Highly efficient and highly stable terpolymer-based all-polymer solar cells with broad complementary absorption and robust morphology
Aesun KimChang Geun ParkSu Hong ParkHyung Jong KimSuna ChoiYoung Un KimChoel Hun JeongWeon‐Sik ChaeMin Ju ChoDong Hoon Choi
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All-PSC based on Ter-3MTTPD:NDI-Se blend exhibited a high power conversion efficiency of 7.66% due to relatively smooth surface and fine internal morphology.Keywords:
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The radical homopolymerization of styrene or copolymerization of styrene (S) with N-butyl maleimide (I) initiated by tetraethylthiuram disulfide was used to prepare macroinitiators having thiyl end groups. The S–I copolymers from the feeds containing 30–70 mol % I showed approximately alternating composition. The rate of copolymerization and molecular weights decreased with increasing maleimide derivative concentration in the feed; homopolymerization of I alone did not proceed. The macroinitiators served for synthesis of further S–I copolymers. Using polystyrene macroinitiator and the S–I copolymer with thiyl end groups in the polymerization of S–I mixture and styrene, respectively, the copolymers containing blocks of both polystyrene and alternating S–I copolymer were obtained. The copolymerization of S–I mixture initiated with the S–I copolymer bearing thiyl end groups led to the extension of macroinitiator chains by the blocks of alternating copolymer. The presence of the blocks in the polymer products was corroborated using elemental analysis, size exclusion chromatography, and differential scanning calorimetry. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 755–762, 1998
Maleimide
Polystyrene
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Abstract Copolymerizations of combinations of 1.3‐dioxolane (DOL), styrene (St) and 3.3‐bis(chloromethyl) oxacyclobutane (BCMO), and terpolymerization of these monomers were investigated with the use of Et 3 OBF 4 as an initiator. A random copolymer of DOL and St with molecular weight as high as 3 × 10 5 was prepared. By utilizing a “living” nature of the polymerization of DOL by this initiator, a block copolymer (I) consisting of a DOL homopolymer block and a DOL‐St copolymer block was synthesized by two step copolymerization in which St monomer was added to a solution of “living” DOL polymer In a similar way, a block copolymer (II) was also prepared from DOL and BCMO: Terpolymerization of DOL, St and BCMO gave a resinous material, partly insoluble in hot benzene. At least the insoluble part was confirmed to be a terpolymer by elemental analysis and solubility tests. Two step terpolymerization by adding BCMO monomer into a solution of “living” DOL‐St copolymer yielded a benzene soluble product which was supposed to be a block copolymer (III) composed of a DOL‐St copolymer block and a DOL‐St‐BCMO terpolymer block: It is concluded by the successful preparation of terpolymers of DOL, St and BCMO that the latter two monomers which do not copolymerize with each other can be incorporated into a copolymer chain through the intermediary of DOL monomer.
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Abstract A series of polycarbonate copolymers were synthesized by the ring‐opening bulk polymerization of 2‐phenyl‐5,5‐bis(hydroxymethyl) trimethylene carbonate (PTC) and 5,5‐dimethyl trimethylene carbonate (DTC) with tin(II) 2‐ethylhexanoate and aluminum isopropoxide as initiators. The copolymers obtained were characterized by 1 H‐NMR, Fourier transform infrared, and ultraviolet. The influence of the molar ratio of the monomers, the initiators, and their concentrations, the reaction time, and the reaction temperature on the copolymerization was also studied. The copolymerization of monomers DTC and PTC was a nonideal copolymerization, and the copolymerization reactivity ratio of the monomer DTC was higher than that of PTC in the copolymerization process. In vitro release profiles of fluorouracil from the copolymers showed that the copolymer had a steady drug‐release rate and good controlled‐release property. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008
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Polycarbonate
Trimethylene carbonate
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Abstract Diblock copolymers of α‐methylstyrene and isoprene were synthesized anionically. The morphology of the copolymers and of their blends with the homopolymers was studied by transmission electron microscopy. Based on this, a scheme is proposed to predict the morphological behavior associated with the blending of block copolymers with homopolymers. Two blending systems are discussed. They are (i) copolymer AB with homopolymers A and B and (ii) copolymers AB of two different molecular weights with homopolymer A. Two factors are considered to be the most crucial. One is the morphology of the predominant polymer (50 wt %), and the other is the weight ratio of the blends. The solubilizing effect of the block copolymer AB in the blend must also be taken into account. When the two copolymers are blended, the one with lower molecular weight was emulsified by higher one and restricted around the longer chain. It is shown that the present scheme is successful in predicting the morphology of diblock copolymers and their blends.
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Isoprene
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In this paper the copolymerization of styrene and 4-vinylpyridine at 125°C in the presence of benzoyl peroxide (BPO) and 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) on the one hand and in the presence of a TEMPO-terminated polystyrene on the other is described. The molecular weights of the synthesized copolymers and block copolymers were found to increase with increasing conversion. Various nitroxides were used to prepare poly-[styrene-co-(4-vinylpyridine)] copolymers with BPO as the initiator. We found the use of 4-Oxo-TEMPO yielded high polymerization rates and high molecular weights. However, the polymerization in the presence of 4-NH2-TEMPO exhibits a slow rate and leads to copolymers with broad polydispersities. The influence of the other investigated nitroxides (4-OH- and 4-ACETAMIDO-TEMPO) on the copolymerization range between these both limits. The TEMPO-mediated copolymerizations of styrene and 4-vinylpyridine are slower than the comparable autopolymerization. However, the addition of an initiator which decomposes at the reaction temperature, such as dicumyl peroxide, leads to a considerable acceleration. By means of the Kelen-Tüdös method, the monomer reactivity ratios rS (styrene) and r4-VPy (4-vinylpyridine) were determined. The calculation for the TEMPO-mediated copolymerization at 125°C results in rS = 0.73 ± 0.09 and r4-VPy = 0.96 ± 0.15. The values for the spontaneous copolymerization at this temperatures are rS = 0.58 ± 0.04 and r4-VPy = 0.91 ± 0.05.
Polystyrene
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Peroxide
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Abstract Kinetics of the anionic ring opening copolymerization of 2,4,6‐tris(3,3,3‐trifluoropropyl)‐2,4,6‐trimethylcyclotrisiloxane (F 3 ) with hexamethylcyclotrisiloxane (D 3 ) was studied in THF using BuLi as the initiator. The apparent reactivity ratios were estimated by computer simulation to r = 0.10 ± 0.02, r = 51.8 ± 5.5, which were used to predict the copolymer composition. As a result of so much different reactivities, simultaneous copolymerization leads to copolymers of blocky structure containing a narrow intermediate fragment with gradient distribution of siloxane units. Polymers having more uniform distribution of the trifluoropropyl groups along the chain were obtained by the semibatch process, adding F 3 to the polymerization of less reactive D 3 . The resulted copolymers were characterized by SEC chromatography, 29 Si NMR, DSC, DMA, and SAXS. Thermal and mechanical properties of the copolymers obtained by simultaneous copolymerization were similar to those of block copolymers. Only the copolymers obtained by semibatch method showed properties typical for gradient copolymers. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1204–1216, 2009
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Reactivity
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Abstract 1H,1H,2H,2H ‐Perfluorooctyloxymethylstyrene (FS) was prepared and copolymerized with chloromethylstyrene (CMS). Conventional radical copolymerization of both these aromatic monomers led to poly(CMS‐ co ‐FS) random copolymers for which CMS was shown to be more reactive than the fluorinated comonomer. Their controlled radical copolymerization based on degenerative transfer, namely iodine transfer polymerization (ITP), led to various poly(CMS)‐ b ‐poly(FS) block copolymers. Molecular weights of poly(CMS‐ co ‐FS) copolymers reached 33,000 g mol −1 while those of poly(CMS)‐ b ‐ poly(FS) block copolymers were 22,000 g mol −1 . Their composition ranged from 18 to 61 mol.% in FS. These copolymers were modified via a cationization step, aiming at replacing the chlorine atom in CMS unit by a trimethylammonium group, leading to the formation of cationic sites. The resulting functionalized copolymers exhibited different solubilities. If both copolymerization techniques led to water‐insoluble copolymers, the block architecture enabled incorporating lower FS proportion, resulting in more cationic sites. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011
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Cationic polymerization
Atom-transfer radical-polymerization
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Abstract Polysiloxane diblock copolymers containing a pure polysiloxane backbone were prepared by the functionalization of poly(dimethylsiloxane)‐ b ‐poly(methylvinylsiloxane) copolymers. The copolymers were obtained by the sequential anionic copolymerization of either 1,3,5,7‐tetramethyl‐1,3,5,7‐tetravinylcyclotetrasiloxane or 1,3,5‐trimethyl‐1,3,5‐trivinylcyclotrisiloxane with hexamethylcyclotrisiloxane. The two vinyl monomers showed large differences in the propagation rates, but both could be used for the formation of polysiloxane block copolymers. Differences in the polymerization sequences were investigated and revealed that better control was obtained if the slower propagating monomer was polymerized first. The method permitted the synthesis of block copolymers with molecular weight distributions around 1.4 and lower and high block purities. The vinyl groups of the block copolymers were quantitatively and selectively functionalized by hydrosilation or epoxidation reactions. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1539–1551, 2002
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Tetrahydrofuran
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Abstract ABC triblock copolymers are known to exhibit a wide variety of unique types of morphologies compared to AB diblock copolymers. In the present study, poly(styrene‐block‐(ethylene‐alt‐propylene)‐block‐(methyl methacrylate)) (SEPM) triblock copolymers were synthesized and their morphologies were extensively studied by transmission electron microtomography (TEMT). In the SEPM triblock copolymer, two kinds of morphologies coexist: One was the well‐known knitting morphology, and the other was a novel morphology called the “ladder morphology”. The ladder morphology was a major morphology in the SEPM copolymer, the stability of which was discussed in terms of the interfacial area and the solubility parameters between the three components.
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