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1.
Kikue S. Burnham Robert Roth Faith Zhou Wenya Fan Emma Brouk Mehari Stifanos 《Journal of polymer science. Part A, Polymer chemistry》2006,44(24):6909-6925
In an attempt to develop a low‐k interlayer dielectric, adamantane‐diphenyldiethynyl moiety containing oligomer is prepared. Oligomerization of 1,3,5,7‐tetrakis[3/4‐ethynylphenyl]adamantane ( 4 ) is accomplished by a Glaser–Hay oxidative coupling with 1,3,5‐triethynylbenzene and phenylacetylene end‐capping agent. The CHCl3 soluble oligomer is then thermally treated by step‐curing at 200, 300, 380, and 450 °C for 30 min at each temperature under nitrogen flow to render a shiny void‐free black polymer. TGA analysis indicates that the polymer is stable under nitrogen up to 500 °C with a marginal decomposition up to 800 °C. Solid‐state 13C NMR, Raman scattering, and FTIR are used to characterize the structure of the polymer. The polymer consists of amorphous carbon networks with the adamantane moieties and nanosized graphitic regions (clusters), which are generated from the thermal crosslinking of the diphenyldiethynyl units. It shows a remarkably low linear coefficient of thermal expansion (~25 ppm/°C), presumably due to the presence of the disordered graphitic structure. Its high density (~1.21 g/cm3), refractive index (~1.80 at 632 nm), and Young's modulus (~17.0 GPa) are also consistent with the interpretation. This study reveals important details about the effect of microscopic structure on the macroscopic properties of the highly crosslinked polymer. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6909–6925, 2006 相似文献
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Takakazu Yamamoto Abla Mahmut Masahiro Abe Shin‐Ichi Kuroda Tatsuya Imase Shintaro Sasaki 《Journal of Polymer Science.Polymer Physics》2005,43(16):2219-2224
An alternating copolymer, Copoly‐1 , of thiophene and N‐(phenylethynyl)pyrrole was prepared by palladium‐catalyzed polycondensation. Powder X‐ray diffraction (XRD) analysis indicated that Copoly‐1 formed a stacked packing structure with doubly‐running polymer main chains. Optical data support the molecular and packing structures of Copoly‐1 . © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2219–2224, 2005 相似文献
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Multiaxial mechanical behavior of aramid fibers and identification of skin/core structure from single fiber transverse compression testing
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Judith Wollbrett‐Blitz Sébastien Joannès Rémi Bruant Christophe Le Clerc Marc Romero De La Osa Anthony Bunsell Alba Marcellan 《Journal of Polymer Science.Polymer Physics》2016,54(3):374-384
The transverse and longitudinal mechanical properties of aramid fibers like Kevlar? 29 (K29) fibers are strongly linked to their highly oriented structure. Mechanical characterization at the single fiber scale is challenging especially when the diameter is as small as 15 µm. Longitudinal tensile tests on single K29 fibers and single fiber transverse compression test (SFTCT) have been developed. Our approach consists of coupling morphological observations and mechanical experiments with SFTCT analysis by comparing analytical solutions and finite element modeling. New insights on the analysis of the transverse direction response are highlighted. Systematic loading/unloading compression tests enable to experimentally determine a transverse elastic limit. Taking account of the strong anisotropy of the fiber, the transverse mechanical response sheds light on a skin/core architecture. More importantly, results suggest that the skin of the fiber, typically representing a shell of one micrometer in thickness, has a transverse apparent modulus of 0.2 GPa. That is around more than fifteen times lower than the transverse modulus of 3.0 GPa in the core. By comparison, the measured longitudinal modulus is about 84 GPa. The stress distribution in the fiber is explored and the critical areas for damage initiation are discussed. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 374–384 相似文献
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Ji‐Hoon Kim Sunyoung Lee In‐Nam Kang Moo‐Jin Park Do‐Hoon Hwang 《Journal of polymer science. Part A, Polymer chemistry》2012,50(16):3415-3424
An alternating copolymer composed of heal‐to‐tail‐structured 3,4′‐dihexyl‐2,2′‐bithiophene (DHBT) and pyrene units [poly(DHBT‐alt‐PYR)] was synthesized using a Stille coupling reaction for use in photovoltaic devices as a p‐type donor. For the reduction of the bandgap energy of poly(DHBT‐alt‐PYR), 4,7‐bis(3′‐hexyl‐2,2′‐bithiophen‐5‐yl)benzo[c][1,2,5]thiadiazole (BHBTBT) units were introduced into the polymer. Poly(DHBT‐co‐PYR‐co‐BHBTBT)s were synthesized using the same polymerization reaction. The synthesized polymers were soluble in common organic solvents and formed smooth thin films after spin casting. The optical bandgap energies of the polymers were obtained from the onset absorption wavelengths. The measured optical bandgap energy of poly(DHBT‐alt‐PYR) was 2.47 eV. As the BHBTBT content in the ter‐polymers increased, the optical bandgap energies of the resulting polymers decreased. The bandgap energies of poly(50DHBT‐co‐40PYR‐co‐10BHBTBT) and poly(50DHBT‐co‐20PYR‐co‐30BHBTBT) were 1.84 and 1.73 eV, respectively. Photovoltaic devices were fabricated with a typical sandwich structure of ITO/PEDOT:PSS/active layer/LiF/Al using the polymers as electron donors and [6,6]‐phenyl C71‐butyric acid methyl ester as the electron acceptor. The device using poly(50DHBT‐co‐20PYR‐co‐30BHBTBT) showed the best performance among the fabricated devices, with an open‐circuit voltage, short‐circuit current, fill factor, and maximum power conversion efficiency of 0.68 V, 5.54 mA/cm2, 0.35, and 1.31%, respectively. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
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Analysis of diverse direct arylation polymerization (DArP) conditions toward the efficient synthesis of polymers converging with stille polymers in organic solar cells
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Barry C. Thompson Eva Bundgaard 《Journal of polymer science. Part A, Polymer chemistry》2016,54(18):2907-2918
Despite the emergence of direct arylation polymerization (DArP) as an alternative method to traditional cross‐coupling routes like Stille polymerization, the exploration of DArP polymers in practical applications like polymer solar cells (PSCs) is limited. DArP polymers tend to have a reputation for being marginally inferior to Stille counterparts due to the increased presence of defects that result from unwanted side reactions in direct arylation, such as unselective C‐H bond activation and homocoupling. We report ten DArP protocols across the three major classes of DArP to generate poly[(2,5‐bis(2‐hexyldecyloxy)phenylene)‐alt‐(4,7‐di(thiophen‐2‐yl)benzo[c][1,2,5]thiadiazole)] (PPDTBT). Through evaluation of the method and resulting photophysical and electronic properties, we show not all DArP methods are suitable for generating device‐quality alternating copolymers. When DArP PPDTBT was synthesized in superheated THF with Cs2CO3, neodecanoic acid, and P(o‐anisyl)3, it generated polymers of exceptional quality that performed comparably to Stille counterparts in both roll coated ITO‐free and spin‐coated ITO devices. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2907–2918 相似文献
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Chao Wang Felix S. Kim Guoqiang Ren Yongqian Xu Yi Pang Samson A. Jenekhe Li Jia 《Journal of polymer science. Part A, Polymer chemistry》2010,48(21):4681-4690
Head‐to‐tail regioregular poly(3‐heptanoylthiophene) (PHOT) was synthesized by Ni‐catalyzed polycondensation of the 2,2‐dimethyl‐1,3‐propanediol‐protected Grignard monomer followed by deprotection. Cyclic voltammetric (CV) study demonstrates that the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of PHOT are 0.5 eV lower in energy than those of the head‐to‐tail poly(3‐hexylthiophene) (HT‐P3HT). Their optical band gaps are essentially the same. Incomplete photoluminescence (PL) quenching was observed in thin films of the 1:1 blend of PHOT and HT‐P3HT. PHOT displayed a glass transition at ~269 °C and decomposed at ~300 °C according to differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Wide‐angle X‐ray diffraction (WAXD) study showed that PHOT exists in a not highly ordered state in solid films especially in the π‐stacking direction. Only p‐channel activity was observed in field‐effect transistors (FETs) for PHOT. The hole mobility was on the order of 10?4 cm2 V?1 s?1. Photovoltaic devices with an active layer of 1:1 blend of PHOT and PC71BM had a power conversion efficiency (PCE) of ~0.5%. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010 相似文献
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Fabio Fenili Clara Rigamonti Alberto Bossi Paolo Ferruti Amedea Manfredi Stefano Maiorana Clara Baldoli Silvia Cauteruccio Emanuela Licandro Elisabetta Ranucci 《Journal of polymer science. Part A, Polymer chemistry》2010,48(21):4704-4710
A tetrathia‐[7]‐helicene bearing in the 2 and 13 positions cyanovinyl groups was used as comonomer in the Michael‐type polyaddition reaction with N,N′‐bis(β‐mercaptoethyl)piperazine. This led to a new polymer bearing tetrathia‐[7]‐helicene units regularly distributed along the polymer backbone, which may be regarded as the first example of a new family of potentially useful nonlinear optical materials. All products were structurally characterized by 1H and 13C NMR spectroscopy. Differential scanning calorimetry characterizations revealed the presence, in both monomeric and polymeric helicenes, of glass‐transition like temperatures, associated to some conformational variation of the helicene units. The optical properties, the film formation and the morphology of the polymer‐containing tetratia‐[7]‐helicenes were also investigated. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010 相似文献
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Hatsuhiko Harashina Toshio Nakane Takahito Itoh 《Journal of polymer science. Part A, Polymer chemistry》2007,45(11):2184-2193
Semiaromatic poly(ester amide)s (PEAs) were synthesized by the melt polycondensation of ethanolamine (EA) derivatives with dimethyl terephthalate and ethylene glycol in the presence of tetrabutyl titanate as a catalyst, and their crystallization and thermal properties were investigated. The introduction of an amide group into a semiaromatic polyester such as poly(ethylene terephthalate) (PET) produced PEAs (EA-modified PET polymers) with an increase in the melting point. However, these PEAs were found to decompose at a lower temperature than PET on the basis of TGA. Moreover, direct pyrolysis/mass spectrometry measurements suggested that an initial step of the thermal decomposition was a β-CH hydrogen-transfer reaction via asix-member ring transition state at the ester–ethylene–amide unit, at which carbon–oxygen bond scission took place to yield carboxyl and N-vinylamide end groups. Furthermore, molecular orbital calculations using trimer models bis[2-[[4-(methoxycarbonyl)benzoyl]oxy]ethyl]terephthalate, N-[2-[[4-(methoxycarbonyl)benzoyl]oxy]ethyl]-4-[2-[[4-(methoxycarbonyl)benzoyl]oxy]ethyloxycarbonyl]benzamide, and N,N′-bis[2-[[4-(methoxycarbonyl)benzoyl]oxy]ethyl]terephthalamide strongly supported the idea that the β-CH hydrogen-transfer reaction in the thermal decomposition of PEAs might occur more easily at the methylene group next to the amide group in an ester–ethylene–amide unit rather than at the methylene group next to the ester group in an ester–ethylene–ester unit. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2184–2193, 2007 相似文献
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Shigeki Habaue Ryo Muraoka Akiko Aikawa Soichiro Murakami Hideyuki Higashimura 《Journal of polymer science. Part A, Polymer chemistry》2005,43(8):1635-1640
The oxidative coupling polymerization of 2,3‐dihydroxynaphthalene with the novel dinuclear‐type copper(II) catalysts successfully produced poly(2,3‐dihydroxy‐1,4‐naphthylene). For example, the MeOH‐insoluble polymer with a number average molecular weight of 4.4 × 103 from the polymerization using the complex of CuCl2 and N,N′‐bis(2‐morpholinoethyl)‐p‐xylylenediamine ( p ‐ 1 ) at room temperature under an O2 atmosphere followed by acetylation of the hydroxyl groups was obtained in 63% yield. The structures of the tetraamine ligands and the counter anion of the copper(II) salts significantly influenced the catalyst activity. The polymerization of 2,2′‐dimethoxy‐1,1′‐binaphthalene‐3,3′‐diol with the 2CuCl2‐ p ‐ 1 catalyst, however, resulted in a lower yield. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1635–1640, 2005 相似文献