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     

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     

Preparation and characterization of poly(silyl ester)s containing 2,2‐bis(p‐dimethylsiloxy‐phenyl)propane units in the polymer backbones

The two poly(silyl ester)s containing 2,2‐bis(p‐dimethylsiloxy‐phenyl)propane units in the polymer backbones have been prepared via polycondensation reaction of di‐tert‐butyl adipate and di‐tert‐butyl fumarate with 2,2‐bis(p‐chloro dimethylsiloxy‐phenyl)propane to give tert‐butyl chloride as the condensate. The polymerizations were performed under nitrogen at 110°C for 24 h without addition of solvents and catalysts to obtain the poly(silyl ester)s with weight average molecular weights typically ranging from 5000 to 10,000 g/mol. Characterization of the poly(silyl ester)s included ¹H NMR and ¹³C NMR spectroscopies, infrared spectroscopy, ultraviolet spectroscopy, differential scanning calorimetry, thermogravimetric analysis (TGA), gel permeation chromatography, and Ubbelohde viscometer. The glass transition temperatures (T_g) of the obtained polymers were above zero because of the introducing 2,2‐bis(p‐dimethylsiloxy‐phenyl)propane units in the polymer backbones. The TGA/DTG results showed that the obtained poly(silyl ester)s were stable up to 180°C and the residual weight percent at 800°C were 18 and 9%, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1937–1942, 2006     

Synthesis of oxadiazole‐based polymers containing a carbazole–vinylene or fluorene–vinylene group and their hole‐injection/transport behavior in light‐emitting diodes

A series of conjugated (poly{N‐(2‐ethylhexyl)‐3,6‐carbazole–vinylene‐alt‐[(2,5‐bisphenyl)‐1,3,4‐oxadiazole]}) and nonconjugated (poly{N‐(2‐ethylhexyl)‐3,6‐carbazole–vinylene‐alt‐[(2,5‐bisphenol)‐1,3,4‐oxadiazole]}) and poly{9,9‐dihexyl‐2,7‐fluorene–vinylene‐alt‐[(2,5‐bisphenol)‐1,3,4‐oxadiazole]}) polymers containing oxadiazole and carbazole or fluorene moieties in the polymer backbone were synthesized with a multiple‐step procedure. The properties of the polymers, including the photophysical and electrochemical characteristics, could be fine‐tuned by adjustment of the components or structures in the polymer chains. The polymers were used to examine the hole‐injection/transport behavior as hole‐injection/hole‐transport layers in double‐layer indium tin oxide (ITO)/polymer/aluminum tris(8‐hydroxyquinoline)/LiF/Al devices by the determination of their energy levels. The effects of the polymers in these devices on the charge‐transport behavior were compared with a control device fabricated with poly(ethylenedioxythiophene) (PEDOT)–poly(styrene sulfonate) (PSS). Devices containing the synthesized polymers showed comparable adhesion to the ITO anode and good hole‐injection/transport performance. In addition, they exhibited higher electroluminescence over an identical range of current densities than the control device. This was attributed to the prevention of radiative exciton quenching caused by the PEDOT–PSS interfaces and the improvement of electron/exciton blocking due to the higher electron affinity of the synthesized polymers. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and characterization of binary blends composed of poly(dioctylfluorene‐alt‐hexylsulfonylthiophene) and nonconjugated polymers

The solutions and the thin films of poly[9,9‐dioctyl‐2,7‐fluorene‐alt‐2,5–(3‐hexyl‐sulfonylthiophene)] (PFSO₂T) and its binary blends with other nonconjugated polymers such as poly(methyl methacrylate) (PMMA), polycarbonate (PC), and ethylene vinyl acetate copolymer (EVA) can be prepared by different concentrations from a polymer solution. Binary polymer blends can increase the absorbance and photoluminescence intensities in the solid state due to nonconjugated polymers can act as dispersion agents which can reduce the interchain interaction or the aggregation of the conjugated polymers. Photoluminescence intensity of the thin films of fluorescent polymers blending with ethylene vinyl acetate copolymers exhibited six times higher than that of the neat fluorescent polymers. The PFSO₂T/EVA binary blends reveal the least extent of optical degradation of around 20% compared to those binary blends in both absorption and emission intensities after the irradiation under the UV‐light for 20 h. The cross‐sectional morphology of fluorescent polymers blending with ethylene vinyl acetate copolymers reveals little aggregation and better phase separation among the other binary polymer blends. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44969.     

Photophysical properties of fluorene‐based copolymers synthesized by connecting twisted biphenyl units with fluorene via para‐ and meta‐linkages

BACKGROUND: Wide bandgap semiconducting polymers are of great interest in the development of organic and polymeric emissive materials for display purposes since they can be used to generate light of all colors either by irradiation of luminescent dyes or by energy transfer to emissive dopants. The aim of the present work is to construct new fluorene‐based semiconducting polymers with a wide bandgap. RESULTS: A novel polyfluorene derivative, poly[(9,9‐dihexyl‐2,7‐fluorene)‐alt‐(5,7‐dihydrodibenz[c,e]oxepin)], with a wide bandgap, was synthesized by connecting rigidly twisted biphenyl monomers with dihexylfluorene via para‐linkages and it was compared with poly[(9,9‐dihexyl‐2,7‐fluorene)‐alt‐(spirocyclohexane‐1,6′‐dibenzo[d,f][1,3]dioxepin)], which has meta‐linkages. Both polymers emit in the ultraviolet and blue regions. Electronic spectral absorption data and electrochemical measurements demonstrate that ca 40° torsion angle of the biphenyl units induces an increase in the HOMO–LUMO gap of 0.18 eV, and that meta‐linkage of the twisted segment in the polymer induces another increase of 0.24 eV compared to polydihexylfluorene. CONCLUSION: The new twisted biphenyl compounds are efficient segments to tune the bandgaps of conjugated polymers. The two fluorene‐based copolymers have wide bandgaps and exhibit potential as host materials. Copyright © 2008 Society of Chemical Industry     

Synthesis and properties of three kinds of phenylenevinylene copolymers with dialkoxyphenylene units

Two random copolymers, poly(p-phenylenevinylene-co-2,5-didodecyloxy-p-phenylenevinylene) and poly(2,5-dimethoxy-p-phenylenevinylene-co-2,5-didodecyloxy-p-phenylenevinylene), were synthesized via the chlorine precursor route followed by thermal elimination. One alternating copolymer, poly(p-phenylenevinylene-alt-2,5-didodecyloxy-p-phenylenevinylene), was prepared via the Heck coupling reaction. The effects of molar ratio of monomers on yield and composition of the precursor copolymers were studied. The two precursor copolymers and the alternating copolymer were characterized by gel permeation chromatography, differential scanning calorimetry, elemental analysis, and infrared spectroscopy. The UV-visible absorption spectra and photoluminescence spectra, as well as solubility and conductivity of these copolymers, were compared. © 1998 John Wiley & Sons, Inc. J Appl Polm Sci 68: 937–946, 1998     

Novel 1,4‐diketo‐3,6‐diphenyl pyrrolo[3,4‐c]pyrrole (DPP)‐based copolymers with large Stokes shift

Two novel alternating π‐conjugated copolymers, named PDPPDOPV and PDPPDOPE, constituted of 1,4‐diketo‐3,6‐diphenyl pyrrolo[3,4‐c]pyrrole (DPP) with 2,5‐dioctyloxy‐1,4‐phenylenevinylene (DOPV) or 2,5‐dioctyloxy‐1,4‐phenyleneethynylene (DOPE), respectively, were synthesized and characterized by UV‐vis, FT‐IR, and photoluminescence spectroscopy. They are dark red solid readily soluble in various common organic solvents including THF and chloroform. The UV‐vis absorption spectra of the polymers show strong absorption bands, which correspond to the π‐π* transition of π‐conjugated segments. Photoluminescence (PL) spectra show that both polymer films and solution have large Stokes shifts. From their fluorescence behavior, Stokes shifts of 173 nm and 199 nm are derived for the films of PDPPDOPV and PDPPDOPE, respectively, which are the largest two values ever reported for DPP‐containing polymers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and properties of fluorenyl–pyridinyl alternatingcopolymers for light‐emitting diodes

A novel series of well‐defined alternating poly[2,7‐(9,9‐di(2‐ethylhexyl)fluorenyl)‐alt‐pyridinyl] (PDEHFP) copolymers were synthesized using palladium(0)‐catalyzed Suzuki coupling reaction in high yields. These polymers were characterized using ¹H NMR, UV‐visible and fluorescence spectroscopies, gel permeation chromatography, thermal analysis and cyclic voltammetry. The optical properties of the copolymers, including photoluminescence (PL) and electroluminescence (EL), were studied. The difference in linkage position of pyridinyl units in the polymer backbone has significant effects on the electronic and optical properties of polymers in solution and in film state. Meta‐linkage (3,5‐ and 2,6‐linkage) of pyridinyl units in the polymer backbone is more favorable for pure blue emission and prevention of aggregation of polymer chains. PDEHFPs with 2,6‐ and 3,5‐linkage of pyridinyl units have relatively high PL efficiency of 37 and 44% in the film state. In comparison with homopolymer PDEHF, the copolymers with pyridinyl units possess low lowest unoccupied molecular orbital energy levels for easy electron injection from a cathode. Strong EL is observed and light‐emitting diodes (LEDs) exhibit typical rectifying characteristics. The emission intensity starts to increase at around 12 V. The emission peak wavelengths of the polymers roughly coincide with those of PL. This series of fluorene–pyridine‐based alternating copolymers seem to be candidates for polymeric LEDs. © 2013 Society of Chemical Industry     

Novel Poly(linolenic acid) Graft Copolymers: Synthesis,Characterization and Electrical Properties

A poly(linolenic acid)‐g‐poly(tert‐butyl acrylate) graft copolymer was synthesized from polymeric linolenic acid peroxide possessing peroxide groups in the main chain by free radical polymerization of tert‐butyl acrylate. Graft copolymers having structures of poly(linolenic acid)‐g‐poly(caprolactone)‐g‐poly(tert‐butyl acrylate) were synthesized from polymeric linolenic acid, possessing peroxide groups on the main chain by the combination of free radical polymerization of tert‐butyl acrylate and ring‐opening polymerization of ε‐caprolactone in one‐pot. The obtained graft copolymers were characterized by proton nuclear magnetic resonance, gel permeation chromatography, thermal gravimetric analysis, differential scanning calorimetry, and scanning electron microscopy techniques. Furthermore, Au/n‐Si diodes were fabricated with and without poly(linolenic acid)‐g‐poly(caprolactone)‐g‐poly(tert‐butyl acrylate)‐4 to form a new interfacial polymeric layer for the purpose of investigating this polymer's conformity in electronic applications. Some main electrical characteristics of these diodes were investigated using experimental current–voltage measurements in the dark and at room temperature.     

Synthesis and luminescence properties of new blue‐light‐emitting polyconjugated poly{1,1′‐biphenyl‐4,4′‐diyl‐[1‐(4‐t‐butylphenyl)]vinylene} polymers and copolymers

Three new soluble polyconjugated polymers, all of which emitted blue light in photoluminescence and electroluminescence, were synthesized, and their luminescence properties were studied. The polymers were poly{1,1′‐biphenyl‐4,4′‐diyl‐[1‐(4‐t‐butylphenyl)]vinylene}, poly((9,9‐dioctylfluorene‐2,7‐diyl)‐alt‐{1,4‐phenylene‐[1‐(4‐t‐butylphenyl)vinylene‐1,4‐phenylene]}) [P(DOF‐PVP)], and poly([N‐(2‐ethyl) hexylcarbazole‐3,6‐diyl]‐alt‐{1,4‐phenylene‐[1‐(4‐t‐butylphenyl)]vinylene‐1,4‐phenylene}). The last two polymers had alternating sequences of the two structural units. Among the three polymers, P(DOF‐PVP) performed best in the light‐emitting diode devices of indium–tin oxide/poly(ethylenedioxythiophene) doped with poly(styrene sulfonate) (30 nm)/polymer (150 nm)/Li:Al (100 nm). This might have been correlated with the balance in and magnitude of the mobility of the charge carriers, that is, positive holes and electrons, and also the electronic structure, that is, highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) levels, of the polymers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 307–317, 2006     

Synthesis and characterization of poly(p‐phenylene)‐graft‐poly(ε‐caprolactone) copolymers by combined ring‐opening polymerization and cross‐coupling processes

2,5‐Dibromo‐1,4‐(dihydroxymethyl)benzene was used as initiator in ring‐opening polymerization of ε‐caprolactone in the presence of stannous octoate (Sn(Oct)₂) catalyst. The resulting poly(ε‐caprolactone) (PCL) macromonomer, with a central 2,5‐dibromo‐1,4‐diphenylene group, was used in combination with 1,4‐dibromo‐2,5‐dimethylbenzene for a Suzuki coupling in the presence of Pd(PPh₃)₄ as catalyst or using the system NiCl₂/bpy/PPh₃/Zn for a Yamamoto‐type polymerization. The poly(p‐phenylenes) (PPP) obtained, with PCL side chains, have solubility properties similar to those of the starting macromonomer, ie soluble in common organic solvents at room temperature. The new polymers were characterized by ¹H and ¹³C NMR and UV spectroscopy and also by GPC measurements. The thermal behaviour of the precursor PCL macromonomer and the final poly(p‐phenylene)‐graft‐poly(ε‐caprolactone) copolymers were investigated by thermogravimetric analysis and differential scanning calorimetry analyses and compared. Copyright © 2004 Society of Chemical Industry     

Thermooxidative stability of spectra of fluorene-based copolymers

The origin of the low-energy emission of fluorene-based homo- and copolymers still remains controversial. In this work, the effect of thermal treatment on the emission properties of poly[(9,9-dihexylfluorene)-alt-co-(1,4-phenylene)] (PF6P) and its four derivatives modified by attaching different lengths of alkoxy side chains on the phenylene rings has been systematically investigated. By comparing the photoluminescence (PL) spectra of PF6P and the modified polymers, Fourier-transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD) and PL lifetime measurements have revealed that the long wavelength emission could be attributed to the formation of fluorenone-based excimers rather than to the localized fluorenone π-π* transition, the energy transfer from fluorene segments to the fluorenone moieties, or the fluorenone defects generated by thermal oxidation during thermal treatment. Compared with PF6P, the attachment of alkoxy side chains on the phenylene rings effectively inhibits the aggregation of backbone chains, thus restrains the formation of fluorenone-based excimers and remarkably improves thermal stability of the spectra.     

Dependence of optical properties on the preparation methods of poly[(9,9′‐dialkylfluorene‐2,7‐diyl)‐alt‐(1,3,4‐oxadiazole‐2,5‐diyl)]

A blue‐light‐emissive fluorene‐based polyoxadiazole, an n‐type polyfluorene derivative, was synthesized by both one‐step and two‐step methods. Directly polymerized poly[(9,9′‐didodecylfluorene‐2,7‐diyl)‐alt‐(1,3,4‐oxadiazole‐2,5‐diyl)] (PFOx‐DP) exhibited a higher molecular weight and a more efficient photoluminescence quantum yield than poly[(9,9′‐didodecylfluorene‐2,7‐diyl)‐alt‐(1,3,4‐oxadiazole‐2,5‐diyl)] (PFOx) prepared via a polyhydrazide precursor, poly[9,9′‐didodecylfluorene‐2,7‐(2,5‐dihydrazide‐ 1,3,4‐oxadiazole). Both polymers, differently prepared, showed similar photoluminescent properties in 1,2‐dichloroethane. However, in a film state, the influence of the interchain interactions on the photoluminescence of PFOx with the lower molecular weight was larger than on the photoluminescence of PFOx‐DP. The electron‐deficient property of an oxadiazole group in the polymer backbone resulted in low‐lying highest occupied molecular orbital and lowest unoccupied molecular orbital energy levels of ?6.29 and ?3.26eV, respectively, of the polymer suitable for electron‐transport/hole‐blocking layers and emissive layers in multilayer electroluminescence devices. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3112–3118, 2004     

Graft copolymers from commercial chlorinated polypropylene via Cu(0)‐mediated atom transfer radical polymerization

Commercially available chlorinated polypropylene has been used as a macroinitiator for the Cu(0)‐mediated atom transfer radical polymerization of methyl methacrylate and tert‐butyl acrylate to obtain well‐defined graft copolymers. The relatively narrow molecular weight distribution in the graft copolymers and linear kinetic plots indicated the controlled nature of the copolymerization reactions. Both Fourier transform infrared and ¹H NMR studies confirmed that the graft reactions had taken place successfully. After graft copolymer formation, tert‐butyl groups of poly(tert‐butyl acrylate) side chains were completely converted into poly(acrylic acid) chains to afford corresponding amphiphilic graft copolymers. © 2016 Society of Chemical Industry     

Synthesis and properties of novel deep red‐emitting copolymers based on a poly(p‐phenylenevinylene) derivative

A series of novel copolymers based on a poly(p‐phenylenevinylene) (PPV) derivative with different content of narrow band‐gap unit 2,1,3‐benzoselenadiazolevinylene (BSeV) was prepared via Stille coupling reaction. The copolymers emit light from deep red to near‐infrared (NIR) depending on BSeV content in the copolymers. The electroluminescence (EL) emission peaked at 752 nm for the copolymer with the content of 30 mol % BSeV is among the longest reported so far for the PPV polymers. The best device performance is observed for the copolymer with 1 mol % BSeV content with external quantum efficiency (QE_ext) of 0.26% and CIE coordinate 0.65, 0.34 (x,y). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4321–4327, 2006     

Synthesis and characterization of poly(fluorene vinylene) copolymers containing thienylene–vinylene units

Narrow‐band‐gap 2,5‐thienylene‐divinylene (ThV) units were incorporated into the poly(fluorene vinylene) backbone via a Gilch reaction as an energy trap with various feed ratios; this yielded pronounced changes in the electrochemical and optical properties of the material. The energy levels of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of the polymers {poly(9,9‐di‐iso‐octylfluorene vinylene) [poly(fluorene vinylene‐co‐thiophene vinylene (FV))], C1, and C2 } were estimated to be ?5.53 to ?5.10 eV and ?2.98 to ?2.84 eV, respectively, by cyclic voltammetry measurements. In comparison with poly(FV), the HOMO energy levels of polymers poly(fluorene vinylene‐co‐thiophene vinylene (FV) (90 : 10) ( C1 ) and poly(fluorene vinylene‐co‐thiophene vinylene (FV) (80 : 20) ( C2 ) were significantly increased, but their LUMO energy levels were slightly decreased. The optical properties were investigated by absorption and emission spectra of the polymers. The good spectral overlap between the emission of poly(FV) and the absorption of polymers C1 and C2 revealed a sufficient energy transfer from the majority of 9,9‐di‐iso‐octylfluorene vinylene units to the minority of ThV units. The reduction of self‐absorption losses of polymers C1 and C2 due to spectral separation caused by the incorporation of ThV units could be indirectly confirmed by nonlinear optical (NLO) properties. The result of the NLO properties of the polymers showed that the third‐order NLO coefficients of poly(FV), C1, and C2 were 8.1 × 10^?10, 1.35 × 10^?9, and 1.51 × 10^?9 esu, respectively. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis of complex architectures of comb block copolymers

The synthesis of comb block copolymers by ring opening metathesis polymerization (ROMP), ring opening polymerization (ROP), and atom transfer radical polymerization (ATRP) is described. Block copolymers were synthesized by the ROMP of oxanorbornene and norbornene monomers followed by hydrogenation of the olefins along the backbone. One block of these diblock copolymers possessed initiators either for the ROP of (3S)-cis-3,6-dimethyl-1,4-dioxane-2,5-dione or the ATRP of butyl acrylate. The synthesis and characterization of comb polymers with arms composed of poly(lactic acid) and poly(butyl acrylate) are described. These polymers had well-defined peaks in the size exclusion chromatography spectra which indicated that no homopolymers were synthesized. A comb block copolymer with polymeric arms of poly(styrene-b-vinylpyridine) is described. Vinylpyridine was polymerized from a comb polymer with poly(styrene) arms by ATRP at high dilution of the comb polymer.     

Synthesis and properties of liquid‐ crystalline triblock copolymers by ATRP,having electron‐transporting thiadiazole unit

ABA‐type block copolymers composed of 2,5‐diphenyl‐1,3,4‐thiadiazole (DPTD) oligoester and poly(methyl methacrylate) (PMMA) segments (M_n = 16 200 and 23 000) were synthesized by atom‐transfer radical polymerization and their liquid‐crystalline (LC) and photoluminescence (PL) properties were examined. The structures of block copolymers were identified by Fourier transform infrared and ¹H NMR spectroscopies. Differential scanning calorimetry measurement, polarizing microscopy observation and wide‐angle X‐ray analysis revealed that the block copolymers form thermotropic LC phase (smectic C) independent of molecular weights of PMMA segments, but a model polymer (PMMA segments having the DPTD unit in the central part) has no LC melt. Solution and solid‐state PL spectra indicated that all the block copolymers display blue emission arising from the DPTD unit. Their quantum yields are 17–21%, which increase with the PMMA chain lengths. The block copolymers have good aligned structures in the LC states, but their order parameter (S) values in sheared LC states were lower than those in the sheared LC compounds. The PL properties in the LC states were independent of the LC aligned structures. Cyclic voltammetry measurements showed that these block copolymers have deep HOMO levels compared with polymers composed of oxadiazole rings. Copyright © 2007 Society of Chemical Industry     

Synthesis and characterization of hyperbranched poly(silyl ester)s

Hyperbranched poly(silyl ester)s were synthesized via the A₂ + B₄ route by the polycondensation reaction. The solid poly(silyl ester) was obtained by the reaction of di‐tert‐butyl adipate and 1,3‐tetramethyl‐1,3‐bis‐β(methyl‐dicholorosilyl)ethyl disiloxane. The oligomers with tert‐butyl terminal groups were obtained via the A₂ + B₂ route by the reaction of 1,5‐dichloro‐1,1,5,5‐tetramethyl‐3,3‐diphenyl‐trisi1oxane with excess amount of di‐tert‐butyl adipate. The viscous fluid and soft solid poly(silyl ester)s were obtained by the reaction of the oligomers as big monomers with 1,3‐tetramethyl‐1,3‐bis‐β(methyl‐dicholorosilyl)ethyl disiloxane. The polymers were characterized by ¹H NMR, IR, and UV spectroscopies, differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). The ¹H NMR and IR analysis proved the existence of the branched structures in the polymers. The glass transition temperatures (T_g's) of the viscous fluid and soft solid polymers were below room temperature. The T_g of the solid poly(silyl ester) was not found below room temperature but a temperature for the transition in the liquid crystalline phase was found at 42°C. Thermal decomposition of the soft solid and solid poly(silyl ester)s started at about 130°C and for the others it started at about 200°C. The obtained hyperbranched polymers did not decompose completely at 700°C. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3430–3436, 2006