Bis- or tetra-maleimides of substituted s-triazines chain-extended by imide,amide, and urea groups for fire- and heat-resistant applications

Novel phosphorylated bismaleimides and nonphosphorylated tetramaleimides containing substituted s-triazine rings (chain-extended by imide, amide, or urea groups) were prepared and polymerized. These polymer precursors were prepared by reacting 2,4-bis(4-aminophenoxy)-6-diethoxyphosphinyl-s-triazine or 2,4,6-tris(4-aminophenoxy)-s-triazine with maleic anhydride in combination with a bridging agent such as pyromellitic or benzophenone tetracarboxylic dianhydride, terephthaloyl chloride, and tolylene diisocyanate. The structure of polymer precursors was confirmed by infrared (IR) and proton nuclear magnetic resonance (¹H-NMR) spectroscopy and their curing behavior was investigated by differential thermal analysis (DTA). The phosphorylated bismaleimides were thermally polymerized at a lower temperature than did the corresponding nonphosphorylated tetramaleimides. Dynamic thermogravimetric analysis (TGA) showed that the nonphosphorylated and phosphorylated cured resins were stable up to 320–370 and 312–327°C, respectively, in nitrogen or air atmosphere. In addition, the latter afforded a relatively higher char yield. The relative thermal and thermooxidative stability of polymers with regard to the chemical structure of the bridging group was of the order imide > amide > urea. Upon isothermal aging the phosphorylated polymers exhibited a lower weight loss than did the corresponding nonphosphorylated polymers.     

Synthesis and photophysical properties of hyperbranched polyfluorenes containing 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine as the core

A series of new hyperbranched polymers containing a 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine core unit and polyfluorene chain arms have been synthesized via Suzuki coupling, and characterized by NMR, IR and GPC. All the polymers exhibit good thermal stability with a high decomposition temperature. By changing the 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine/fluorene ratio the UV-vis absorption and emission spectra can be partially tuned. It has been found that the polymers containing a low ratio of 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine units (P1-P3) have an absorption maximum around 385 nm, localized in the polyfluorene chain, and a shoulder around 425 nm ascribable to a charge transfer state involving the fluorene and the 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine core. Increasing the molar ratio of the 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine unit enhances the charge transfer band which becomes dominant for P4. The LUMO level of these polymers is relatively low due to the electron affinity of the triazine group. The polymers show dual emission, with a structured band in the blue (410-440 nm), attributed to the polyfluorene, and a broad band in the red (470-500 nm) associated with the charge transfer state. All the polymers exhibit two-photon absorption activity in the range of 660 to 900 nm with the maximum two-photon absorption (TPA) cross-section red-shifted from the corresponding linear absorption. The values of the TPA cross-sections vary from 1000 to 5000 GM, following the 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine/fluorene ratio.     

High-strength fire- and heat-resistant imide resins containing cyclotriphosphazene and hexafluoroisopropylidene groups

High-strength fire- and heat-resistant polymers were obtained by the thermally induced melt-polymerization of maleimido-phenoxy cyclotriphosphazenes linked by hexafluoroisopropyliden-ediphthalimide groups. These polymers show good thermal stability and high char yields: 78–80% at 800°C in nitrogen and 60–68% in air at 700°C. Graphite-fabric laminates did not burn in pure oxygen, even at 300°C (LOI = 100%), and were tested for shear, flexural, and tensile strengths. Two monomers were synthesized by reacting tris(4-aminophenoxy)-tris(phenoxy) cyclotriphosphazene with maleic anhydride and hexafluoroisopropylidenediphthalic anhydride. The triamine was synthesized by a stepwise reaction of hexachlorocyclotriphosphazene with phenol and 4-nitrophenol to give tris(4-nitrophenoxy)-tris(phenoxy)cyclotriphosphazene and reducing the nitro groups. The structures of cyclic phosphazene-trimeric precursors and the polymers were characterized by FT-IR, ¹H-NMR, ³¹P-NMR, and mass spectroscopy. The curing behaviors of polymer precursors were evaluated by differential scanning calorimetry and thermogravimetric analyses.     

Hexasubstituted donor-acceptor benzenes as nonlinear optically active molecules with multiple charge-transfer transitions

The synthesis of three novel nonlinear optical (NLO) chromophores with threefold symmetry, namely 1,3,5-tris(4-N,N-diethylaminophenyl)-2,4,6-tris(4-nitrophenyl)benzene (3), 1,3,5-tris(4-N,N-dihexylaminophenylbutadiynyl)-2,4,6-tris(4-nitrophenyl)benzene (13) and 1,3,5-tris(4-N,N-dihexylaminophenylethynyl)-2,4,6-tris(4-nitrophenylethynyl)benzene (4 b), is reported. We used the [Co(2)(CO)(8)]-catalysed trimerisation of 4-N,N-diethylamino-4'-nitrotolane (5) to prepare 3. The trimerisation experiment carried out with 1-(4-N,N-diethylaminophenyl)-6-(4-N,N-nitrophenyl)hexatriyne (6) and [Rh(PPh(3))(3)Cl] afforded 13. A stepwise approach was used to prepare 4 b. 1,3,5-Trichloro-2,4,6-triiodobenzene (8 b) was coupled with 4-nitrophenyl-acetylene (14) under Pd(0) catalysis to yield 1,3,5-trichloro-2,4,6-tris(4-nitrophenylethynyl)benzene (15). The coupling reaction of 15 with 4-N,N-dihexylaminophenylethynyltributylstannane (21) led to 4 b. X-ray investigations on 3, 4 b and 13 confirmed the structural assignments and revealed that the peripheral aryl rings in 4 b are less twisted around the connecting bonds than in 3 and 13. A large second-order polarisability (beta) of 4 b relative to 3 and 13 was determined by hyper-Rayleigh scattering (HRS). Compound 4 b represents an NLO chromophore with second-order polarisabily among the highest obtained so far for two-dimensional nondipolar NLO chromophores.     

Synthesis and characterization of a new soluble conducting polymer and its electrochromic device

A mixture of isomers 2,5-di(4-methyl-thiophen-2-yl)-1-(4-nitrophenyl)-1H-pyrrole, 2-(4-methyl-thiophen-2-yl)-5-(3-methyl-thiophen-2-yl)-1-(4-nitrophenyl)-1H-pyrrole and 2,5-di(3-methyl-thiophen-2-yl)-1-(4-nitrophenyl)-1H-pyrrole (Me-SNS(NO₂)) were synthesized. Resulting monomers were polymerized chemically, producing soluble polymers in common organic solvents. The average molecular weight has been determined by gel permeation chromatography (GPC) as Mn=5.6×10³ for the chemically synthesized polymer. The monomers were also electrochemically polymerized in the presence of LiClO₄, NaClO₄ (1:1) as the supporting electrolyte in acetonitrile solvent. Resulting polymers were characterized via CV, FTIR, NMR, SEM and UV–Vis spectroscopy. Spectroelectrochemistry analysis of polymer revealed Π–Π^* transition below 300 nm, with an electronic band gap of 2.18 ev. Switching ability of the polymer was evaluated by kinetic study measuring percent transmittance (%T) at the maximum contrast point, indicating that poly(Me-SNS(NO₂)) is a suitable material for electrochromic devices.     

Perylene diimide copolymers with dithienothiophene and dithienopyrrole: Use in n‐channel and ambipolar field‐effect transistors

Solution‐processable polymers consisting of perylene diimide (PDI) acceptor moieties alternating with dithienothiophene (DTT), N‐dodecyl‐dithienopyrrole (DTP), or oligomers of these donor groups have been synthesized. We have, in addition to varying the donor, varied the N,N′ substituents of the PDIs. The thermal, optical, electrochemical, and charge‐transport properties of the polymers have been investigated. The polymers show broad absorption extending from 300 to 1000 nm with optical band gaps as low as 1.2 eV; the band gap decreases with increasing the conjugation length of donor block, or by replacement of DTT by DTP. The electron affinities of the polymers, estimated from electrochemical data, range from ?3.87 to ?4.01 eV and are slightly affected by the specific choice of donor moiety, while the estimated ionization potentials (?5.31 to ?5.92 eV) are more sensitive to the choice of donor. Bottom‐gate top‐contact organic field‐effect transistors based on the polymers generally exhibit n‐channel behavior with electron mobilities as high as 1.7 × 10^–2 cm²/V/s and on/off ratios as high as 10⁶; one PDI‐DTP polymer is an ambipolar transport material with electron mobility of 4 × 10^–4 cm²/V/s and hole mobility of 4 × 10^–5 cm²/V/s in air. There is considerable variation in the charge transport properties of the polymers with the chemical structures. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Polyether azomethines. I. Synthesis and characterization

Six new polyether azomethines were synthesized by melt and solution polycondensation of six different diamines with 4,4′-[1,4-phenylene bis(oxy)] bisbenzaldehyde. The polymers synthesized by solution method are yellow to white in color and had inherent viscosities up to 0.59 dL/g in concentrated H₂SO₄. The polymers obtained by melt condensation show higher viscosity. Except polymer IV , others are insoluble in common organic solvents. The polymers were characterized by IR, x-ray, elemental analysis, and DSC study. The thermal stability of the polymers was evaluated by TGA and IGA study. Polymers I-III are highly thermally and thermooxidatively stable and exhibit no appreciable decomposition up to 420°C both in air and nitrogen atmosphere. It was shown that the curing of the polyazo-methines takes place by opening up of the ? CH?N? linkages at higher temperature. The electrical conductivities of the virgin and iodine doped polymers were as high as 10^?11?10^?16 and 10^?6?10^?8S cm^?1, respectively, at 30°C. Electronic spectra of the undoped polymers ( I-III ) indicated a large bathochromic shift of the ? – ?^* absorptions band (376 nm) due to ? C?N? bonds of the model compound. This can be attributed to extensive delocalization of the electrons along the polymer chain. © 1995 John Wiley & Sons, Inc.     

Preparation,surface morphology,and optical properties of indium(III) oxide nanoparticles by thermolysis of indium–poly(vinyl alcohol) coordination polymer

First report on the preparation of well-dispersed, indium(III) oxide (In₂O₃) nanoparticles with 22–35?nm size by polymer thermolysis is presented. Indium–poly(vinyl alcohol) (PVA) coordination polymer films were prepared by ‘solution casting technique’ from the homogeneous aqueous solution of coordination polymer prepared using PVA and indium(III) nitrate as starting materials; subsequently the films were calcined at 550?°C to yield In₂O₃ nanoparticles. Both indium–PVA coordination polymer that served as the precursor and the titled nanoparticles were characterized by Fourier transform-infrared spectroscopy, photoluminescence (PL), powder X-ray diffraction (XRD), transmission electron microscopy, and thermal analysis. Room temperature PL spectra of the prepared indium oxide nanoparticles showed intense blue emissions around 360, 410 and 430?nm, characteristic of indium oxide nanoparticles due to oxygen vacancies. The lower energy PL emission decreases with an increase of indium(III) content in the precursor. The size of the nanoparticles calculated from line broadening of XRD pattern (cubic; JCPDS: 06-0416) was found to be around 24?nm. The average particle size of the synthesized nanoparticles increased with metal ion content in the precursor coordination polymer.     

基于1,3,5-三嗪的具有力致变色性质的聚集诱导荧光化合物的合成及性质

以1,3,5-三嗪为核, 四苯基乙烯为端基, 合成了两种新型的星状结构分子2,4,6-三(4-(1,2,2-三苯基乙烯基)苯基)-1,3,5-三嗪(TTPE-Tr)和2,4,6-三(4-(1,2,2-三苯基乙烯基)-4-联苯基)-1,3,5-三嗪(TTPE-Ph-Tr), 并利用核磁共振(NMR)、离子化质谱(MALDI-MS)及元素分析等对其进行了结构表征. 通过混合溶剂四氢呋喃(THF)/水析出实验显示, 化合物TTPE-Tr和TTPE-Ph-Tr在纯THF溶剂中无荧光, 而在THF/水混合溶剂中, 当水体积分数增加时呈现荧光增强现象. 通过紫外-可见(UV-Vis)光谱、荧光(PL)光谱、扫描电子显微镜(SEM)证实荧光量子效率的提高是由于分子内电子旋转受限(RIR)导致的. 同时发现化合物TTPE-Tr具有力致变色性质, 简单的研磨使其发光颜色(蓝绿光到黄绿光)及发光强度(Φ_F, 24.4%到14.7%)发生了明显的改变. UV-Vis光谱、PL光谱、X射线衍射(XRD)、荧光寿命和荧光量子效率等测试结果显示, 这种现象是由于力刺激改变了TTPE-Tr的分子堆积形式导致的. 热分析结果显示化合物TTPE-Tr和TTPE-Ph-Tr的热分解温度分别为464和385℃, 具有良好的热稳定性.     

Synthesis and properties of new orange red light‐emitting hyperbranched and linear polymers derived from 3,5‐dicyano‐2,4,6‐tristyrylpyridine

Two new orange red light‐emitting hyperbranched and linear polymers, poly(pyridine phenylene)s P1 and P2, were prepared by the Heck coupling reaction. In particular, an A₂ + B₃ approach was developed to synthesize conjugated hyperbranched polymer P2 via one‐pot polycondensation. The polymers were characterized by NMR, Fourier transform infrared, ultraviolet–visible, and elemental analysis. They showed excellent solubility in common solvents such as tetrahydrofuran, CH₂Cl₂, CHCl₃, and N,N‐dimethylformamide and had high molecular weights (up to 6.1 × 10⁵ and 5.8 × 10⁵). Cyclic voltammetry studies revealed that P2 had a low‐lying lowest unoccupied molecular orbital energy level of ?3.22 eV and a highest occupied molecular orbital energy level of ?5.43 eV. The thin film of P2 emitted strong orange‐red photoluminescence at 595 nm. A double‐layer light‐emitting diode fabricated with the configuration of indium tin oxide/P2/tris(8‐hydroxy‐quinoline)aluminum/Al emitted orange‐red light at 599 nm, with a brightness of 662 cd/m² at 7 V and a turn‐on voltage of 4.0 V; its external quantum efficiency was calculated to be 0.19% at 130.61 mA/cm². This indicated that this new electroluminescent polymer (P2) based on 3,5‐dicyano‐2,4,6‐tristyrylpyridine could possibly be used as an orange‐red emitter in polymer light‐emitting displays. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 493–504, 2005     

Narrow band gap D–A copolymer of indacenodithiophene and diketopyrrolopyrrole with deep HOMO level: Synthesis and application in field‐effect transistors and polymer solar cells

A novel fused ladder alternating D–A copolymer, PIDT–DPP, with alkyl substituted indacenodithiophene (IDT) as donor unit and diketopyrrolopyrrole (DPP) as acceptor unit, was designed and synthesized by Pd‐catalyzed Stille‐coupling method. The copolymer showed good solubility and film‐forming ability combining with good thermal stability. PIDT–DPP exhibited a broad absorption band from 350 to 900 nm with an absorption peak centered at 735 nm. The optical band gap determined from the onset of absorption of the polymer film was 1.37 eV. The highest occupied molecular orbital level of the polymer is as deep as ?5.32 eV. The solution‐processed organic field‐effect transistor (OFETs) was fabricated with bottom gate/top contact geometry. The highest FET hole mobility of PIDT–DPP reached 0.065 cm² V^?1 s^?1 with an on/off ratio of 4.6 × 10⁵. This mobility is one of the highest values for narrow band gap conjugated polymers. The power conversion efficiency of the polymer solar cell based on the polymer as donor was 1.76% with a high open circuit voltage of 0.88 V. To the best of our knowledge, this is the first report on the photovoltaic properties of alkyl substituted IDT‐based polymers. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Poly(fluorenevinylene) derivatives by Heck coupling: Synthesis,photophysics, and electroluminescence

Three new poly(fluorenevinylene) derivatives were synthesized, characterized, and used as emissive materials in light‐emitting diodes (LEDs). They were synthesized by Heck coupling of 9,9‐dihexyl‐2,7‐divinylfluorene with 2,7‐dibromo‐9,9‐dihexylfluorene, 2,3‐bis(4‐bromophenyl)quinoxaline, or 2,5‐bis(4‐bromophenyl)‐3,4‐diphenylthiophene to afford the polymers F , Q , and T , respectively. Polymers F and Q had medium number–average molecular weights (M_n ? 14,000) with relatively narrow polydispersity (1.3–1.6), while T was obtained as an oligomer (M_n ? 4000). All polymers were soluble in common organic solvents, such as tetrahydrofuran (THF), chloroform, dichloromethane, and toluene. They emitted blue‐greenish fluorescence light in dilute THF solution (444–491 nm), with photoluminescence (PL) quantum yields of 0.32–0.54, and in thin film (453–488 nm). LEDs with the configuration of ITO/PEDOT‐PSS/Polymer/Li:Al were fabricated and evaluated. The electroluminescence (EL) spectra of the Q and F polymers were very broad covering the blue–green–red region, whereas the spectrum of the polymer T was almost purely blue. The threshold electrical field for light emission of the devices was almost the same (?1.75 MV/cm). The external quantum efficiency of the devices of polymers Q and F was about 1.0 × 10^?3%, whereas that of polymer T was ?3.0 × 10^?5%. The fluorescence lifetime of polymers F and Q was significantly longer than that of the polymer T . © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4494–4507, 2006     

Low bandgap π‐conjugated copolymers based on fused thiophenes and benzothiadiazole: Synthesis and structure‐property relationship study

A series of low bandgap conjugated polymers consisting of benzothiadiazole alternating with dithienothiophene (DTT) or dithienopyrrole (DTP) unit with or without 3‐alkylthiophene bridge have been synthesized. Effect of the fused rings and 3‐alkylthiophene bridge on the thermal, optical, electrochemical, charge transport, and photovoltaic properties of these polymers have been investigated. These polymers show broad absorption extending from 300 to 1000 nm with optical bandgaps as low as 1.2 eV; the details of which can be varied either by incorporating 3‐alkylthiophene bridge or by replacing DTT with DTP. The LUMO levels (?2.9 to ?3.3 eV) are essentially unaffected by the specific choice of donor moiety, whereas the HOMO levels (?4.6 to ?5.6 eV) are more sensitive to the choice of donor. The DTT and DTP polymers with 3‐alkylthiophene bridge were found to exhibit hole mobilities of 8 × 10^?5 and 3 × 10^?2 cm² V^?1 s^?1, respectively, in top‐contact organic field‐effect transistors. Power conversion efficiencies in the range 0.17–0.43% were obtained under simulated AM 1.5, 100 mW cm^?2 irradiation for polymer solar cells using the DTT and DTP‐based polymers with 3‐alkylthiophene bridge as donor and fullerene derivatives as acceptor. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5498–5508, 2009     

Spectroscopic and Discharge Studies on Graphene Oxide Doped PVA/PVP Blend Nanocomposite Polymer Films

Graphene oxide (GO) nanoparticles were synthesized by modified Hummers method. The synthesized GO nanoparticles were incorporated in polyvinyl alcohol/polyvinyl pyrrolidone (PVA/PVP) blend polymers for the preparation of nanocomposite polymer films by solution cast technique. Different characterizations such as XRD, UV–Vis and FTIR were carried-out on to the prepared nanocomposite polymer films. The thermal analysis of the films was studied by DSC. The morphology of PVA/PVP:GO polymer films confirms GO was exfoliated within the PVA/PVP matrix and also reveals the heterogeneous phase of nanocomposite polymer electrolyte systems. From the conductivity studies the highest conductivity of PVA/PVP: GO (0.45: 0.3) was found to be 8.05 × 10^–4 S/cm at room temperature. Solid state battery has been fabricated with the configuration of Mg⁺/(PVA/PVP:GO)/(I₂ + C + electrolyte) and its cell parameters were calculated for a constant load of 100 kΩ.     

New biocidal metal complexes of bisphenol-A formaldehyde polymer containing piperazine

The polymeric ligand (BFP) was synthesized by condensation of bisphenol-A, formaldehyde, and piperazine in alkaline medium at 70–80°C. The polymer–metal complexes were synthesized by the reaction of BFP with Mn(II), Co(II), Ni(II), Cu(II), and Zn(II) acetates in 1?:?0.5 (ligand?:?metal) molar ratio. All the synthesized polymers were characterized by elemental, spectral (infrared, ¹H-NMR, and UV-Vis), magnetic moment measurements, and thermal (TGA) analysis. The ligand-field and nephelauxetic parameters have been determined from UV-Vis spectra using ligand-field theory. Elemental analyses indicate the association of water with metal for Mn(II), Co(II), and Ni(II), which is also supported by TGA. The antimicrobial activities of the synthesized polymers were studied by agar well diffusion methods against Bacillus subtilis, Bacillus megaterium, Staphylococcus aureus, Escherichia coli, Salmonella typhi, Pseudomonas aeruginosa, and Shigella boydii. The antimicrobial activity and thermal stability of Cu(II)–polymer were higher than the other polymer–metal complexes due to the higher stability constant of Cu(II).     

Fire- and heat-resistant matrix resins based on ethynyl-substituted aromatic cyclotriphosphazenes

A novel class of fire- and heat-resistant matrix resins has been synthesized by thermal polymerization of ethynyl-substituted aromatic cyclotriphosphazenes. Thermal polymerization of new tris[4-(4′-ethynylbenzanilido)phenoxy]tris(phenoxy) cyclotriphosphazene ( III ) and tris[4-(4′-ethynylphthalimido)phenoxy]tris(phenoxy)cyclotriphosphazene ( VII ) at 250°C for 1–1.5 h gave tough polymers. The thermal stabilities of the polymers were evaluated in nitrogen and in air by thermogravimetric analysis (TGA). The synthesised polymers were stable to 400–410°C and showed char yield of 78–65% at 800°C in nitrogen and of 78–69% at 700°C in air. The ethynyl-substituted polymer precursor ( III ) was synthesised by the reaction of tris(4-aminophenoxy)tris(phenoxy)cyclotriphosphazene ( I ) with 4-ethynylbenzoyl chloride. The polymer precursor ( VII ) was synthesised by a solution condensation of I with 4-ethynylphthalic anhydride followed by in situ thermal cyclodehydration at 150°C. The structure of polymer precursors was characterized using proton nuclear magnetic resonance (¹H-NMR), infrared (IR) spectroscopy, and elemental analysis. The curing of polymer precursors was monitored by differential scanning calorimetery (DSC) and IR spectroscopy. The synthesised matrix resins are potential candidates for the development of heat- and fire-resistant fiber-reinforced composites. © 1993 John Wiley & Sons, Inc.     

Hydroxyl‐ and amine‐terminated hyperbranched polyurethanes using AB2‐type azide monomers: Synthesis,characterization, fluorescence,and charge‐transfer complexation studies

Novel AB₂‐type azide monomers such as 3,5‐bis(4‐methylolphenoxy)carbonyl azide (monomer 1) , 3,5‐bis(methylol)phenyl carbonyl azide (monomer 2) , 4‐(methylol phenoxy) isopthaloyl azide (monomer 3) , and 5‐(methylol) isopthaloyl azide (monomer 4) were synthesized. Melt and solution polymerization of these monomers yielded hydroxyl‐ and amine‐terminated hyperbranched polyurethanes with and without flexible ether groups. The structures of theses polymers were established using FT‐IR and NMR spectroscopy. The molecular weights (M_w) of the polymers were found to vary from 3.2 × 10³ to 5.5 × 10⁴ g/mol depending on the experimental conditions used. The thermal properties of the polymers were evaluated using TGA and DSC: the polymer obtained from monomer ( 1 ) exhibited lowest T_g and highest thermal stability and the polymer obtained from monomer ( 2 ) registered the highest T_g and lowest thermal stability. All the polymers displayed fluorescence maxima in the 425–525 nm range with relatively narrow peak widths indicating that they had pure and intense fluorescence. Also, the polymers formed charge transfer (CT) complexes with electron acceptor molecules such as 7,7,8,8‐tetracyano‐quino‐dimethane (TCNQ) and 1,1,2,2‐tetracyanoethane (TCNE) as evidenced by UV‐visible spectra. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3337–3351, 2009     

Effect of fluorinated nematic mesogens on phase behaviors and optical properties of chiral liquid crystalline polysiloxanes

A series of new chiral side-chain liquid crystalline polymers (P₁–P₇) have been synthesized with poly(methylhydrogeno)siloxane, two chiral liquid crystalline monomers, cholesteryl-4-allyloxybenzoate (M₁) and cholesteryl 4-(10-undecylen-1-yloxy) benzoate (M₂), and a nematic liquid crystalline monomer, 4-(trifluoromethyl)phenyl 4-(undec-10-enoyloxy)benzoate (M₃). The chemical structures and liquid crystalline properties of the synthesized polymers have been investigated by FTIR, ¹H-NMR, differential scanning calorimetry (DSC), polarizing optical microscopy (POM), thermogravimetric analysis (TGA), and X-ray diffraction (XRD). All chiral polymers show wide mesophase temperature ranges and a high thermal stability with decomposition temperatures (T _d) at 5 % weight loss greater than 300 °C. P₁–P₄ display a single cholesteric phase, but P₅–P₇ containing more fluorinated units show a smectic A (SA) phase besides a cholesteric phase. The optical properties of the polymers have been characterized by circular polarization spectra and optical rotation analysis. The cholesteric polymers P₃ and P₄ exhibit different colors at room temperature, and the color can remain over 24 months. The maximum reflection bands of polymers P₁–P₄ shift to long wavelength with increasing the content of M₃ in the polymer systems. For P₅–P₇, the reflection wavelengths change sharply around the temperature of the SA–Ch phase transition. The specific rotation value of P₂ smoothly decreases from ?8.2° to ?0.29° when it is heated, but the specific rotation value of polymer P₇ changes from negative value to positive value on heating cycle. The optical properties of the polymers offer tremendous potential for various optical applications.     

Synthesis and electro-optical features of a high T g polymer system with excellent electro-optic activity and thermal stability

Three chromophores with tricyanofuran and tricyanopyrroline electron acceptors were synthesized and doped in high glass transition temperature (T _g) polymer poly(N-(4-acetoxylphenyl)maleimide-co-styrene, NAPMI-co-ST). The electro-optic (EO), optical, and thermal properties of the doped poly(NAPMI-co-ST) were characterized and discussed. After being corona poled under 12?kV, this high T _g polymer material showed excellent EO activity and thermal stability. The highest EO coefficient (r ₃₃) reached 48.2?pm?V^?1 (1,310?nm) and could remain 90?% of the original value for 100?h at 85?°C. The EO coefficient was relatively higher compared with other high T _g EO polymers. The thermal stability was also very good and the manufacture process was convenient and applicable for device fabrication.     

Synthesis and characterization of new blue‐light‐emitting polymers based on PPP and PPV having fluorene pendant at vinyl bridge

The new poly(arylene vinylene) derivatives, which are composed of biphenylene vinylene phenylene vinylene, biphenylene vinylene m‐phenylene vinylene, terphenylene vinylene phenylene vinylene, and terphenylene vinylene m‐phenylene vinylene as backbone and bulky fluorene pendants at each vinyl bridge, were designed, synthesized, and characterized. The obtained polymers showed weight‐average molecular weights of 11,100–39,800 with polydispersity indexes ranging from 1.5 to 2.1. The resulting polymers were amorphous with high thermal stability and readily soluble in common organic solvents. The obtained polymers showed blue emission (λ_max = 456–475 nm) in PL spectra, and polymer 4 containing terphenylene vinylene m‐phenylene vinylene showed the most blue shifted blue emission (λ_max = 456 nm). The double layer light‐emitting diode devices fabricated by using obtained polymers as emitter emitted bright blue light. The device showed turn on voltage around 6.5 V and brightness of 70–250 cd/m². © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4923–4931, 2006