectroscopy, DSC- and WAXD-measurements and optical microscopy. The poly(ester-imide)s derived from chiral, aliphatic spacers form layer structures in the solid state, but no liquid crystalline phase. With nonsymmetrical, nonchiral semialiphatic spacers, poly(ester-imide)s were obtained, which form a smectic E or H phase in the solid state, a smectic-A or -C phase in the melt, and a nematic phase, when the spacer possesses an odd number of CH₂ groups. The polycondensation of a chiral semialiphatic spacer yielded thermotropic poly(ester-imide)s with either S- or R-configuration. WAXD patterns measured with synchrotron radiation at various temperatures proved that a layer structure exists in the solid state (smectic-E^* or H^*) and a chiral smectic-A^* or -C^* phase plus a cholesteric phase in the melt. A 1 : 1 blend of the S- and R-polyesters was also studied, but did not show unusual features. © 1995 John Wiley & Sons, Inc.     

Synthesis of poly(p‐phenylene) macromonomers and multiblock copolymers

Rigid‐rod poly(4′‐methyl‐2,5‐benzophenone) macromonomers were synthesized by Ni(0) catalytic coupling of 2,5‐dichloro‐4′‐methylbenzophenone and end‐capping agent 4‐chloro‐4′‐fluorobenzophenone. The macromonomers produced were labile to nucleophilic aromatic substitution. The molecular weight of poly(4′‐methyl‐2,5‐benzophenone) was controlled by varying the amount of the end‐capping agent in the reaction mixture. Glass‐transition temperatures of the macromonomers increased with increasing molecular weight and ranged from 117 to 213 °C. Substitution of the macromonomer end groups was determined to be nearly quantitative by ¹H NMR and gel permeation chromatography. The polymerization of a poly(4′‐methyl‐2,5‐benzophenone) macromonomer [number‐average molecular weight (M_n) = 1.90 × 10³ g/mol; polydispersity (M_w)/M_n = 2.04] with hydroxy end‐capped bisphenol A polyaryletherketone (M_n = 4.50 × 10³ g/mol; M_w/M_n = 1.92) afforded an alternating multiblock copolymer (M_n = 1.95 × 10⁴ g/mol; M_w/M_n = 6.02) that formed flexible, transparent films that could be creased without cracking. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3505–3512, 2001     

Synthesis of a novel [60]fullerene pearl-necklace polymer,poly(4,4′-carbonylbisphenylene trans-2-[60]fullerenobisacetamide)

A novel [60]fullerene pearl-necklace polymer, poly(4,4′-carbonylbisphenylene trans-2-[60]fullerenobisacetamide), was synthesized by a direct polycondensation of trans-2-[60]fullerenobisacetic acid with 4,4′-diaminobenzophenone in the presence of large excesses of triphenyl phosphite and pyridine. In the present polymer, [60]fullerene pearls and diamine linkers were attached to each other by methano-carbonyl connectors. The molecular weight M_w of the polymer was determined to be 4.5 × 10⁴ on the basis of the TOF-MS, and a GPC analysis of the polymer using polystyrene standards showed a weight-average molecular weight of 5.3 × 10⁴. The UV-vis spectrum of the resultant polymer in N,N-dimethylacetamide (DMAc) exhibited a broad absorption (λ_max 310 nm, ε 2.1 × 10⁴ L · mol⁻¹ · cm⁻¹), tailing to longer wavelengths, and a fluorenscence peak centered at 550 nm was observed in DMAc. There was observed a large downfield-shift of the cyclopropane methyne proton in the ¹H-NMR spectra from 4.57 ppm of the ethyl ester to 5.78 ppm of the polyamide. These observations indicate that the present polyamide is a high-molecular-weight [60]fullerene pearl-necklace polymer and that the cyclopropane rings are efficient to make the [60]fullerene cages and the diamine components conjugatable. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3632–3637, 1999     

Synthesis of functionalized fluorine-containing hyperbranched poly(aryl ether ketones) for optical applications

Hyperbranched poly(aryl ether ketones) with terminal fluorine atoms (OH: F = 0.48: 1.00) or hydroxyl groups (OH: F = 2.02: 1.00) have been obtained through the polycondensation of bis(4,4′-dihydroxydiphenyl-2,2-hexafluoropropane) with 1,3,5-tris[4-(4-fluorobenzoyl)phenoxy]benzene in tetramethylene sulfone. Both polymers have M _n = (7.1?7.3) × 10³ and M _w = (8.4?8.8) × 10³ and are transparent in the near-IR region, in particular, at 1.30 and 1.55 μm.