Synthesis and characterization of a new network polymer electrolyte containing polyether in the main chains and side chains

A new network polymer electrolyte matrix with polyether in the side chains and main chains was synthesized by the azo-macroinitiator method and urethane reaction. The macroinitiator, polymer and network polymer were confirmed by Fourier-transform infrared (FT-IR) spectroscopy and ¹H NMR. FT-IR was also used to study the environment of lithium ions doped in these network polymer electrolytes. Three important groups are considered: N-H, carbonyl, and ether groups. The thermal properties of the polymer electrolytes were measured by differential scanning calorimetry and thermogravimetric analysis. The T_g value of this polymer is less than that of a general comb-like polymer. Added lithium ions interact with the oxygen atoms on ether groups, causing the T_g of the polymer electrolyte to increase. Moreover, the interaction between lithium ions and ether groups decreases the decomposition temperature of the polymer. The conductivity measured by AC impedance reached a maximum of 10⁻⁴ S cm⁻¹. A plot of conductivity vs. temperature fit the Vogel-Tamman-Fulcher equation, indicating that ionic mobility in this network polymer electrolyte is coupled to segmental chain movements.     

Charge distributions in polyacetylene chains containing a positively charged defect

We present a comparative study of the AIM, CHELPG, GAPT, MK, Mulliken, NPA, and RESP charge distributions associated with a positively charged soliton on increasingly large trans‐polyacetylene chains, at HF, MP2, and DFT levels of theory. The charge storage in the soliton‐bearing systems is explored in detail, including charge magnitude, charge separation, charge alternation, and chain length effects. The grouping of the charge distributions at a given level of theory, as well as the sensitivity of a given charge distribution to the inclusion of electron correlation in its computation, are investigated using similarity analysis. Several of the charge definitions have been applied for the first time for charged soliton‐bearing systems, and there are substantial differences between the charge distributions for the charged and neutral systems. Thus, AIM charges are no longer one of the largest charge values, the AIM charges can be in counterphase with other definitions, and the GAPT charges for neutral systems are quite different from the GAPT charges for charged systems, e.g., the magnitudes of the GAPT charges are anomalously large and increase with the size of the charged system. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

Synthesis and properties of an ionic polyacetylene with aromatic heterocycles

A new ionic polyacetylene with two aromatic heterocycles (pyridyl and thienyl) was prepared by the activation polymerization of 2‐ethynylpyridine by using 3‐(6‐bromohexyloxy)methylthiophene without any additional initiator or catalyst. The activated acetylenic triple bond of N‐substituted‐2‐ethynylpyridinium bromide, formed at first quaternarization process, was susceptible to linear polymerization. The instrumental analysis data on the polymer structure revealed that the polymer have the conjugated polyene backbone structure with the designed two aromatic heterocycles. The photoluminescence peak is located at 510 nm corresponding to a photon energy of 2.43eV. The electrochemical properties of this ionic polyacetylene were also measured and discussed. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5679–5685, 2007     

Synthesis and characterization of white‐light‐emitting polyfluorenes containing orange phosphorescent moieties in the side chain

Two orange phosphorescent iridium complex monomers, 9‐hexyl‐9‐(iridium (III)bis(2‐(4′‐fluorophenyl)‐4‐phenylquinoline‐N,C^2′)(tetradecanedionate‐11,13))‐2,7‐dibromofluorene (Br‐PIr) and 9‐hexyl‐9‐(iridium(III)bis(2‐(4′‐fluorophenyl)‐4‐methylquinoline‐N,C^2′)(tetradecanedionate‐11,13))‐2,7‐dibromofluorene (Br‐MIr), were successfully synthesized. The Suzuki polycondensation of 2,7‐bis(trimethylene boronate)‐9,9‐dioctylfluorene with 2,7‐dibromo‐9,9‐dioctylfluorene and Br‐PIr or Br‐MIr afforded two series of copolymers, PIrPFs and MIrPFs, in good yields, in which the concentrations of the phosphorescent moieties were kept small (0.5–3 mol % feed ratio) to realize incomplete energy transfer. The photoluminescence (PL) of the copolymers showed blue‐ and orange‐emission peaks. A white‐light‐emitting diode with a configuration of indium tin oxide/poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate)/PIr05PF (0.5 mol % feed ratio of Br‐PIr)/Ca/Al exhibited a luminous efficiency of 4.49 cd/A and a power efficiency of 2.35 lm/W at 6.0 V with Commission Internationale de L'Eclairage (CIE) coordinates of (0.46, 0.33). The CIE coordinates were improved to (0.34, 0.33) when copolymer MIr10PF (1.0 mol % feed ratio of Br‐MIr) was employed as the white‐emissive layer. The strong orange emission in the electroluminescence spectra in comparison with PL for these kinds of polymers was attributed to the additional contribution of charge trapping in the phosphorescent dopants. © 2007 Wiley Periodicals, Inc. JPolym Sci Part A: Polym Chem 45: 1746–1757, 2007     

Synthesis and electrical properties of polyacetylene derivatives

Cyclopolymerization of 1,6‐heptadiyne derivatives containing the bulky substitutents was carried out by metathesis catalyst systems. The catalytic activity of molybdenum (V) chloride (MoCl₅) in homopolymerization is greater than that of the MoCl₅‐cocatalyst system, and copolymerization is vice versa in catalytic activity. Newly synthesized homo‐ and copolymers were soluble in common organic solvents and could afford thin film by solution‐casting onto the indium–tin oxide coated glass substrate. The NMR, Fourier transform infrared spectroscopic, and UV–visible spectra indicated that these polymers have a linear conjugated cyclic polyene structure having a bulky substitutent as a pendant group. The number‐average molecular weight of these polymers was in the range of 2.4–6.27 × 10³. The copolymers exhibited a relatively higher molecular weight than that of the homopolymers. The copolymers were stable up to 380 °C. The electrical conductivities of the I₂‐doped copolymer thin film by the four‐point probe method and surface plasmon resonance spectroscopy were about 500 and 600 S/cm, respectively. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 958–964, 2002     

Synthesis and characterization of conjugated polymers containing a carbazole moiety

Two series of conjugated polymers with a carbazole moiety were synthesized by Knovenagel and Wittig condensations. The chemical structure, thermogravimetric, photophysical and electrochemical properties of the polymers were characterized by ¹H‐NMR, IR, GPC, TG, UV‐vis, FL, and CV. The results indicated that PBM is the most thermally stable one and PBP is the most thermally instable one. The absorption and emission properties of the polymers were adjusted by the modification of chemical structures. The quenching effect of cyano group and oxygen atom results in the lower fluorescence quantum efficiency. The fitted emission spectra suggested that the emission spectra of all the polymers come from different vibronic transitions and aggregation emission. Copyright © 2008 John Wiley & Sons, Ltd.     

Synthesis and characterization of an acrylate polymer containing chlorine-1,3-dioxalane groups in side chains

Poly[2-（4-chlorophenyl）-1,3-dioxolan-4-yl]methyl acrylate,poly（CPhDMA）,was synthesized with radical polymerization process using 2,2′-azobisisobutyronitrile as radical initiator in 1,4-dioxane at 60℃.The structure of poly（CPhDMA） was confirmed by means of UV-Vis,FT-IR,¹H-NMR,and ¹³C-NMR spectral techniques.The molecular weight distribution values of the polymer were determined with gel permeation chromatography（GPC）.The number-average molecular weight（M_n）,weight-average molecular weight（M_W） and polydispersity index（PDI） values of poly（CPhDMA） were determined to be 10300,21600 and 2.097,respectively.The thermal degradation kinetics of the polymer was investigated by using TG/DTG-DTA and DSC analyses at different heating rates in dynamic nitrogen atmosphere.The apparent activation energy values obtained by Flynn-Wall-Ozawa and Friedman methods were found to be 91.68 and 85.23 kJ mol^-1,respectively,for thermal decomposition of poly（CPhDMA）.Also,the thermal degradation activation energy value of poly（CPhDMA） was calculated by using the Kissinger method based on the DTG,DTA and DSC data.Then the mechanism function of it was determined by master plots method.Finally,electrical and optical properties of poly（CPhDMA） were determined by four-point probe and UV-Vis techniques,respectively.     

Synthesis of conjugated copolymers containing phenothiazinylene vinylene moieties and their electrooptic properties

Four different types of conjugated copolymers, consisting of alternating structures of phenothiazinylene vinylene and phenylene vinylene derivatives such as phenylene vinylene, 1,1′‐biphenyl‐4,4′‐ylene vinylene, 2‐methoxy‐5‐(2‐ethylhexyloxy)‐1,4‐phenylene vinylene, and 9,10‐anthrylene vinylene, were prepared by Horner–Emmons condensation between appropriate diphosphonates and dialdehydes. Single‐layer and double‐layer light‐emitting diodes were fabricated with the synthesized conjugated polymers, and their electroluminescent properties were investigated. Poly(N‐2‐ethylhexyl‐3,6‐phenothiazinylene vinylene‐alt‐9,10‐anthrylene vinylene), containing phenothiazinylene vinylene and anthrylene vinylene as repeat units, emitted a reddish‐orange color with Commission Internationale de l'Eclairage coordinates of x = 0.6173 and y = 0.3814 that was very similar to the National Television System Committee standard red, and it showed a bipolar carrier‐injection/transporting capability caused by electron‐withdrawing anthracene and electron‐donating amino groups. Poly[N‐2‐ethylhexyl‐3,6‐phenothiazinylene vinylene‐alt‐2‐methoxy‐5‐(2‐ethylhexyloxy)‐1,4‐phenylene vinylene], containing phenothiazinylene vinylene and dialkoxy phenylene vinylene moieties, showed excellent hole‐injection/transporting capability. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2502–2511, 2003     

Synthesis and characterization of new polystyrenes containing tributyltin moieties linked to the aromatic ring through a methylenic spacer

Novel polymeric derivatives bearing tributyltin carboxylate moieties in the side chain were synthesized. The coordination at tin in solution and in the solid state was investigated by both Sn‐NMR and FT‐IR: the metal atom appears completely tetracoordinated in chloroform solution, while in the solid state all polymeric products exhibit both tetra‐ and pentacoordination at tin, the latter increasing with the amount of tin containing units. No evidence of tin leaching by hydrolysis of the organometallic ester was observed for these materials. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5372–5383, 2004     

Synthesis and characterization of polymers containing linear sugar moieties as side groups

The synthesis of a water-soluble monomer, namely 4-vinylphenyl-d-gluco(d-manno)hexitol (4) derived from d-gluconolactone, is here presented. The homopolymerization of the vinylsugar has been conducted in both aqueous and organic media using free-radical initiators. High-molar-mass water-soluble polymers are obtained. The copolymerization behavior of the vinylphenyl sugar monomer with a hydrophilic monomer such as acrylamide, as well as with a hydrophobic monomer such as styrene, has been investigated. Statistical- and block-type copolymers have thus been prepared. The structures of the polymers were confirmed by NMR and their thermal properties examined by DSC.     

Synthesis and properties of a soluble and widely conjugated polyacetylene with anthryl pendant

The metathesis polymerization of an anthrylacetylene bearing an alkyl ester group, 9‐(10‐hexoxycarbonyl)anthrylacetylene ( 1 ), was conducted with various transition‐metal catalysts. A completely soluble black polymer was obtained from 1 in a good yield when W‐based catalysts were employed. The polymerization at a high monomer concentration (1 M) and a high temperature (80 °C) led to the formation of poly( 1 ) with a weight‐average molecular weight of 297 × 10³ in an 80% yield. The use of cocatalysts unexpectedly decreased both the yield and molecular weight of poly( 1 ). Rh‐catalyzed and Mo‐catalyzed polymerizations, however, resulted in poor yields of the polymer. The ultraviolet–visible spectrum of poly( 1 ) showed a significantly redshifted absorption (λ_max = 571) with a cutoff at 780 nm, which verified the very high order of conjugation of the main chain. Poly( 1 ) exhibited the largest third‐order nonlinear optical susceptibility [χ⁽³⁾ (−ω; ω, 0, 0) = − 1.9 × 10⁻¹⁰ esu] among the polymers from the monosubstituted polyacetylenes synthesized so far. The electrical conductivity of poly( 1 ) in an I₂‐doped state was 8.77 × 10⁻⁴ at 293 K. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4717–4723, 2000     

Synthesis,characterization and properties of polycarbonate containing carboxyl side groups

Diphenolic Acid, DPA [bis(4-hydroxyphenyl)pentanoic acid] can be made from cellulose-rich waste. The t-butyl ester was converted to homo- and copolycar- bonates (with bis-phenol-A, BPA). Deblocking the ester yielded polycarbonates with pendent carboxyl groups that exhibit all the properties of polyelectrolytes and retain solubility in aqueous base without degradation for long periods.     

Synthesis and photovoltaic properties of conjugated side chains polymers with different electron‐withdrawing and donating end groups

A series of novel low band gap polymers containing conjugated side chains with 4,7‐dithien‐5‐yl‐2,1,3‐benzodiathiazole and different electron‐withdrawing end groups of aldehyde ( PT‐DTBTCHO ), 2‐ethylhexyl cyanoacetate ( PT‐DTBTCN ), 1,3‐diethyl‐2‐thiobarbituric acid ( PT‐DTBTDT ), and electron‐donating end group of 2‐methylthiophene ( PT‐DTBTMT ) have been designed and synthesized. All polymers exhibit good solubility in common organic solvents, film‐forming ability, and thermal stability. These conjugated polymers show the broad ultraviolet‐visible absorption and the narrow optical band gaps in the range of 1.65–1.90 eV. Through changing the end group of conjugated side chains, the photophysical properties and energy levels of the polymers were tuned effectively. Bulk heterojunction solar cells based on the blend of these polymers and (6,6)‐phenyl‐C₆₁‐butyric acid methyl ester (PC₆₁BM) reached the best power conversion efficiency (PCE) of 2.72%. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis of conjugated polymers with azobenzene moieties in the main chain

Poly(phenylenevinylene)‐based conjugated polymers with azobenzene groups in the main chains were prepared by the Pd‐catalyzed coupling polymerization of divinylarenes with dihaloarenes. The Pd‐catalyzed coupling polymerization of 4,4′‐divinylazobenzene with dihaloarenes such as 1,3‐dibromobenzene, 1,4‐dibromo‐2,5‐dihexylbenzene, 4,4′‐dibromoazobenzene, and 4,4′‐diiodoazobenzene resulted in polymers with poor solubility. In contrast, soluble polymers containing azobenzene moieties in the main chains were attainable from divinylbenzenes with 4,4′‐dihaloazobenzenes if either or both of the monomers possessed hexyl groups on the aromatic rings. The number‐average molecular weight of the polymer exceeded 10,000 under optimized conditions, and the polymer showed a remarkably redshifted absorption in the visible region (456 nm). ¹H NMR and IR spectra supported that the polymers having only trans‐geometry for the double bonds. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1057–1063, 2000     

Synthesis and properties of polyurethanes bearing urethane moieties in the side chain

Polyurethanes bearing urethane groups in the side chains were prepared by the addition of isocyanates to the hydroxyl groups in poly(hydroxyurethane) prepared by the polyaddition of a bifunctional cyclic carbonate with 1,12‐diaminododecane. The urethanization proceeded quantitatively in the presence of a catalytic amount of di‐n‐butyltin dilaurate. The resulting polyurethane had a higher glass transition temperature than the original poly(hydroxyurethane), although its esterified product had a lower glass transition temperature. The urethanization with 3‐(triethoxysilyl)propyl isocyanate also proceeded effectively to afford both soluble and insoluble polymers, depending on the reaction conditions. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3408–3414, 2007     

Synthesis and properties of new polyimides containing flourinated alkoxy side chains

A series of new polyimides containing fluorinated alkoxy side chains are prepared from novel fluorinated alkoxy diamines. The dieletric constant at 1 kHz in the fluorinated polyimides decreases from 3.3 to 2.6 as fluorine content increases. The refractive index also changes from 1.58 to 1.48, dependent on the fluorine content. In addition, the fluorinated polyimides exhibit lower water absorption than the reference polyimides prepared from m-phenylenediamine.     

Synthesis and characterization of new metal-free and metallophthalocyanines containing macrocyclic moieties

The synthesis and characterization of new metal-free 7 and metallophthalocyanines 8, 9 carrying macrocyclic N₂S₂O₄ donor groups on peripheral positions have been investigated. Phthalonitrile derivative 6 was synthesized according to Rosenmund von Braun procedure from compound 5. The novel compounds were characterized by elemental analysis, IR, ¹H and ¹³C NMR, UV-Vis and MS spectra data.     

Synthesis and photovoltaic properties of poly(p‐phenylenevinylene) derivatives containing oxadiazole

A novel poly(p‐phenylenevinylene) PPV‐based copolymer (3C‐OXD‐PPV) with electron‐deficient oxadiazole segments as the side chain has been successfully synthesized through the Gilch polymerization. The obtained copolymer is soluble in common organic solvents such as chloroform, tetrahydronfuran, and 1,1,2,2‐tetrachloroethane. The copolymer was characterized by ¹H NMR, elemental analysis and GPC. TGA measurement of the copolymer shows it has good thermal stability with decomposition temperature higher than 350 °C. The absorption, electrochemical properties of the 3C‐OXD‐PPV were investigated and also compared with the properties of MEH‐PPV. The HOMO and LUMO levels of 3C‐OXD‐PPV were estimated from the electrochemical cyclic voltammograms. Bulk‐heterojunction PVCs were fabricated by using 3C‐OXD‐PPV blended PCBM as an active layer. The PCE of the PVC is 1.60% under 100 mW cm^?2 AM 1.5 illumination, which indicates that 3C‐OXD‐PPV is a potential candidate for the application of polymer PVC. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1003–1012, 2009     

Synthesis and characterization of blue‐light emissive carbazole containing perfluorocyclobutyl arylene ether polymers

A series of N‐alkyl/aryl carbazole 3,6‐substituted arylene trifluorovinyl ether (TFVE) monomers were synthesized in high purity and yield from a concise four‐step synthesis using carbazole as a starting material. Condensate‐free, step‐growth chain extension of the monomers afforded perfluorocyclobutyl (PFCB) arylene ether homo‐ and copolymers as solution processable, optically transparent blue‐light emissive materials. Arylene TFVE monomers and conversion to PFCB arylene ether polymers were structurally elucidated and purity confirmed by high resolution mass spectroscopy, NMR (¹H, ¹³C, and ¹⁹F) spectroscopy, gel permeation chromatography, and attenuated total reflectance Fourier transform infrared analysis. Thermal analysis by differential scanning calorimetry and thermogravimetric analysis revealed glass transition temperatures >150 °C and onset of decomposition in nitrogen >410 °C with 40 wt % char yield up to 900 °C. Optical and electrochemical studies included solution (tetrahydrofuran) and solid state (spin cast thin film) UV–vis/fluorescence spectroscopy and cyclic voltammetry which showed structure dependence of these blue emissive systems on the nature of the N‐alkyl/aryl carbazole substitution in either homo‐ or copolymer configurations. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 552–560