Enhanced charge collection in polymer photovoltaic cells by using an ethanol-soluble conjugated polyfluorene as cathode buffer layer

We report enhanced polymer photovoltaic (PV) cells by utilizing ethanol-soluble conjugated poly (9, 9-bis (6'-diethoxylphosphorylhexyl) fluorene) (PF-EP) as a buffer layer between the active layer consisting of poly(3-hexylthiophene)/[6, 6]-phenyl C61-butyric acid methyl ester blend and the Al cathode. Compared to the control PV cell with Al cathode, the introduction of PF-EP effectively increases the shunt resistance and improves the photo-generated charge collection since the slightly thicker semi-conducting PF-EP layer may restrain the penetration of Al atoms into the active layer that may result in increased leakage current and quench photo-generated excitons. The power conversion efficiency is increased ca. 8% compared to the post-annealed cell with Al cathode.

聚3—羟基丁酸酯与聚丙撑碳酸酯共混体系研究

本论文对完全生物降解聚（3—羟基丁酸酯）（PHB）和聚丙撑碳酸酯（PPC）共混体系进行了全面研究，目的是提高PHB的综合性能，加深对共混高聚物的基本物理问题的认识，进一步明晰高聚物的结构和性能之间的关系.1.在分析判断PPC的热降解机理的基础上，对PPC进行了封端处理，阻止了以端羟基回咬“解拉链”方式引起的热降解，增加了PPC热降解反应活化能，显著地提高了PPC的稳定性（提高30K以上）.2.经热性能和形态结构等方面的表征，PHB/PPC共混体系为不相容体系，直接在PHB中加入PPC不能改善PHB的韧性和其它力学性能.3.PCL-PEG-PCL嵌段共聚物能够作为PHB/PPC的增容剂，在PHB/PPC共混体系中加入PCL-PEG-PCL三嵌段共聚物能显著减小分散相的平均尺寸.4.选用增塑剂对PPC进行增塑能够在很大范围内（80K）调节PPC的玻璃化转变温度，使PPC表现出弹性体的特性，拓宽了PPC的应用范围.5.增塑剂1,2丙二醇碳酸酯（PGC）对PHB有一定的增塑作用，但不能明显改善PHB的力学性能.6.增塑后的PPC是PHB的良好增韧剂，使PHB由脆性断裂转变为韧性断裂，最佳增韧效果可使PHB的抗冲击强度由36J/m增加到70PHB/30PPC/20PGC的307J/m，增加8倍.7.增塑后的PPC能够实现对PHB增韧，是增塑剂使得PPC在冲击实验条件下仍然保持弹性体的性质，由此引发空洞化、多重银纹和剪切屈服共存的增韧方式提高PHB的性能.

聚（3-羟基烷酸酯）的改性研究

该论文目的是改性细菌合成的聚(3-羟基丁酸酯)(PHB)及其共聚物(PHBV),采用交联或共混的方法,改变其聚集态结构或超分子结构,从而改善其力学性能.加深对高聚物结构与性能之间关系,高聚物结晶规律、及特殊相互作用在高聚物中作用的认识.1.采用反应性加工,用过氧化二异丙苯(DCP)引发PHBV的自由基链转移反应,产生了支化和交联的化学结构.2.用交联助剂二苯甲撑双马来酰亚胺(BMI)实现了PHBV的γ-辐射交联.交联的PHBV熔点和结晶度下降.3.双酚A(BPA)在PHBV/BPA共混物中起到了物理交联剂的作用.4.氢键交联结构使PHBV的链段运动受限,结晶速率下降.5.对叔丁基苯酚(TBP)在PHBV中形成了氢键接枝的超分子结构.6.经过溶液共混,BPA在PHB中起到了物理交联剂的作用,使PHB的断裂伸长率从3%提高到45%.8.二醋酸纤维素(CDA)与PHBV经溶液共混(混合溶剂氯仿/丙酮),PHBV的力学性能没有改善,原因可能是CDA-PHBV分子间的氢键作用较弱,组分间发生严重相分离,不利于性能提高.

聚3-羟基烷酸酯异相成核结晶的研究

本论文以具有巨大应用前景的PHBV作为研究对象，针对PHBV结晶速率低，易产生二次结晶，从而严重影响其加工性能和力学性能的稳定性等方面的缺点，根据PHBV的分子结构和脆性的机理分析，试图采用添加成核剂的方法，提高PHBV的结晶速率和结晶度，从而缩短PHBV的加工成型周期，控制其聚集态结构，提高其制品的稳定性，改善材料的物理力学性能。并在此基础上，探讨PHBV异相成核结晶的机理，加深成核剂对聚合物有效成核机理的认识，更好的理解聚合物结晶过程。1．添加成核剂的量达到0.5wt％时，对苯二甲酸（TPA）对PHBV起到了显著的结晶成核作用。结晶起始温度提高了约20℃，结晶速率达到最大值所对应的温度T_p提高了30℃，结晶烙增加了15J/g，结晶速率提高了4.4倍。这些数据表明，TPA是一种对PHBV极为有效的成核剂。2．加入成核剂TPA的PHBV表现出典型的双熔融行为，主要原因是TPA对PHBV的结晶成核作用和PHBV的熔融再结晶。低温侧的熔融峰对应着PHBV自熔体降温过程形成的结晶，高温侧的对应着PHBV升温过程中形成的结晶。3．TPA的成核作用大大的改变了PHBV的形态结构，使PHBV的球晶尺寸明显减小，球晶数量增大。4．TPA使PHBV晶体在（110）和（020）方向上微晶尺寸变大，晶区和非晶区的电子密度差增大。5．添加0.5wt％的TPA后，PHBV的断裂伸长率从4％提高到10％。6．TPA、IPA、淀粉和山梨醇对PHBV的结晶都具有很明显的成核作用，其原因可能是化学结构上都具有极性基团。7．红外光谱研究没有能够有效的给出PHBV与TPA是否存在特殊相互作用，从而导致TPA对PHBV的结晶成核作用的证据，但是，PHBV拨基伸缩振动谱带随温度的变化却给出了TPA对PHBv的结晶成核作用始于160℃高温。

White electroluminescence from a single-polymer system with simultaneous two-color emission: Polyfluorene as blue host and 2,1,3-benzothiadiazole derivatives as orange dopants on the side chain

Four single polymers with two kinds of attachment of orange chromophore to blue polymer host for white electroluminescence (EL) were designed. The effect of the side-chain attachment and main-chain attachment on the EL efficiencies of the resulting polymers was compared. The side-chain-type single polymers are found to exhibit more efficient white EL than that of the main-chain-type single polymers. Based on the side-chain-type white single polymer with 4-(4-alkyloxy-phenyl)-7-(4-diphenylamino-phenyl)-2,1,3-benzothiadiazoles as the orange-dopant unit and polyfluorene as the blue polymer host, white EL with simultaneous orange (lambda(max) = 545 nm) and blue emission (lambda(max) = 432 nm/460 nm) is realised. A single-layer device (indium tin oxide/poly(3,4-ethylenedioxythiophene)/polymer/Ca/Al) made of these polymers emits white light with the Commission Internationale de l'Eclairage coordinates of (0.30,0.40), possesses a turn-on voltage of 3.5 V, luminous efficiency of 10.66 cd A(-1), power efficiency of 6.68 lm W-1, and a maximum brightness of 21240 cd m(-2).

Effect of poly(propylene carbonate) on the crystallization and melting behavior of poly(beta-hydroxybutyrate-co-beta-hydroxyvalerate)

The crystallization and melting behavior of poly(beta-hydroxybutyrate-co-beta-hydroxyvalerate) (PHBV) and a 30/70 (w/w) PHBV/poly(propylene carbonate) (PPC) blend was investigated with differential scanning calorimetry (DSC) and Fourier transform infrared (FTIR). The transesterification reaction between PHBV and PPC was detected in the melt-blending process. The interaction between the two macromolecules was confirmed by means of FTIR analysis. During the crystallization process from the melt, the crystallization temperature of the PHBV/PPC blend decreased about 8 degreesC, the melting temperature was depressed by 4 degreesC, and the degree of crystallinity of PHBV in the blend decreased about 9.4%; this was calculated through a comparison of the DSC heating traces for the blend and pure PHBV. These results indicated that imperfect crystals of formed, crystallization was inhibited, and the crystallization ability of PHBV was weakened in the blend. The equilibrium melting temperatures of PHBV and the 30/70 PHBV/PPC blend isothermally crystallized were 187.1 and 179 degreesC, respectively.

White electrolumineseence from a single-polymer system with simultaneous two-color emission: Polyfluorene as the blue host and a 2,1,3-benzothiadiazole derivative as the orange dopant on the main chain

New single-polymer electroluminescent systems containing two individual emission species - polyfluorenes as a blue host and 2,1,3-benzothiadiazole derivative units as an orange dopant on the main chain - have been designed and synthesized. The resulting single polymers are found to have highly efficient white electroluminescence with simultaneous blue(lambda(max) = 421 nm/445 nm) and orange emission (lambda(max) = 564 nm)from the corresponding emitting species. The influence of the photoluminescence (PL) efficiencies of both the blue and orange species on the electroluminescence (EL) efficiencies of white polymer light-emitting diodes (PLEDs) based on the single-polymer systems has been investigated. The introduction of the highly efficient 4,7-bis(4-(N-phenyl-N-(4-methylphenyl)amino)phenyl)-2,1,3-benzothiadiazole unit to the main chain of polyfluorene provides significant improvement in EL efficiency. For a single-layer device fabricated in air (indium tin oxide/poly(3,4-ethylenedioxythiophene): poly(styrene sulfonic acid/polymer/Ca/Al), pure-white electroluminescence with Commission Internationale de l'Eclairage (CIE) coordinates of (0.35,0.32), maximum brightness of 12 300 cd m(-2), luminance efficiency of 7.30 cd A(-1), and power efficiency of 3.34 lm W-1 can be obtained.

Characterization and properties of biodegradable poly(hydroxyalkanoates) and 4,4-dihydroxydiphenylpropane blends: Intermolecular hydrogen bonds, miscibility and crystallization

Intermolecular hydrogen bonds, miscibility, crystallization and thermal stability of the blends of biodegradable poly(3-hydroxybutyrate) (PHB), poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) [P(3HB-3HHx)] with 4,4-dihydroxydiphenylpropane (DOH2) were investigated by FTIR, C-13 Solid state NMR, DSC, WAXD and TGA. Intermolecular hydrogen bonds were found in both blend systems, which resulted from the carbonyl groups in the amorphous phase of both polyesters and the hydroxyl groups of DOH2. The intermolecular interaction between P(3HB-3HHx) and DOH2 is weaker than that between PHB and DOH2 owing to the steric hindrance of longer 3HHx side chains. Because of the effect of the hydrogen bonds, the chain mobility of both PHB and P(3HB-3HHx) components was limited after blending with DOH2 molecules. Single glass transition temperature depending on the composition was observed in all blends, indicating that those blends were miscible in the melt. The addition of DOH2 suppressed the crystallization of PHB and P(3HB-3HHx) components. Moreover, the crystallinity of PHB and P(3HB-3HHx) components also decreased with increasing DOH2 content in the blends.

Thermotropic liquid crystallinity, thermal decomposition behavior, and aggregated structure of poly(propylene carbonate)/ethyl cellulose blends

Maleic anhydride end capped poly(propylene carbonate) (PPC-MA) was blended with ethyl cellulose (EC) by casting from dichloromethane solutions. The thermotropic liquid crystallinity, thermal decomposition behavior, and aggregated structure were investigated by differential scanning calorimetry (DSC), thermogravimetry (TGA), and wide angle X-ray diffraction (WAXD). DSC exhibits thermotropic liquid crystallinity in the rich EC composition range. TGA shows that thermal decomposition temperatures were elevated upon interfusing EC into PPC-MA. WAXD corroborates that EC and PPC-MA/EC blend films cast from dilute dichloromethane solution possessed cholesteric liquid crystalline structure in the rich EC composition range, and that dilution of PPC-MA with EC increased the dimension of noncrystalline region, leading to a more ordered packed structure.

Syntheses of biphenyl polyimides via nickel-catalyzed coupling polymerization of bis(chlorophthalimide)s

A facile method for the synthesis of biphenyl polyimides, which involves the nickel-catalyzed coupling of aromatic dichlorides containing imide structure in the presence of zinc and triphenylphosphine, has been developed. The polymerizations proceeded smoothly under mild conditions and produced biphenyl polyimides with inherent viscosities of 0.13-0.98 dL/g. The polymerizations of bis(4-chlorophthalimide)s with bulky side substituents gave high molecular weight polymers. Low molecular weight polymers from bis(4-chlorophthalimide)s containing rigid diamine moieties and bis(3-chlorophthalimide)s were obtained because of the formations of polymer precipitate and cyclic oligoimides, respectively. The effects of various factors, such as amount of catalyst, solvent volume, ligand, reaction temperature, and time, on the polymerization were studied. The random copolymerization of two bis(chlorophthalimide)s in varying proportions produced medium molecular weight material. The TgS of prepared polyimides were observed at 245-311 degreesC, and the thermogravimetry of polymers showed 10% weight loss in nitrogen at 470-530 degreesC.

Synthesis and characterization of poly(beta-hydroxybutyrate) and poly(epsilon-caprolactone) copolyester by transesterification

To synthesize the copolyester of poly(beta-hydroxybutyrate) (PHB) and poly(epsilon-caprolactone) (PCL), the transesterification of PHB and PCL was carried out in the liquid phase with stannous octoate as the catalyzer. The effects of reaction conditions on the transesterification, including catalyzer concentration, reaction temperature, and reaction time, were investigated. The results showed that both rising reaction temperature and increasing reaction time were advantageous to the transesterification. The sequence distribution, thermal behavior, and thermal stability of the copolyesters were investigated by C-13 NMR, Fourier transform infrared spectroscopy, differential scanning calorimetry, wide-angle X-ray diffraction, optical microscopy, and thermogravimetric analysis. The transesterification of PHB and PCL was confirmed to produce the block copolymers. With an increasing PCL content in the copolyesters, the thermal behavior of the copolyesters changed evidently. However, the introduction of PCL segments into PHB chains did not affect its crystalline structure. Moreover, thermal stability of the copolyesters was little improved in air as compared with that of pure PHB.

Miscibility, crystallization kinetics, and morphology of poly(beta-hydroxybutyrate) and poly(methyl acrylate) blends

The miscibility, spherulite growth kinetics, and morphology of binary blends of poly(beta-hydroxybutyrate) (PHB) and poly(methyl acrylate) (PMA) were studied with differential scanning calorimetry, optical microscopy, and small-angle X-ray scattering (SAXS). As the PMA content increases in the blends, the glass-transition temperature and cold-crystallization temperature increase, but the melting point decreases. The interaction parameter between PHB and PMA, obtained from an analysis of the equilibrium-melting-point depression, is -0.074. The presence of an amorphous PMA component results in a reduction in the rate of spherulite growth of PRE. The radial growth rates of spherulites were analyzed with the Lauritzen-Hoffman model. The spherulites of PHB were volume-filled, indicating the inclusion of PMA within the spherulites. The long period obtained from SAXS increases with increased PMA content, implying that the amorphous PMA is entrapped in the interlamellar region of PHB during the crystallization process of PHB. All the results presented show that PHB and PMA are miscible in the melt. (C) 2000 John Wiley & Sons, Inc.

Study on the properties of poly(beta-hydroxybutyrate) grafted with maleic anhydride

The thermal stability, crystallization behavior and biodegradability of poly(beta -hydroxybutyrate) (PHB) grafted with maleic anhydride (MA) were studied by DSC,TGA, optical microscopy and WAXD. The results showed that thermal stability of maleated PHB was obviously improved, comparing with that of pure PHB. The temperature of decomposition was enhanced about 20 degreesC After grafting MA, the crystallization behavior of PHB changed evidently. The rate of spherulite growth decreased, the crystallization temperature from the melt state reduced, and the cold crystallization temperature from the glass state increased. With the increase in graft degree, the banding texture of spherulite became more distinct and orderly. Moreover, the introduction of MA groups promoted the biodegradation of PHB.

Miscibility and crystallization of poly(beta-hydroxybutyrate) and poly(p-vinylphenol) blends

The miscibility and crystallization behavior of poly(beta-hydroxybutyrate) (PHB) and poly(p-vinylphenol) (PVPh) blends were studied by differential scanning calorimetry and optical microscopy (OM). The blends exhibit a single composition-dependent glass transition temperature, characteristic of miscible systems, A depression of the equilibrium melting temperature of PHB is observed. The interaction parameter values obtained from analysis of the melting point depression are of large negative values, which suggests that PHB and PVPh blends are thermodynamically miscible in the melt. Isothermal crystallization kinetics in the miscible blend system PHB/PVPh was examined by OM. The presence of the amorphous PVPh component results in a reduction in the rate of spherulite growth of PHB. The spherulite growth rate is analyzed using the Lauritzen-Hoffman model, The isothermally crystallized blends of PHB/PVPh were examined by wide-angle X-ray diffraction and smell-angle X-ray scattering (SAXS). The long period obtained from SAXS increases with the increase in PVPh component, which implies that the amorphous PVPh is squeezed into the interlamallar region of PHB.