Substituent effect on the optoelectronic properties of poly(p‐phenylenevinylene) based conjugated‐nonconjugated copolymers

Two classes of light emitting Poly(p‐phenylenevinylene) (PPV) based conjugated‐nonconjugated copolymers (CNCPs) have been synthesized. The conjugated chromophores containing 2‐methoxy‐5‐(2′‐ethylhexyloxy)‐1,4‐phenylenevinylene (MEHPV) and 2,5‐dimethyl‐1,4‐phenylenevinylene (DMPV) moieties are rigid segments and nonconjugated portion containing hexyl units are flexible in nature. All copolymers were synthesized by well‐known Wittig reaction between the appropriate bisphosphonium salts and the dialdehyde monomers. The resulting polymers were found to be readily soluble in common organic solvents like chloroform, THF and chlorobenzene. The effect of chromophore substituents on the optical and redox properties of the copolymers has been investigated. Color tuning was carried out by varying the molar percentage of the comonomers. The UV‐Vis absorption and PL emission of the copolymers were in the range 314–395 nm and 494–536 nm respectively. All the polymers show good thermal stability. Polymer light‐emitting diodes (PLEDs) were fabricated in ITO/PEDOT:PSS/emitting polymer/cathode configurations of selected polymers using double‐layer, LiF/Al cathode structure. The emission maxima of the polymers were around 499–536 nm, which is a blue‐green part of the color spectrum. The threshold voltages of the EL polymers were in the range of 5.4–6.2 V. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

New light emitting materials: Alternating copolymers with hole transport and emitting chromophores

A new type of novel high‐efficiency light‐emitting nitrogen‐containing poly(phenylene vinylene) (PPV)‐related copolymers, which have hole‐transfer moieties such as triphenylamine (TPA) and conjugated aromatic units such as 4,4′‐biphenylene, 1,4‐phenylene, 2,5‐dimethyl‐1,4‐phenylene, 1,4‐ or 1,5‐naphthylene, and 9,10‐anthrylene, was designed and synthesized by the well‐known Wittig–Hornor reaction. The resulting alternating copolymers were highly soluble in common organic solvents. They can spin‐cast onto various substrates to give highly transparent homogeneous thin films without heat treatment. The introduction of TPA units in the PPV backbone improved processibility and limited the π‐conjugation length. Furthermore, the additional π‐electron delocalization between the lone‐paired electron in the nitrogen atom and π‐electrons in the conjugated units contributed to the improvement of the fluorescence quantum yields of these copolymers. All these alternating copolymers except TPA–PAV have high‐efficiency photoluminescence and they are very promising for light‐emitting diodes (LEDs). It is very promising that TPA–PAV will emit white light when used in LED device due to the broad emission spectra. The origin of the broad spectrum is contributed by the charge‐transfer complex formation, which can be proved by the absorption and emission spectra of TPA–PAV solutions. When the aromatic units were 1,4‐phenylene, 1,4‐ or 1,5‐naphthylene, 4,4′‐biphenylene, and 9,10‐anthrylene, respectively, with increase of the capability to accept electrons in aromatic units, the charge transfer from TPA to aromatic units occurred; consequently, the fluorescence quantum yield decreased. The introduction of the alkoxy‐substitute group on the aromatic units in the polymer backbone caused the red shift of the absorption and emission spectra of the copolymers due to the stronger delocalization of the π‐conjugated system. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 3351–3358, 1999     

Synthesis and characterization of novel phenyl‐substituted poly(p‐phenylene vinylene) derivatives

Two novel phenyl‐substituted poly(p‐phenylene vinylene) derivatives, poly{2‐[3′,4′‐(2″‐ethylhexyloxy)(3″,7″‐dimethyloctyloxy)benzene]‐1,4‐phenylenevinylene} (EDP‐PPV) and poly{2‐[3′,4′‐(2″‐ethylhexyloxy)(3″,7″‐dimethyloctyloxy)benzene]‐5‐methoxy‐1,4‐phenylenevinylene} (EDMP‐PPV), and their copolymer, poly{2‐[3′,4′‐(2″‐ethylhexyloxy)(3″,7″‐dimethyloctyloxy)benzene]‐1,4‐phenylene‐vinylene‐co‐2‐[3′,4′‐(2″‐ethylhexyloxy)(3″,7″‐dimethyloctyloxy)benzene]‐5‐methoxy‐1,4‐phenylenevinylene} (EDP‐co‐EDMP‐PPV; 4:1, 1:1, and 1:4), were successfully synthesized according to the Gilch route. The structures and properties of the monomers and the resulting conjugated polymers were characterized with ¹H‐NMR, ¹³C‐NMR, elemental analysis, gel permeation chromatography, thermogravimetric analysis, ultraviolet–visible absorption spectroscopy, and photoluminescence and electroluminescence (EL) spectroscopy. The EL polymers possessed excellent solubility in common solvents and good thermal stability with a 5% weight loss temperature of more than 380°C. The weight‐average molecular weights and polydispersity indices of EDP‐PPV, EDMP‐PPV, and EDP‐co‐EDMP‐PPV were 1.40–2.58 × 10⁵, and 1.19–1.52, respectively. Double‐layer light‐emitting diodes with the configuration of indium tin oxide/polymer/tris(8‐hydroxyquinoline)aluminum/Al devices were fabricated, and EDP‐co‐EDMP‐PPV (1:1) showed the highest EL performance and exhibited a maximum luminance of 1050 cd/m² at 19.5 V. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1259–1266, 2005     

Poly(pyridinium salt)s with organic counterions derived from an aromatic diamine containing tetraoxyethylene units exhibiting amphotropic liquid‐crystalline and photoluminescence properties

Several poly(pyridinium salt)s containing various organic counterions and tetraoxyethylene units in their backbones were synthesized by either ring‐transmutation polymerization reaction of 4,4'‐(1,4‐phenylene)bis(2,6‐diphenylpyrylium tosylate) with bis(2‐(2‐(4‐aminophenoxy)ethoxy)ethyl) ether on heating in dimethyl sulfoxide or metathesis reaction of the tosylate polymer with the corresponding lithium or sodium salts in acetonitrile. Their chemical structures were determined by ¹H‐NMR and ¹³C‐NMR spectroscopy, and elemental analyses. Their number‐average molecular weights and polydispersity indices were in the range of 34,000–52,000 and 1.14–1.38, respectively, as determined by gel permeation chromatography. They were characterized both for their thermotropic and lyotropic liquid‐crystalline properties by using differential scanning calorimetry and polarizing optical microscopy. As these polymers exhibited liquid‐crystalline phase both in the melt and in solutions, they are classified as an amphotropic class of ionic polymers. Their light‐emitting properties in a large number of organic solvents that ranged from nonpolar to polar solvents and in films cast from methanol and acetonitrile were also studied by using spectrofluorometry. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and properties of polyether with short alternating conjugated and nonconjugated blocks containing oxadiazole units

A polyether, poly[(2,5‐dimethylene‐1,3,4‐oxadiazole)dioxy‐1,4‐phenylene‐1,2‐ethenylene‐1,4‐phenylene‐1,2‐ethenylene‐1,4‐phenylene], based on short alternating conjugated oxadiazole units, has been synthesized, which is a kind of PPV derivative that emits blue light. The resulting polymer is fairly soluble in chloroform. The synthesized polymer shows a UV–visible absorbency maximum wavelength around 310 nm in solution. The photoluminescence maximum wavelength for the resulting polymer appears around 470 nm. The polymer also exhibits good thermal stability up to 300°C under N₂ atmosphere. It is also observed that the onset temperature of thermal decomposition is as high as 355°C. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2682–2686, 2002     

Syntheses and properties of new poly(amide–imide)s based on 1,4‐bis(4‐aminophenoxy)naphthalene and various diimide–diacids

A series of new alternative poly(amide–imide)s (PAIs, III_a–j ) was synthesized by the direct polycondensation of 1,4‐bis(4‐aminophenoxy)naphthalene (1,4‐BAPON) with various aromatic diimide–diacids. These polymers were obtained in quantitative yields with inherent viscosities of 0.71–1.03 dL/g. Except for III_a, most of the polymers were soluble in aprotic polar solvents such as NMP, DMAc, DMF, and DMSO and could be solution‐cast into transparent, flexible, and tough films. The glass transition temperatures of these PAIs were in the range of 235–280°C. Thermogravimetric analyses established that these polymers were fairly stable up to 450°C, and 10% weight loss temperatures were recorded in the range of 520–569°C under nitrogen and 506–566°C under an air atmosphere. Compared with the PAIs with the 1,4‐bis(4‐aminophenoxy)benzene structure (series IV), the solubility of series III was better than that of series IV. Series III also exhibited lower crystallinity and better processability than those of series IV. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 217–225, 2000     

Synthesis and electroluminescence properties of a novel poly(paraphenylene vinylene)‐based copolymer with tri(ethylene oxide) segments on the backbone

A novel light‐emitting copolymer [tri(ethylene oxide)–poly(paraphenylene vinylene) (TEO–PPV)] containing alternating rigid, conjugated distyrylbenzene [poly(paraphenylene vinylene) model oligomer] as light‐emitting units and flexible tri(ethylene oxide) as ionic conductive units was synthesized. The polymer was characterized with Fourier transform infrared, ¹H‐NMR, ultraviolet–visible spectroscopy, differential scanning calorimetry, and gel permeation chromatography. TEO–PPV has excellent solubility in conventional organic solvents such as tetrahydrofuran, chloroform, benzene, and toluene. The estimated lowest unoccupied molecular orbital, highest occupied molecular orbital, and band gap are 2.35, 5.29, and 2.94 eV, respectively. Single‐layer and double‐layer light‐emitting diodes with indium tin oxide anodes and calcium cathodes were fabricated, and the photoluminescence (PL) and electroluminescence (EL) properties were investigated. The maximum EL emissive peak (475 nm) of the devices is essentially the same as that of PL. Anomalous current–voltage characteristics were observed in both devices. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2195–2200, 2002     

Studies on the synthesis and optical properties of novel blue light‐emitting polymers containing phosphorus and oxadiazole structures

Novel phosphorus‐containing polymers with high‐electron‐affinity oxadiazole were synthesized and characterized by thermal analysis and spectroscopy (infrared, ultraviolet‐visible, photoluminescence, cyclic voltammetry) measurements. These new polymers can be used as blue electroluminescent materials and as electron‐transport layers in polymer light‐emitting diodes. In this study, aromatic polyethers containing electron‐transporting chromophores and emission chromophores were synthesized from 2,5‐bis‐(4‐fluoroaryl)‐1,3,4‐oxadiazole and 2‐(6‐oxido‐6H‐dibenz<c,e><1,2> oxaphosphorin‐6‐yl)‐1,4‐naphthalenediol (DOPO‐NBQ). The effects of reaction temperature and time on the formation of polyethers were investigated to obtain optimum conditions for polyether manufacturing. All the resulting polymers were thermally stable at <460 °C. The absorption peaks of these polymers were at 350–365 nm, whereas the photoluminescent peaks were at 460–481 nm. But, the intensity of polymer absorption decreased and a blue shift was observed in the photoluminescent spectra as the temperature increased. In addition, these polymers containing the electron‐transporting oxadiazole indeed showed extra reduction potentials in cyclic voltammetry measurements. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2367–2376, 2002     

Electroluminescence and photovoltaic properties of poly(p‐phenylene vinylene) derivatives with dendritic pendants

A copolymer of dendronized poly(p‐phenylene vinylene) (PPV), poly{2‐[3′,5′‐bis (2′‐ethylhexyloxy) bnenzyloxy]‐1,4‐phenylene vinylene}‐co‐poly[2‐methoxy‐5‐(2′‐ethylhexyloxy)‐1,4‐phenylene vinylene] (BE‐co‐MEH–PPV), was synthesized with the Gilch route to improve the electroluminescence and photovoltaic properties of the dendronized PPV homopolymer. The polymer was characterized by ultraviolet–visible absorption spectroscopy, photoluminescence spectroscopy, and electrochemical cyclic voltammetry and compared with the homopolymers poly{2‐[3′, 5′‐bis(2‐ethylhexyloxy) benzyloxy‐1,4‐phenylene vinylene} (BE–PPV) and poly[2‐methoxy‐5‐(2′‐ethylhexyloxy)‐1,4‐phenylenevinylene] (MEH–PPV). Polymer light‐emitting diodes based on the polymers with the configuration of indium tin oxide (ITO)/poly(3,4‐ethylene dioxythiophene) : poly(styrene sulfonate) (PEDOT : PSS)/polymer/Ca/Al were fabricated. The electroluminescence efficiency of BE‐co‐MEH–PPV reached 1.64 cd/A, which was much higher than that of BE–PPV (0.68 cd/A) and a little higher than that of MEH–PPV (1.59 cd/A). Photovoltaic properties of the polymer were studied with the device configuration of ITO/PEDOT : PSS/polymer : [6,6J‐phenyl‐C₆₁‐butyric acid methyl ester] (PCBM)/Mg/Al. The power conversion efficiency of the device based on the blend of BE‐co‐MEH–PPV and PCBM with a weight ratio of 1 : 3 reached 1.41% under the illumination of air mass 1.5 (AM1.5) (80 mW/cm²), and this was an improvement in comparison with 0.24% for BE–PPV and 1.32% for MEH–PPV under the same experimental conditions. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Functional copolymers of p‐cumyl phenyl methacrylate and glycidyl methacrylate: Synthesis,characterization, and reactivity ratios

Free‐radical polymerization of p‐cumyl phenyl methacrylate (CPMA) was performed in benzene using bezoyl peroxide as an initiator at 80°C. The effect of time on the molecular weight was studied. Functional copolymers of CPMA and glycidyl methacrylate (GMA) with different feed ratios were synthesized by free‐radical polymerization in methyl ethyl ketone at 70°C, and they were characterized by FTIR and ¹H‐NMR spectroscopy. The molecular weights and polydispersity indexes of the polymers and copolymers were determined by gel permeation chromatography. The copolymer composition was determined by ¹H‐NMR. The glass‐transition temperature of the polymer and the copolymers was determined by differential scanning calorimetry. The reactivity ratios of the monomers were determined by the Fineman–Ross and Kelen–Tudos methods. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 336–347, 2005     

Block polymers from isocyanate-terminated intermediates. IV. Properties of cured butadiene–ε-caprolactam block polymers

Butadiene–ε-caprolactam block polymers containing a high proporation of 1,2 units in the butadiene-segments were synthesized and physical properties were measured on the cured copolymers. Flexural strength and impact resistance both increase regularly with increasing ε-caprolactam content in peroxide cured copolymers. This behavior is explained by the higher values of flexural modulus and impact resistance for poly(ε-caprolactam) compared with peroxide-cured polybutadiene resins. Copolymers reinforced with silica showed higher heat distortion temperatures but lower impact resistance than corresponding unfilled samples. Arrhenius plots of flexural properties at various test temperatures were linear. Both flexural modulus and strength decreased regularly with increasing test temperature. Flexural properties of filled copolymers were relatively unaffected by heat aging up to 204°C for several weeks, however, dramatic decreases in these properties were noted in a matter of days when heat aging was done at 260–316°C. These results are explained by the rapid degradation of poly(ε-caprolactam) above its melting point. Block polymers whose butadiene segments contained a high proportion of 1,4 units were also synthesized. These copolymers were elastomeric when cured with either sulfur or peroxide.     

Effects of a tert‐butylphenylene substituent on the structure and optical,fluorescent and thermal properties of the poly(p‐phenylenevinylene) derivatives

Two soluble fluorescent polymers, poly(2‐decyloxy‐5‐(4′‐tert‐butylphenyl)‐1,4‐phenylenevinylene) (DtBP‐PPV) and poly(2‐decyloxy‐1,4‐phenylenevinylene) (DO‐PPV), were prepared by a method similar to the Gilch procedure. The DtBP‐PPV and DO‐PPV have a same chemical structure except for the conjugated tert‐bytulphenyl substituents in the former. The polymers are characterized by using ¹H NMR, FTIR, UV–vis, photoluminescence (PL), and electroluminescence (EL) spectroscopies and thermogravimetric analysis (TGA). The ¹H NMR spectra show no tolane‐bis‐benzyl (TBB) structure defects in DtBP‐PPV but some in DO‐PPV. Both UV–vis absorption and PL emission peaks of the DtBP‐PPV exhibit a red‐shift phenomenon as compared with those of the DO‐PPV. Moreover, with the DtBP‐PPV and DO‐PPV acting as light‐emitting polymers separately, EL devices were fabricated with a sequential lamination of ITO/PEDOT/DtBP‐PPV (or DO‐PPV)/Ca/Ag. The DtBP‐PPV‐based device shows a lower turn‐on voltage, a longer EL emission wavelength, and a higher brightness than the DO‐PPV‐based device. The maximum brightness of DtBP‐PPV‐based device is 57 cd/m² at an applied voltage of 12 V. POLYM. ENG. SCI., 47:1380–1387, 2007. © 2007 Society of Plastics Engineers     

Phosphorus‐containing poly(ester‐imide)–polydimethylsiloxane copolymers

New phosphorus‐containing poly(ester‐imide)‐polydimethylsiloxane copolymers were prepared by solution polycondensation of 1,4‐[2‐(6‐oxido‐6H‐dibenz < c,e > < 1, 2 > oxaphosphorin‐6‐yl)]naphthalene‐bis(trimellitate) dianhydride with a mixture of an aromatic diamine (1,3‐bis(4‐aminophenoxy)benzene) and α,ω‐bis(3‐aminopropyl)oligodimethylsiloxane of controlled molecular weight, in various ratios. Poly(amic acid) intermediates were converted quantitatively to the corresponding polyimide structures using a solution imidization procedure. The polymers are easily soluble in polar organic solvents, such as N‐methyl‐2‐pyrrolidone and N,N‐dimethylformamide, as well as in less polar solvents such as tetrahydrofuran. They show good thermal stability, the decomposition temperature being above 370 °C. The glass transition temperatures are in the range 165–216 °C. Solutions of the polymers in N‐methyl‐2‐pyrrolidone exhibit photoluminescence in the blue region. Copyright © 2010 Society of Chemical Industry     

New poly(arylene ether)s containing phthalimidine group in the main chain

Five new poly(arylene ether)s containing phthalimidine group in the main chain and pendent trifluoromethyl group have been prepared by the reaction of 4,4′‐(bis‐4‐fluoro‐3‐trifluoromethylphenyl)benzene (BTF) with bisphenols. Different molar ratios of N‐phenyl‐3,3‐bis(4‐hydroxyphenyl)phthalimidine (PA) and 4,4′‐isopropylidenediphenol (BPA) have been used to generate different copolymers. The polymers obtained by step growth polymerization exhibited weight‐average molecular weight upto 134,000 g/mol with a polydispersity index of 2.1–2.4. The homopolymer from BTF and PA showed very high glass transition temperature of 258°C and outstanding thermal stability upto 536°C for 5% weight loss under nitrogen. The polymers were soluble in a wide range of organic solvents. Transparent thin films of these polymers exhibited tensile strengths upto 65 MPa and elongation at break upto 45% depending on the exact repeat unit structures. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and properties of poly(amide imide)s based on 2,2′‐ or 4,4′‐bis(4‐aminophenoxy)biphenyl and various bis(trimellitimide)s

Three series of isomeric poly(amide imide)s (series III, IV, and V) were synthesized by the direct polycondensation of 2,2′‐bis(4‐aminophenoxy)biphenyl (2,2′‐BAPB), 4,4′‐bis(4‐aminophenoxy)biphenyl (4,4′‐BAPB), or their equimolar mixture (2,2′‐BAPB/4,4′‐BAPB = 1/1) with 12 diimide diacids and with triphenyl phosphite and pyridine as condensing agents. A comparison of the physical properties of these three series was also made. The inherent viscosities of series III, IV, and V were 0.25–0.84, 0.25–1.52, and 0.43–1.30 dL g^?1, respectively. Most of the series III polymers showed better solubility because of the non‐para structure, with the solubility order found to be III > V > IV. According to X‐ray diffraction patterns, the amorphous poly(amide imide)s had excellent solubility, whereas the crystalline polymers were less soluble. All the soluble polymers afforded transparent, flexible, and tough films, which had tensile strengths of 57–104 MPa, elongations at break of 3–20%, and initial moduli of 2.05–2.86 GPa. The glass‐transition temperatures (measured by differential scanning calorimetry) were highest for series IV, which contained the rigid 4,4′‐biphenyl units (254–299°C); copolymer series V ranked second (237–277°C), and series III, with crank 2,2′‐biphenyl structures, had the lowest values (227–268°C). The 10% weight‐loss temperatures (measured by thermogravimetric analysis) were close to one another, ranging from 527 to 574°C in nitrogen and from 472 to 543°C in air. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2763–2774, 2002     

Gas‐phase ethylene polymerization using zirconocene supported on mesoporous molecular sieves

Mesoporous molecular sieves, with pore diameters of 2.6–25 nm, were impregnated with methylaluminoxane and bis(butylcyclopentadienyl)zirconium dichloride and tested as catalysts for the gas‐phase homopolymerization of ethylene at ethylene pressures of 200 psi and temperatures of 50–100°C and for 1‐hexene/ethylene copolymerization at 70°C. The activities and activity profiles, at constant Zr and Al contents, depended on the pore size of the supports and the polymerization temperature. Maximum activities for both the homopolymerizations and copolymerizations were observed for catalysts made with supports having pore diameters of 2.6 and 5.8 nm. Homopolymerization activities were highest at temperatures of 70–80°C; average homopolymerization and copolymerization activities up to 9000 kg of polyethylene/(mol of Zr h) were obtained. The weight‐average molecular weights (M_w's) were not a function of the support pore size but decreased with increasing reaction temperatures, from about 260,000 at 50°C to about 165,000 at 100°C. The polydispersities were essentially constant at 2.5 ± 0.2 for the homopolymers. M_w's for the 1‐hexene/ethylene copolymers had an average value of 117,000 with an average polydispersity of 2.8. The amount of triisobutyl aluminum added to the reactor significantly affected the activity and activity profiles. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1161–1177, 2003     

Polyimides derived from 1,4‐bis [3‐oxy‐(N‐aminophthalimide)] benzene

A novel diamine, 1,4‐bis [3‐oxy‐(N‐aminophthalimide)] benzene (BOAPIB), was synthesized from 1,4‐bis [3‐oxy‐(N‐phenylphthalimide)] benzene and hydrazine. Its structure was determined via IR, ¹H NMR, and elemental analysis. A series of five‐member ring, hydrazine‐based polyimides were prepared from this diamine and various aromatic dianhydrides via one‐step polycondensation in p‐chlorophenol. The inherent viscosities of these polyimides were in the range of 0.17–0.61 dL/g. These polymers were soluble in polar aprotic solvents and phenols at room temperature. Thermogravimetric analysis (TGA) showed that the 5% weight‐loss temperatures of the polyimides were near 450°C in air and 500°C in nitrogen. Dynamic mechanical thermal analysis (DMTA) indicated that the glass‐transition temperatures (T_gs) of these polymers were in the range of 265–360°C. The wide‐angle X‐ray diffraction showed that all the polyimides were amorphous. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Novel blue‐light‐emitting polymers based on a diphenylanthracene moiety

New luminescent copolyethers with diphenylanthracene‐emitting segments and electron‐transporting benzoxazole phenyl were successfully synthesized by aromatic nucleophilic substitution. The polymers, characterized by NMR and IR spectroscopy, were obtained in high yields, showed good solubility in various organic solvents, and had high thermal stability with high glass‐transition temperatures (125–129). The number‐average molecular weights of the polymers were 10,000–20,000, and they had polydispersity indices of 1.2–1.4. The optical and electrochemical properties of the polymers were also investigated. The pure blue emission for the polymers (maximum wavelength = 430–440 nm) was obtained with high photoluminescence quantum efficiency (76–78%) in a chloroform solution. The blue electroluminescence for the poly(TDPB) (maximum wavelength = 440 nm) was obtained with a turn‐on voltage of 15–20 V when simple light‐emitting diodes (indium tin oxide/polymer/Al) were fabricated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2151–2157, 2006     

Copolymerization of ethylene/nonconjugated dienes over a Bis(2‐methyl indenyl) zirconium dichloride/methylaluminoxane catalyst system

Ethylene was copolymerized with 1,5‐hexadiene (1,5‐HD), 1,4‐hexadiene (1,4‐HD) and 1,7‐octadiene (1,7‐OD) with bis(2‐methyl indenyl) zirconium dichloride/methylaluminoxane. 1,5‐HD units formed the trans‐structured cyclopentane rings and 1‐butenyl side chains, and cross‐linking took place during ethylene/1,5‐HD (E15HD) copolymerizations. The lower the polymerization temperature was, the larger the amount of hot xylene (XYL)‐insoluble faction was. Copolymers of ethylene/1,7‐OD (E17OD) did not have any cyclic structures and were nearly insoluble in XYL when produced below 60°C. In contrast, all the copolymers of ethylene/1,4‐HD (E14HD) were completely soluble in XYL. The broadest differential scanning calorimetry melting peak was found for E15HD and then for E17OD, and the narrowest was found for E14HD due to the presence or the absence of the cyclic structures and cross‐linking. Addition of 1,7‐OD or 1,4‐HD as a comonomer reduced the polymerization rate and the molecular weight of the respective copolymers much more than that of 1,5‐HD. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1048–1058, 2002; DOI 10.1002/app.10397     

Synthesis and study of new polyamides with side oxadiazole rings

A series of six new aromatic polyamides with side oxadiazole rings has been synthesized by polycondensation reaction of aromatic diamines containing pendent substituted oxadiazole groups with a silicon‐containing diacid chloride [namely, bis(p‐chlorocarbonyl‐phenylene)diphenylsilane] or with a fluorine‐containing diacid chloride [namely, hexafluoroisopropylidene‐bis(p‐benzoyl chloride)]. All polymers were easily soluble in amidic solvents, such as N‐methylpyrrolidinone and dimethylformamide, and gave thin transparent films by casting such solutions. Very thin coatings were deposited onto silicon wafers and exhibited smooth, pinhole‐free surfaces in atomic force microscopy investigations. The polymers showed high thermal stability, with decomposition temperature >400°C. Some of them did exhibit a glass transition, in the range 152–276°C, with a reasonable interval between glass transition and decomposition. Four of these polymers showed blue photoluminescence, in the range 460–480 nm, which makes them promising candidates for future use as high‐performance materials in the construction of light‐emitting devices. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 714–721, 2003