Synthesis and bulk polymerization kinetics of monomer dehydroabietic acid-(2-acryloyloxy-ethoxy)-ethyl ester

A bulk polymerization monomer dehydroabietic acid-(2-acryloyloxy-ethoxy)-ethyl ester(DHADG-AC) was synthesized from dehydroabietic acid(DHA). The chemical structure of DHA-DG-AC was characterized by1~HNMR,(13)~CNMR, MS and FT-IR. The kinetics of the bulk polymerization of DHA-DG-AC was investigated by Differential Scanning Calorimeter(DSC).Two kinds of kinetic model(nth-order model and autocatalytic model) were used to investigate the polymerization process. The results showed that the experim e nt al DSC c u r ve s w e r e c o n si st e nt wi th t he computational data generated by the autocatalytic kinetic model, and the value of E_a was 95.73 k J·mol^(–1).

Visualization of Bulk Polymerization by Fluorescent Probe with Aggregation-induced Emission Characteristics

Bulk polymerization is one of the most commonly used techniques in polymer preparing due to its relatively simple process,low cost and easier aftertreatment of the product[1-5].Bulk polymerization has attracted much attention in both academic researches and industrial productions of commodity polymers,such as poly(methyl methacrylate)(PMMA)[6]and polystyrene(PS)[7].During the process of bulk polymerization,an autoacceleration phenomenon,which is also referred to as the gel or Trommsdorff effect,is often observed[8].

“LIVING”/CONTROLLED RADICAL POLYMERIZATION OF ETHYL METHYLACRYLATE WITH 2,2’-AZOBISISOBUTYRONITRILE/FERRIC CHLORIDE/TRIPHENYLPHOSPHINE INITIATION SYSTEM

'Living'/controlled radical polymerization of ethyl methacrylate (EMA) was carried out with a 2,2'-azobisisobutyronitrile (AIBN)/ferric chloride (FeCl_3)/triphenylphosphine (PPh_3) initiation system at 85℃. Thc numberaverage molecular weight (M_n) increases linearly with monomer conversion and the rate of polymerization is first order withrespect to monomer concentration. The M_w of PEMA ranges from 3900 to 17600 and the polydispersity indices are quitenarrow (1.09～1.22). The conversion can reach up to～100% and M_w of the polymers obtained is close to that designed. Thepolymerization mechanism belongs to the reverse atom transfer radical polymerization (ATRP). The polymer was end-functionalized by chlorine atom, which acts as a macroinitiator to proceed extension polymerization in the presence ofCuBr/bipy catalyst system via an ATRP process. The presence of ω-chlorine in the PEMA obtained was identified by ~1H-NMR spectrum.

Thermal Stability and Crystallinity Study of Polystyrene/SiO2 Nano-Composites Synthesis via Microwave-Assisted In Situ Polymerization

Serials of polystyrene/SiO2 Nano composites (PS/SiO2) with different content of inorganic fillers were successfully prepared by the in situ bulk radical polymerization of styrene under microwave irradiation. The effect of the amount of Nano SiO2 on the properties of the PS/SiO2 Nanocomposites along with the average relative molecular masses (Mn, Mz and Mw) was investigated by thermal analysis and X-Ray Diffraction (XRD). Their structural model was proposed on the basis of the Optical Microscopy, FTIR (Fourier Transform Infrared) analysis, differential scanning calorimetry (DSC), gel permeation chromatography (GPC) and X-Ray Diffraction (XRD). The dispersion of nanoparticles in Polystyrene is observed in the magnified image. The effect of microwave irradiation power on molecular weight of polystyrene was also studied. It was found that, the microwave assisted reaction needs less time as compare to conventional polymerization and found to be in between 10 to 15 min.

Effect of Crystallinity of Fullerene Derivatives on Doping Density in the Organic Bulk Heterojunction Layer in Polymer Solar Cells

Polymer solar cells （PSCs） based on poly（3-hexylthiophene） （P3HT） and [6,6]-phenyl-C61-butyric acid methyl ester （PCBM） are fabricated by using 1,8-diiodooctane （DIO） as a solvent additive to control the doping density of the PSCs. It is shown that the processing of DIO does not change the doping density of the P3HT phase, while it causes a dramatic reduction of the doping density of the PCBM phase, which decreases the doping density of the whole blend layer from 3.7 × 10^16 cm-3 to 1.2 ×10^16 cm-3. The reduction of the doping density in the PCBM phase originates from the increasing crystallinity of PCBM with DIO addition, and it leads to a decreasing doping density in the blend film and improves the short circuit current of the PSCs.

Influence of small-molecule material on performance of polymer solar cells based on MEH-PPV:PCBM blend

In this work, the influence of a small-molecule material, tris（8-hydroxyquinoline） aluminum （Alq3）, on bulk heterojunction （BHJ） polymer solar cells （PSCs） is investigated in devices based on the blend of poly（2-methoxy-5-（2- ethylhexyloxy）-1,4-phenylenevinylene） （MEH-PPV） and [6,6]-phenyl-C61-butyric acid methyl ester （PCBM）. By doping Alq3 into MEH-PPV：PCBM solution, the number of MEH-PPV excitons can be effectively increased due to the energy transfer from Alq3 to MEH-PPV, which probably induces the increase of photocurrent generated by excitons dissociation. However, the low carrier mobility of Alq3 is detrimental to the efficient charge transport, thereby blocking the charge collection by the respective electrodes. The balance between photon absorption and charge transport in the active layer plays a key role in the performance of PSCs. For the case of 5 wt.% Alq3 doping, the device performance is deteriorated rather than improved as compared with that of the undoped device. On the other hand, we adopt Alq3 as a buffer layer instead of commonly used LiF. All the photovoltaic parameters are improved, yielding an 80% increase in power conversion efficiency （PCE） at the optimum thickness （1 nm） as compared with that of the device without any buffer layer. Even for the 5 wt.% Alq3 doped device, the PCE has a slight enhancement compared with that of the standard device after modification with 1 nm （or 2 nm） thermally evaporated Alq3. The performance deterioration of Alq3-doped devices can be explained by the low solubility of Alq3, which probably deteriorates the bicontinuous D-A network morphology; while the performance improvement of the devices with Alq3 as a buffer layer is attributed to the increased light harvesting, as well as blocking the hole leakage from MEH-PPV to the aluminum （Al） electrode due to the lower highest occupied molecular orbital （HOMO） level of Alq3 compared with that of MEH-PPV.

Synthesis and Photovoltaic Properties of A Dithieno[6,5-b：10,11-b＇]-8H-Cyclopentyl[1,2-b：4,3-b＇]Diphenanthrene based Donor-Acceptor Alternating Copolymer

A novel fused nonacyclic monomer of dithieno[6,5-b：10,11-b＇]-8 H-cyclopentyl[1,2-b：4,3-b＇]diphenanthrene（DTCPDP） was synthesized by combining the structural features of ladder-type and multiple fused multi-cyclic aromatics. DTCPDP has a single sp3-hybridized carbon bridge between fused multi-cyclic aromatics. The copolymerization of DTCPDT with the electron accepting unit of 4,7-di（thiophen-2-yl）benzo[c][1,2,5]thiadiazole（DTBT） via Stille coupling afforded a novel donor-acceptor（D-A） alternating copolymer PDTCPDT-DTBT. The copolymer exhibited good chemical and thermal stabilities, with an optical band gap of 1.82 eV and a low-lying highest occupied molecular orbital（HOMO） energy level of-5.32 eV. When the copolymer was incorporated into polymer： fullerene（PC_（71）BM） blends to fabricate bulk heterojunction polymer solar cell devices, the devices exhibited a moderate maximum power conversion efficiency（PCE） of 5.90%.

Copolymerization of α-Methylstyrene and Styrene

In this paper, the effects of temperature from 60 ℃ to 80 ℃ and the molar ratios in monomer feed on the copolymerization of α-methylstyrene （AMS） and styrene （St） were studied. The resulting copolymers, designated as PAS, were characterized by FTIR, GPC, NMR and TGA. When the reaction temperature was below 75 ℃, the molecular weights increased almost linearly as the evolution of the copolymerization. The phenomenon revealed that AMS could mediate the conventional free radical polymerization having some features of a controlled system. As the AMS/St = 50/50 （molar） in feed, the overall fraction of the AMS unit incorporated into the copolymer was as high as 42 mol%, the monomer conversion could be more than 90 wt% and the molecular weights could reach as high as 4400. However, since the styrene is more reactive than AMS, the AMS fraction in copolymer increased with the overall monomer conversion. The 13C-NMR revealed the products were random copolymers which had triads, such as -AMS-AMS-AMS-, -St-AMS-AMS- （-AMS-AMS-St-） and -St-AMS-St-. TGA curves demonstrated that the degradation temperature of the resulting copolymers went down from about 356.9 ℃ （0 mol% AMS） to 250.2 ℃ （42 tool% AMS）. This behavior demonstrated that there exist weak bonds in the AMS- containing sequences which could be used as potential free radical generators.

Enhanced Power Conversion Efficiency in Bulk Heterojunction Polymer Solar Cells Through Dual-Interface Morphology Modification

Efficient bulk heterojunction（BHJ） polymer solar cells with a poly（3,4-ethylenedioxythiophene）：poly（styrenesulfonate） hole transfer layer（HTL） were fabricated via controlling the spin coating speed of the HTL solution on a particular fluorinated tin oxide substrates of a high roughness.It shows that the functions of the photovoltaic devices increase with the increase of the HTL surface roughness.Then,an imprinting technique was employed to transfer a suitable pattern of nanostructure arrays to the surface of active layers.At the optimized spin coating speed,the photovoltaic devices exhibited a 28.4% increase in efficiency after this imprinting treatment compared with that of nonimprinted photovoltaic devices.It is mainly attributed to the achievement of high interface areas between active layers and electrodes,which not only increases optical absorption by scattering but also facilitates charge carrier collection.

Inverted polymer solar cells with Zn_2SnO_4 nanoparticles as the electron extraction layer

In this study, we report narrow-size distribution Zn_2SnO_4（ZSO） nanoparticles, which are produced by low-temperature solution-processed used as the electron extraction layer（EEL） in the inverted polymer solar cells（i-PSCs）. Moreover, poly[（9,9-bis（30-（N,N-dimethylamino）propyl）-2,7-fluorene）-alt-2,7-（9,9-dioctylfluorene）]（PFN） is used to modify the surface properties of ZSO thin film. By using the ZSO NPs/PFN as the EEL, the i-PSCs fabricated by poly[4,8-bis（2-ethylhexyloxyl）benzo[1,2-b：4,5-b0] dithio-phene-2,6-diyl-altethylhexyl-3-fluorothithieno [3,4-b]thiophene-2-carboxylate-4,6-diyl]（PTB7） blended with（6,6）-phenyl-C_（71）-butyric acid methylester（PC_（71）BM） bulk heterojunction（BHJ） composite, exhibits a power conversion efficiency（PCE） of 8.44%, which is nearly 10% enhancement as compared with that of7.75% observed from the i-PSCs by PTB7：PC_（71）BM BHJ composite using the ZnO/PFN EEL. The enhanced PCE is originated from improved interfacial contact between the EEL with BHJ active layer and good energy level alignment between BHJ active layer and the EEL. Our results indicate that we provide a simple way to boost efficiency of i-PSCs.