HYPERBRANCHED CONJUGATIVE MACROMOLECULES CONSTRUCTED FROM TRIPLE-BOND BUILDING BLOCKS

Polycyclotrimerization and polycoupling of acetylenic monomers respectively furnish hyperbranched polyarylenes and polyynes with high molecular weights(up to 1×10~6)in high yields(up to 99.9%).The polymers possess low intrinsic viscosities and high thermal stabilities,losing little of their weights when heated to＞400℃.Upon pyrolysis at＞800℃,the polymers graphitize with high char yields(up to 86%).Hyperbranched polyarylenes efficiently emit deep-blue to blue-green lights with fluorescence quantum yields up to 98% and strongly attenuate intense laser pulses with optical power-limiting performances superior to that of C_(60),a well-known optical lirniter.Poly(alkenephenylenes),poly(aroylarylenes)and polyynes are readily cross-linkable by UV irradiation,serving as excellent photoresist materials for the generation of patterns with nanometer resolution.Thin films of hyperbranched polyynes exhibit very high refractive indexes(n up to 1.86).The internal and terminal acetylene moieties of the polyynes readily form complexes with cobalt carbonyls,which can be transformed into soft ferromagnetic ceramics with high magnetic susceptibilities(M_s up to ca.118 emu/g)and near-zero magnetic losses.     

SYNTHESIS OF HYPERBRANCHED CONJUGATIVE POLY（ARYLENEETHYNYLENE）S BY ALKYNE POLYCYCLOTRIMERIZATION

A series of new hyperbranched poly(aryleneethynylene)s are synthesized by the copolycyclotrimerizations oftetraynes(Ⅰand Ⅱ)with aliphatic monoynes(A-C)catalyzed by tantalum-,niobium-,and cobalt-based catalysts.All thereactions proceed smoothly and soluble polymers of high molecular weights(M_w up to 3.8×10~4)are obtained in high yields(up to 97%).     

SYNTHESIS,CHARACTERIZATION AND OPTICAL PROPERTIES OF THE COPOLYMERS OF C_(60) AND 1-PHENYL-1-PROPYNE*

While WCl_6-Ph_4Sn fails to polymerize 1-phenyl-1-propyne (PP) at room temperature, highmolecular weight (M_w up to 410×10~3) polymers are obtained in high yields (up to 80%) when thepolymerizations of PP are carried out in the presence of C_(60) using the W catalyst under the same conditions.The polymers are soluble in common organic solvents such as THF, chloroform, and toluene. Molecularstructures of the polymers are characterized by FT-IR, UV, NMR, GPC and XRD, and it is found that C_(60) iscopolymerized with PP. Thus C_(60) plays the dual roles of comonomer and cocatalyst in the polymerizationreaction. C_(60) contents of the copolymers can be easily changed by varying the C_(60) amounts in the feedmixtures. The copolymers effectively limit strong 532 nm laser pulses, whose limiting performance issuperior to that of parent C_(60).     

Rylene diimide and dithienocyanovinylene copolymers for polymer solar cells

Two polymers containing(E)-2,3-bis(thiophen-2-yl)acrylonitrile(CNTVT) as a donor unit, perylene diimide(PDI) or naphthalene diimide(NDI) as an acceptor unit, are synthesized by the Stille coupling copolymerization, and used as the electron acceptors in the solution-processed organic solar cells(OSCs). Both polymers exhibit broad absorption in the region of 300–850 nm. The LUMO energy levels of the resulted polymers are ca. –3.93 eV and the HOMO energy levels are –5.97 and –5.83 eV. In the binary blend OSCs with PTB7-Th as a donor, PDI polymer yields the power conversion efficiency(PCE) of up to 1.74%, while NDI polymer yields PCE of up to 3.80%.     

LINEAR AND HYPERBRANCHED POLYMERS WITH HIGH THERMAL STABILITY AND LUMINESCENCE EFFICIENCY

New acetylene monomers, 6-{[(1-naphthylethynyl-4-phenyl)carbonyl]oxy}-1-pheny-1-hexyne (1), 2, 5-diethynyl-thiophene (3), and 4,4'-diethynylbiphenyl(6) were synthesized. Homopolymerization of 1 and copolycyclotrimerizations of 3and 6 with 1-heptyne and 1-octyne have been achieved with WCl_6- and TaCl_5-Ph_4Sn catalysts, respectively, giving solublelinear disubstituted polyacetylene (2) and hyperbranched polyarylenes (5 and 8) with high molecular weights (up to 1.2×10~5) in high yields (up to 98%). The trictures and properties of the polymers are characterized and evaluated by IR, NMR,TGA, UV, photoluminescence (PL), and electroluminescence (EL) analyses. All the polymers possess high thermal stabilityand emit strong blue ligh upon photoexcitation. The intensity of the emitted light is greater than that of poly(1-phenyl-1-octyne), a well-known highly luminescent disubstituted polyacetylene. Little aggregation-induced red shift in the PL wasobserved in the thin films of the polymers. By constructing a multi-layer EL device, high EL quantum yield (0.18%) has beenachieved in 2, which are the best results for substituted polyacetylenes attainable so far.     

Through-space charge transfer blue polymers containing acridan donor and oxygen-bridged triphenylboron acceptor for highly efficient solution-processed organic light-emitting diodes

Three kinds of through-space charge transfer(TSCT) blue polymers containing non-conjugated polystyrene backbone together with spatially-separated acridan donor and oxygen-bridged triphenylboron acceptors having different substituents of tert-butyl,hydrogen and fluorine are designed and synthesized. The designed TSCT blue polymers possess photoluminescence quantum yields up to 70% in solid-state film, single-triplet energy splitting below 0.1 eV, and typical thermally activated delayed fluorescence(TADF) effect. Meanwhile, the resulting polymers exhibit aggregation-induced emission(AIE) effect with emission intensity increased by up to ～27 folds from solution to aggregation state. By changing the substituent of acceptors to tune the charge transfer strength, blue emission with peaks from 444 to 480 nm can be realized for the resulting polymers.Solution-processed organic light-emitting diodes based on the polymers exhibit excellent device performance with Commission Internationale de L'Eclairage(CIE) coordinates of(0.16, 0.27), together with the maximum luminous efficiency of 30.7 cd A~(-1) and maximum external quantum efficiency of 15.0%, which is the best device efficiency for blue TADF polymers.     

SYNTHESIS, HELICITY, AND BIOLOGICAL PROPERTIES OF MONOSACCHARIDE-CONTAINING POLY（PHENYLACETYLENE）S

Poly（phenylacetylene）s beating monosaccharide pendant groups are synthesized in high yields by [Rh（nbd）Cl]2 catalyst. The polymers have high molecular weights and give satisfactory spectroscopic data corresponding to their molecular structures. They are thermally quite stable （≥ 300℃） and show strong circular dichroism signals in the visible spectral region owing to the helicity of the polyene backbone. The monosaccharide-containing polyacetylenes are cytophilic and can stimulate the growth of living cells.     

Eco-friendly fast synthesis and thermal degradation of optically active polyamides under microwave accelerating conditions

<正>An optically active bulky aromatic diacid chiral monomer,(2S)-4-[(4-methyl-2-phthalimidylpentanoyl-amino) benzoylamino]isophthalic acid(1),containing a rigid phthalimide and flexible L-leucine pendent group was synthesized in five steps.A fast and clean method for direct polyamidation reaction of monomer 1 with various aromatic diamines under microwave irradiation and conventional heating was performed.The polymerization reactions provided optically active polyamides with high yields and inherent viscosities in the range of 0.36-0.74 dL/g.Their thermal properties were evaluated by thermogravimetric analysis(TGA) and differential scanning calorimetry.TGA thermograms show that the polymers are thermally stable,10%weight loss temperatures are in excess of 385℃,and char yields at 800℃are higher than 56%.The data obtained from TGA were used to study the kinetics of thermal decomposition of the resulting polymers. The interpretation of kinetic parameters(E,ΔH,ΔS andΔG) of thermal decomposition stages was evaluated using Coats and Redfern equation.     

Molecular engineering tuning optoelectronic properties of thieno[3,2-b]thiophenes-based electrochromic polymers

Thieno[3,2-b]thiophene(TT)monomers end-capped with 3,4-ethylenedioxythiophene(EDOT)moieties are electropolymerized to formπ-conjugated polymers with distinct electrochromic(EC)properties.Steric and electronic factors(electron donor and acceptor substituents)in the side groups of the TT core,as well as the structure of the polymer backbone strongly affect the electrochemical and optical properties of the polymers and their electrochromic characteristics.The studied polymers show low oxidation potentials,tunable from-0.78 to+0.30 V(vs.Fc/Fc~+)and the band gaps from 1.46 to 1.92 eV and demonstrate wide variety of color palettes in polymer films in different states,finely tunable by structural variations in the polymer backbone and the side chains.EC materials of different colors in their doped/dedoped states have been developed(violet,deep blue,light blue,green,brown,purple-red,pinkish-red,orange-red,light gray,cyan and colorless transparent).High optical contrast(up to 79%),short response time(0.57-0.80 s),good cycling stability(up to 91%at 2000 cycles)and high coloration efficiency(up to 234.6 cm2C~(-1))have been demonstrated and the influence of different factors on the above parameters of EC polymers have been discussed.     

Metal-free multicomponent polymerization of activated diyne,electrophilic styrene and isocyanide towards highly substituted and functional poly(cyclopentadiene)

The development of a facile and efficient polymerization to prepare cyclopentadiene-containing polymers is of vital importance and highly desired. In this work, a metal-free multicomponent polymerization of activated diyne, electrophilic styrene and isocyanide for the preparation of highly substituted poly(cyclopentadiene) was established. Soluble and thermally stable polymers with high molecular weights are obtained in high yields under mild conditions. By introducing the tetraphenylethene or t...     

新型超支化聚芳烃的合成与性能研究

3,6-二乙炔基-9-(三苯胺基)-咔唑、4,4′-二乙炔基-4″-(咔唑基)-三苯胺双炔和1-辛炔单炔在CpCo(CO)2-hν催化的条件下合成了新型超支化聚芳烃.所得的聚合物都溶于普通溶剂(甲苯、THF、氯仿、二氯甲烷等).在光激发的条件下,聚合物在428 nm左右发射蓝光,其荧光量子效率达到62%.所有超支化聚合物都表现出优异的热稳定性,它们的起始分解温度高达484℃.     

9,9-二(4-羟基苯基)呫吨、1,4-二(4-氟苯甲酰基)苯和双酚A三元共聚物聚醚醚酮酮的合成与表征

通过亲核取代反应,将9,9-二(4-羟基苯基)呫吨(BHPX)、1,4-二(4-氟苯甲酰基)苯和双酚A(BPA)进行三元共缩聚反应,合成了几种主链含二甲基甲烷和呫吨结构的聚醚醚酮酮无规共聚物(PEEKK-X/PEEKK-A),并以FTIR、DSC、TG、WAXD等对其结构和性能进行了表征.结果表明,共聚物的玻璃化转变温度(Tg)为185～218℃,均为无定形结构,其数均分子量为39500～41600,多分散性指数为1.94～2.05.在氮气、空气气氛中,在430℃之前不分解,5%的热失重温度(Td5)分别为490～511℃、480～505℃,在氮气中700℃时的残炭率均在40%以上;在常温下易溶于非质子极性溶剂(如NMP和DMAc)以及极性较弱的溶剂(如THF和CHCl3)中.共聚物均可通过溶液浇铸成膜,所得到的薄膜韧性好,透明且耐折,其拉伸强度为58～75MPa,杨氏膜量为1.95～2.70GPa,断裂伸长率为8%～13%.当双酚单体BHPX和BPA摩尔比为60/40～50/50时,所得到的PEEKK-X/PEEKK-A共聚物更有潜在的应用前景.     

Silole‐containing poly(silylenevinylene)s: Synthesis,characterization, aggregation‐enhanced emission,and explosive detection

Hydrosilylation polymerizations of 1,1‐dimethyl‐2,5‐bis(4‐ethynylphenyl)‐3,4‐diphenylsilole with aromatic silylhydrides including 1,4‐bis(dimethylsilyl)benzene, 4,4′‐bis(dimethylsilyl)biphenyl, 2,5‐bis(dimethylsilyl)thiophene, and 2,7‐bis(dimethylsilyl)‐9,9‐dihexylfluorene in the presence of Rh(PPh₃)₃Cl catalyst in refluxed tetrahydrofuran afford a series of silole‐containing poly(silylenevinylene)s. Under optimum condition, the alkyne polyhydrosilylation reactions progress efficiently and regioselectively, yielding polymers with high molecular weights (M_w up to 95,300) and good stereoregularity (E content close to 99%) in high yields (up to 92%). The polymers are processable and thermally stable, with high decomposition temperatures in the range of 420?449 °C corresponding to 5% weight loss. They are weakly fluorescent in the solution state but become emissive in the aggregate and film states, demonstrating their aggregation‐enhanced emission characteristics. The explosive sensing capabilities of the polymers are examined in both solution and aggregate states. The emissions of the polymers aggregates in aqueous mixture are quenched more efficiently by picric acid in an exponential pattern with high quenching constants (up to 27,949 L mol^?1), suggesting that the polymers aggregates are sensitive chemosensors for explosive detection. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Polycyclotrimerization of aromatic diynes: Synthesis,thermal stability,and light‐emitting properties of hyperbranched polyarylenes

New aromatic diyne monomers of 1,4‐diethynyl‐2,5‐(dihexyloxy)benzene ( 1 ), 1,6‐diethynyl‐2‐(hexyloxy)naphthalene ( 2 ), and 9,9‐bis(4‐ethynylphenyl)fluorene ( 3 ) are synthesized. Their homopolymerizations and copolymerizations with 1‐octyne ( 4 ) or phenylacetylene ( 5 ) are effected by TaBr₅–Ph₄Sn and CpCo(CO)₂–hν, giving soluble hyperbranched polyarylenes with high molecular weights (M_w up to ～ 2.9 × 10⁵) in high yields (up to 99%). The structures and properties of the polymers are characterized and evaluated by IR, NMR, UV, PL, and TGA analysis. The polymers show excellent thermal stability (T_d > 400 °C) and carbonize when pyrolyzed at 900 °C. Upon photoexcitation, the polymers emit deep blue light in the vicinity of ～400 nm with fluorescence quantum yields up to 92%. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4249–4263, 2007     

Synthesis and light-emitting properties of disubstituted polyacetylenes carrying chromophoric naphthylethynylphenyl pendants

Poly(1-phenyl-1-alkyne)s bearing chromophoric pendants and containing alkyl spacers (-{(C 6H 5)CC[(CH 2) m OCOC 6H 4CCNp]} n - [P 1( m) ( m = 3, 4, 9); Np = 1-naphthyl]) were synthesized, and the effects of structural variations on the optical properties, especially electroluminescence, of the polymers were investigated. The monomers were prepared in high yields by esterification and coupling reactions of n-phenyl-( n - 1)-alkyn-1-ols. Selective polymerizations of the 1-phenyl-1-alkyne unit of the monomers were effected by WCl 6-Ph 4Sn catalyst, affording polymers with high molecular weights ( M w up to 63 000) in high yields (up to 83%). Structures and properties of the polymers were characterized and evaluated by IR, NMR, TGA, UV, PL, and EL analyses. All the polymers are thermally very stable, losing almost no weight when heated up to 400 degrees C. Photoexcitation of the polymer solutions induces strong blue light emission at 460 nm, with quantum yields up to 98%. No aggregation quenching was observed when the polymers were fabricated into solid films. Multilayer EL devices with the configuration of ITO/P 1( m):PVK/BCP/Alq 3/LiF/Al were fabricated, which emitted blue light with luminance up to 498 cd/m (2). The device performance varied with the spacer length ( m), with P 1(4) giving the highest external quantum efficiency of 0.47%. The value was further enhanced to 0.86% by optimizing the layer thickness and inserting a hole-injection layer.     

高硼含量的SiC陶瓷先驱体的合成和表征

采用经典硼氢化反应, 通过硼烷二级硫醚(BH₃·SMe₂)与二甲基二乙烯基硅烷(DVS)反应, 合成了聚硼碳硅烷(PBCS)陶瓷先驱体, PBCS在氮气中经高温裂解得到了高硼含量的SiC陶瓷.利用红外光谱、核磁共振波谱和热重分析对聚合物的结构和性能进行了表征; 利用元素分析、X射线衍射和扫描电子显微镜对聚合物的裂解产物进行了分析.结果表明, 聚合物的结构中含有B—C, Si—C和C—H键, 在1000℃氮气气氛中, 其陶瓷产率在50%以上.陶瓷产物在1100℃以无定形态存在, 硼含量高达6.46%, 在1300℃时出现明显结晶, 形成B₂O₃, C和β-SiC三相组成的多元复相陶瓷, 在1500℃以下陶瓷产物表面光滑, 结构致密.     

Bipolar Blue Light-emitting Polyfluorenes Containing Dibenzothiophene-S,S-dioxide/Carbazole Units

Bipolar blue light-emitting polyfluorenes(PFSO-Cz) containing electron-deficient dibenzothiophene-S,S-dioxide(SO) and electron-rich carbazole(Cz) unit were synthesized. All the polymers show a high thermal stability with the decomposition temperatures over 400℃ and higher photoluminescence quantum yields. The highest occupied molecular orbital energy levels(E_HOMO's) slightly enhance and the lowest unoccupied molecular orbital energy levels(E_LUMO's) gently depress with the increase of Cz content in the polymers. PL spectra of the polymers display remarkable red shift and broadening with the increase of solvent polarities, indicating significant intramolecular charge transfer(ICT) effect in the polymers. Electroluminescence(EL) spectra of the polymers exhibit a broadening tendency with increasing the content of Cz unit in the polymers. The superior device performances were obtained with the maximum luminous efficiency(LE­_max) of 5.2 cd/A, the maximum external quantum efficiency(EQE_max) of 4.8% and the Internationale de l'Eclairage(CIE)(x,y) coordinates of (0.16, 0.17) for PFSO15-Cz10 based on the single-layer device of ITO/PEDOT:PSS/EL/CsF/Al. The results indicate that the efficient bipolar blue light-emitting polyfluorenes are also constructed by Suzuki copolymerization using the monomers in common use.