Cellulose was reacted with a series of 4-alkoxytrityl chlorides (C(n)TCl, n: number of carbon atoms in a saturated alkyl chain) under homogeneous reaction conditions in LiCl-N,N-dimethyl acetoamide to give a series of 6-O-(4-alkoxytrityl)celluloses (C(n)TC) with a high degree of substitution (DS), from 0.94 to 0.99, and with high regioselectivity at the 6-O position. Solubility of the C(n)TC in nonpolar solvents depended on the alkyl chain length: as the alkyl chain lengthens, cellulose derivatives become more hydrophobic and are readily soluble in nonpolar solvents, but not in polar solvents. Acetates of the C(4)-C(18)TC (C(4)-C(18)TCAc) showed anisotropic structures over melting temperatures (T(m)) examined under a polarized optical microscope (POM). Over isotropization temperatures (T(i)), flow birefringence were detected for C(12)-C(18)TCAc. The T(m) and T(i) decreased linearly with an increasing number of carbon atoms in the alkyl substituent. Wide-angle X-ray scattering (WAXS) studies of C(n)TC indicated that the fully extended side chains were perpendicular to the polymer backbone and interdigitated. These C(n)TC with the improved solubility may be used as starting materials for further derivatization focused on the secondary hydroxyl groups at the C-2 and C-3 positions. 相似文献
We now report the molecular and crystal structure design of muconic ester derivatives on the basis of crystal engineering using halogen-halogen contacts and CH/pi interactions. The solid-state photoreaction pathway of the dibenzyl (Z,Z)-muconates as the 1,3-diene dicarboxylic acid monomers depends on the structure of the ester groups. The substitution of a halogen atom for the aromatic hydrogen of a benzyl group induces topochemical polymerization to produce stereoregular polymers in a crystalline form, whereas the unsubstituted benzyl derivative isomerizes to yield the corresponding E,E isomer under similar conditions. The topochemical polymerization process is directly confirmed by the fact that the single-crystal structures before and after the polymerization are very similar to each other. From the crystal structure analysis for a series of substituted benzyl (Z,Z)- and (E,E)-muconates, it has been revealed that the planar diene moieties are closely packed to form a columnar structure in the crystals. The stacking of the polymerizable monomers is characterized by a stacking distance of 4.9-5.2 A along the columns. This structure is supported by a halogen-halogen interaction between the chlorine or bromine atoms introduced at the p position of the benzyl groups in addition to an aromatic stacking due to the CH/pi interaction between the benzylic methylene hydrogens and aromatic rings. The design of a monomer packing corresponds to the type and position of the introduced halogen atom and also the polymorphs. To make a stacking distance of 5 A using both halogen-halogen and CH/pi interactions as supramolecular synthons is important for the molecular design of muconic ester derivatives appropriate for topochemical polymerization. 相似文献
This paper demonstrates the preparation of chitin nanofibers from crab shells using a simple mechanical treatment. The nanofibers
are small enough to retain the transparency of neat acrylic resin. Possessing hydroxyl and amine/N-acetyl functionalities, water suspension of chitin nanofibers was vacuum-filtered 9 times faster than cellulose nanofibers
to prepare a nanofiber sheet of 90 mm in diameter. This is a prominent advantage of chitin nanofibers over cellulose nanofibers
in terms of commercial application. Interestingly, chitin acrylic resin films exhibited much higher transparency than cellulose
acrylic resin films owing to the close affinity between less hydrophilic chitin and hydrophobic resin. Furthermore, the incorporation
of chitin nanofibers contributes to the significant improvement of the thermal expansion and mechanical properties of the
neat acrylic resin. The properties of high light transmittance and low thermal expansion make chitin nanocomposites promising
candidates for the substrate in a continuous roll-to-roll process in the manufacturing of various optoelectronic devices such
as flat panel displays, bendable displays, and solar cells. 相似文献
We used amorphous silicon oxide (a‐Si1–xOx:H) and microcrystalline silicon oxide (µc‐Si1–xOx:H) as buffer layer and p‐type emitter layer, respectively, in n‐type silicon hetero‐junction (SHJ) solar cells. We proposed to insert a thin (2 nm) intrinsic amorphous silicon (a‐Si:H) thin film between the thin (2.5 nm) a‐Si1–xOx:H buffer layer and the p‐layer to form a stack buffer layer of a‐Si:H/a‐Si1–xOx:H. As a result, a high open‐circuit voltage (VOC) and a high fill factor (FF) were obtained at the same time. Finally, a high efficiency of 19.0% (JSC = 33.46 mA/cm2, VOC = 738 mV, FF = 77.0%) was achieved on a 100 μm thick polished wafer using the stack buffer layer.