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, M...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).展开更多
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 a...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].展开更多
The kinetics and mechanism of the radical polymerization of vinyl monomer have been studied by many scientists, and a large quantity of data have been accumulated. But most studies are limited at the early stage of po...The kinetics and mechanism of the radical polymerization of vinyl monomer have been studied by many scientists, and a large quantity of data have been accumulated. But most studies are limited at the early stage of polymerization when monomer conversion is small, and usually only on the measurement of the ratio k_p/展开更多
It has been noticed that the properties of polymer, such as solubility, crystallinity and flexibility, strongly depend on the stereoregularity of polymer chains. For example, some big differences in glass transition t...It has been noticed that the properties of polymer, such as solubility, crystallinity and flexibility, strongly depend on the stereoregularity of polymer chains. For example, some big differences in glass transition temperature, crystallinity and mechanical behaviors could be found in isotactic, syndiotactic and atactic PMMA, isotactic and atactic pp, isotactic,展开更多
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 dop...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.展开更多
'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...'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.展开更多
Serials of polystyrene/SiO<sub>2</sub> Nano composites (PS/SiO<sub>2</sub>) with different content of inorganic fillers were successfully prepared by the in situ bulk radical polymerization of ...Serials of polystyrene/SiO<sub>2</sub> Nano composites (PS/SiO<sub>2</sub>) 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 SiO<sub>2</sub> on the properties of the PS/SiO<sub>2</sub> 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.展开更多
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...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.展开更多
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-cycli...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%.展开更多
基金supported by the National Natural Science Foundation of China (31470597)
文摘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).
基金supported by the Natural Science Foundation of Zhejiang Province,China(Nos.2012C32007,LQ20B020002).
文摘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].
文摘The kinetics and mechanism of the radical polymerization of vinyl monomer have been studied by many scientists, and a large quantity of data have been accumulated. But most studies are limited at the early stage of polymerization when monomer conversion is small, and usually only on the measurement of the ratio k_p/
文摘It has been noticed that the properties of polymer, such as solubility, crystallinity and flexibility, strongly depend on the stereoregularity of polymer chains. For example, some big differences in glass transition temperature, crystallinity and mechanical behaviors could be found in isotactic, syndiotactic and atactic PMMA, isotactic and atactic pp, isotactic,
基金Supported by the National Natural Science Foundation of China under Grant Nos 21174016 and 11474017the Doctoral Program of Higher Education of China under Grant No 20120009110031
文摘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.
文摘'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.
文摘Serials of polystyrene/SiO<sub>2</sub> Nano composites (PS/SiO<sub>2</sub>) 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 SiO<sub>2</sub> on the properties of the PS/SiO<sub>2</sub> 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.
基金Project supported by the National Natural Science Foundation of China (Grant Nos. 60978060,10804006,10974013 and 10774013)the Research Fund for the Doctoral Program of Higher Education,China (Grant Nos. 20090009110027 and 20070004024)+5 种基金the Research Fund for the Youth Scholars of the Doctoral Program of Higher Education,China (Grant No. 20070004031)the Beijing Nova Program (Grant No. 2007A024)the Beijing Municipal Natural Science Foundation (Grant No. 1102028)the National Natural Science Funds for Distinguished Young Scholar (Grant No. 60825407)the Beijing Municipal Science & Technology Commission (Grant No. Z090803044009001)the National Basic Research Program of China (Grant No. 2010CB327705)
文摘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.
基金Funded by the National Natural Science Foundation of China(21673170)
文摘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%.
