• Title/Summary/Keyword: mesophase

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Design of Mesoporous Silica at Low Acid Concentrations in Triblock Copolymer-Butanol-Water Systems

  • Kleitz, Freddy;Kim, Tae-Wan;Ryoo, Ryong
    • Bulletin of the Korean Chemical Society
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    • v.26 no.11
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    • pp.1653-1668
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    • 2005
  • Assembly of hybrid mesophases through the combination of amphiphilic block copolymers, acting as structuredirecting agents, and silicon sources using low acid catalyst concentration regimes is a versatile strategy to produce large quantities of high-quality ordered large-pore mesoporous silicas in a very reproducible manner. Controlling structural and textural properties is proven to be straightforward at low HCl concentrations with the adjustment of synthesis gel composition and the option of adding co-structure-directing molecules. In this account, we illustrate how various types of large-pore mesoporous silica can easily be prepared in high phase purity with tailored pore dimensions and tailored level of framework interconnectivity. Silica mesophases with two-dimensional hexagonal (p6mm) and three-dimensional cubi (Fm$\overline{3}$m, Im$\overline{3}$m and Ia$\overline{3}$d) symmetries are generated in aqueous solution by employing HCl concentrations in the range of 0.1−0.5 M and polyalkylene oxide-based triblock copolymers such as Pluronic P123 $(EO_{20}-PO_{70}-EO_{20})$ and Pluronic F127 $(EO_{106}-PO_{70}-EO_{106})$. Characterizations by powder X-ray diffraction, nitrogen physisorption, and transmission electron microscopy show that the mesoporous materials all possess high specific surface areas, high pore volumes and readily tunable pore diameters in narrow distribution of sizes ranging from 4 to 12 nm. Furthermore, we discuss our recent advances achieved in order to extend widely the phase domains in which single mesostructures are formed. Emphasis is put on the first synthetic product phase diagrams obtained in $SiO_2$-triblock copolymer-BuOH-$H_2O$ systems, with tuning amounts of butanol and silica source correspondingly. It is expected that the extended phase domains will allow designed synthesis of mesoporous silicas with targeted characteristics, offering vast prospects for future applications.

Effect of Linkage Groups on the Properties of Semi-flexible Liquid Crystalline Polymers (연결기가 반 유연성 액정중합체의 물성에 미치는 영향)

  • Park, Jong-Ryul;Yoon, Doo-Soo;Bang, Moon-Soo
    • Applied Chemistry for Engineering
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    • v.26 no.4
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    • pp.445-451
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    • 2015
  • Semi-flexible liquid crystalline polymers containing a mesogenic group and an octamethylene flexible spacer in the main chain were synthesized by solution polycondensation. The mesogenic group in the polymer consists of four aromatic rings connected by ester and ketone, ether, sulfide, methylene, sulfone, or isopropylidene linkage groups. This paper discusses effects of the central linker of the mesogenic group on polymer properties. The structures and properties of synthesized polymers were investigated by $^1H$-NMR, FT-IR, differential scanning calorimeter (DSC), thermogravimetric analyzer (TGA), X-ray diffractometer (XRD), and polarizing optical microscope (POM). Polymers having bent linkage groups exhibited low thermal transition temperatures, narrow mesophase temperature ranges, low liquid crystallinity, and good solubilities in organic solvents, while those having bulky linkage groups were amorphous and exhibited high glass transition temperatures.

Ionic Conductivities of the LiCF$_3$SO$_3$Complexes with Liquid Crystalline Aromatic Polyesters Having Oligo(oxyethylene) Pendants

  • Lee, Jun-Woo;Joo, Sung-Hoon;Jin, Jung-Il
    • Macromolecular Research
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    • v.12 no.2
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    • pp.195-205
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    • 2004
  • We have synthesized new aromatic polyesters (DiPEG-HQ and DiPEG-BP) by condensation polymerization of a terephthalic acid derivative bearing a pendant oligo(oxyethylene) (DP = 7, MW = 350), which has a methoxy terminal group, and two different aromatic diols, hydroquinone and 4,4'-biphenoI. The synthesized polymers were characterized by differential scanning calorimetry (DSC), polarizing microscopy, and X-ray diffractometry for their liquid crystallinity (LC), thermal transitions, and structural morphologies in mesophases. The morphology of the LC phases depends strongly on the length of the rigid backbone repeating unit. The DiPEG-BP polymer having a longer repeating unit exhibits both layered and nematic structures before isotropization, whereas the DiPEG-HQ polymer having a shorter repeating unit shows only the layered structure in the mesophase. We found that the layer spacing for DiPEG-HQ is larger than that for DiPEG-BP. Both polymers easily form complexes with LiCF$_3$SO$_3$; we studied this complex formation by FT-IR spectroscopy. The layer spacing of the polymer-electrolyte composites increases upon increasing the amount of the lithium salt. The polymer/salt electrolyte mixtures we investigated at molar ratios of EO:salt in the range of 5-20 exhibit electrical conductivity values at 40$^{\circ}C$ of 2.4${\times}$10$\^$5/ and 1.1${\times}$10$\^$-5/ S/cm for DiPEG-HQ/LiCF$_3$SO$_3$ and DiPEG-BP/LiCF$_3$SO$_3$, respectively. At 80 $^{\circ}C$, these values are higher: 4.6${\times}$10$\^$-3/ and 1.1${\times}$10$\^$-4/ S/cm, respectively. The activation energy of conductivity depends strongly on the salt concentration.

Synthesis and Thermotropic Liquid Crystalline Behaviors of 6-[4-(4'-(nitrophenylazo) phenoxycarbonyl)] pentanoated Polysaccharides (6-[4-(4'-(니트로페닐아조)펜옥시카보닐)]펜타노화 다당류들의 합성과 열방성 액정 거동)

  • Jeong, Seung-Yong;Ma, Yung-Dae
    • Polymer(Korea)
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    • v.31 no.1
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    • pp.37-46
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    • 2007
  • Fully or nearly fully 6- [4- (4'- (nitrophenylazo)phenoxycarbonyl)]pentanoated polysaccharide derivatives were synthesized by reacting cellulose, amylose, chitosan, chitin, alginic acid, pullulan or amylopectin with 6- [4- (4'- (nitrophenylazo)phenoxy) ] pentanoyl chloride (NA6C) and their thermotropic liquid crystalline behaviors were investigated. Like in the case of NA6C, all the polysaccharide derivatives formed monotropic nematic phases, suggesting that the mesophase structure of the polysaccharide derivatives is dertermined by the mesogenic side groups and not by the polysaccharide backbone. This is the first report of polysaccharide derivatives, except cellulose derivative, that form thermotropic nematic phases. The thermal stability and degree of order of the nematic phases observed for poly saccharide derivatives were significantly different from those reported for the polymers in which the azobenzene groups are attached to flexible or rigid backbones through flexible spacers. The results were discussed in terms of the difference in the arrangement of the main and side chains and the flexibility of the main chain.

Studies on the Preparation and the Properties of Chitosan Oligosaccharide and its Derivatives (키토산 올리고사카라이드 및 그 유도체의 제조와 특성에 관한 연구)

  • Ha, Byeong-Jo;Kim, Jun-O;Lee, Ok-Seop
    • Journal of the Society of Cosmetic Scientists of Korea
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    • v.23 no.2
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    • pp.48-62
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    • 1997
  • Chitosan oligosaccharides having aldehyde group at reducing end were prepared by oxidative-deamination reaction of chitosan by using sodium nitrite, and the resulting aldehyde group was reduced to 2, 5-anhydro-D-mannitol group. The obtained chitosan oligosaccharides showed an average degree of polymerization 2~3 by gel permeation chromatography analysis. It was highly soluble in hydrophilic solvents and thermally stable. N, N-diacyl, O-acyl chitosan oligosaccharides were obtained from the reaction between chitosan oligosaccharides and acyl chloried under dimethylaminopyridine. From differential scanning calorimetric measurement, N, N-dilauroyl, O-lauroyl chitosan oligosaccharides showed mesophase region, which was confirmed by polarized microscope as a thermotropic liquid crystalline state. X-ray diffraction pattern revealed that N, N-dilauroyl, O-lauroyl chitosan oligosaccharedes were highly crystalline, whereas chitosan oligosaccharides were not.

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New Liquid Crystal Mixtures of Fast Response Time and High Temperature for moving picture on LCD-Device Application

  • Ban, Byeong-Seob;Kim, Bong-Hee;Seo, Bong-Sung;Yun, Yong-Kuk;Lee, Kun-Jong;Souk, Jun-Hyung;Kim, Yong-Bae;Young, Jeong-Ji;Lee, Eun-Kuyng;Jang, Jee-Hwan;Pu, Lyong-Sun;Chung, Sun-Whee;Seong, See-Yearl;Joo, Young-Dae;No, Kyoung-Tai
    • 한국정보디스플레이학회:학술대회논문집
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    • 2003.07a
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    • pp.535-538
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    • 2003
  • Liquid crystal molecules with a new fluoro-isothiocyanate moiety were synthesized. They showed remarkably high $T_{NI}$ (>190 $^{\circ}C$), wide mesophase range of 170 $^{\circ}C$, high dielectric anisotropy (>14) and high optical anisotropy (>0.28). New LC Mixtures of the high $T_{NI}$ (>$85^{\circ}C$) was blended with the novel fluoro-isothiocyanate containing LC molecules, phenylcyclohexanes, bicyclohexanes and ester compounds. The LC mixtures show a fast speed (<10ms) of the below one frame rate in 17" WXGA panel.

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Study of Physico-Chemical Properties of N,N-Diacyl, O-Acyl Chitosan Oligomer (N,N-디아실, O-아실 키토산 올리고머의 물리화학적 특성에 관한 연구)

  • Lee, Ok-Sub;Ha, Byung-Jo;Kim, Jun-Oh;Park, Soeng-Kyu;Lee, Yoon-Sik
    • Applied Chemistry for Engineering
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    • v.8 no.3
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    • pp.365-373
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    • 1997
  • Chitosan oligomer having aldehyde group at reducing end was prepared by oxidative-deamination reaction of chitosan by using sodium nitrite, and the resulting aldehyde group was redeced to 2,5-anhydro-D-mannitol group. The obtained chitosan oligomer showed an average degree of polymerization(DP) 2 by GPC analysis. It was highly soluble in lipophilic solvents. N,N-diacyl, O-acyl chitosan oligomer was obtained trom the reaction between chitosan oligomer and acyl chloride under 4-dimethoxyaminopyridine catalyst. From DSC measurement, N,N-dilauroyl, O-lauroyl chitosan oligomer showed mesophase region, which was confirmed by polarizing microscope as thermotropic liquid crystalline state. X-ray diffraction pattern revealed that N,N-dilauroyl, O-lauroyl chitosan oligomer was highly crystalline, whereas chitosan oligomer was not.

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Preparation of Porous Carbon Fiber by Using MgO Powder and Its Characteristics of Catalysts for Fuel Cell (MgO를 이용한 다공성 탄소 섬유 제조 및 이를 이용한 연료전지용 촉매 특성)

  • Nam, Kidon;Kim, Sang-Kyung;Lim, Seongyop;Peck, Donghyun;Lee, Byoungrok;Jung, Doohwan
    • Korean Chemical Engineering Research
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    • v.46 no.6
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    • pp.1142-1147
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    • 2008
  • Nano-structured porous carbon fiber(PCF) for the catalyst supports of the direct methanol fuel cell (DMFC) were prepared from the mesophase pitch by using the nano-MgO powders. Specific surface area of the PCFs was $8{\sim}58m^2/g$ and surface pore structures had almost meso pore diameter of 10~20 nm which were depending on the amount of MgO spheres. Aqueous reduction method was used to load 60 wt% PtRu on the prepared PCF supports. The electro-oxidation activity and single cell performance of the 60 wt% Pt-Ru catalysts were measured by cyclic voltammetry and unit cell test. The performances of these catalysts increased by 5~10% compared with one of commercial catalyst.

Preparation and Properties of Self-Assembled Discotic Liquid Crystals Formed by Hydrogen Bonding (수소결합에 의한 자기조립된 원반형 액정의 제조와 특성)

  • Lee, Jun Hyup
    • Journal of Adhesion and Interface
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    • v.15 no.4
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    • pp.161-168
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    • 2014
  • New self-assembled discotic liquid crystals have been prepared through single hydrogen bonding between phenol and pyridine moieties, and their liquid crystalline properties were investigated. For the construction of discotic structure, we used phloroglucinol as a core molecule and trans-4-alkoxy-4'-stilbazoles with systematically varied alkyl chain lengths as peripheral units. FTIR results showed that the intermolecular hydrogen bonds between core and peripheral molecules are successfully formed, and the stability of the hydrogen bond is strongly influenced by molecular ordering. Discotic complexes exhibited different liquid crystalline phases depending on the length of alkyl chains around the discotic mesogen. The discotic complexes with longer alkyl chains showed hexagonal columnar mesophases, while the other complexes formed nematic columnar mesophases. These results indicated that the type of mesophase structure was strongly dependent on the alkyl chain length around the aromatic core.

Preparation of Smectic Layered Polymer Networks Using Side Chain Liquid Crystalline Polymers Having Latent Reactive Monomeric Units

  • Oh, Young-Taek;Kim, Woo-Jin;Seo, Sang-Hyuk;Chang, Ji-Young
    • Macromolecular Research
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    • v.17 no.2
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    • pp.84-90
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    • 2009
  • We prepared side-chain liquid crystalline polymers comprising two monomeric units, one having a mesogenic side group that could form a smectic mesophase and the other having a phenolic group attached to the polymer backbone via a thermally reversible urethane bond. The urethane linkage between the isocyanate and phenol groups was stable at room temperature, but it cleaved to generate an isocyanate group when the temperature was increased. When annealed, the copolymers in their smectic mesophases became insoluble in common organic solvents, suggesting the formation of network structures. XRD analysis showed that the annealed polymers maintained their smectic LC structures. The crosslinking process probably proceeded via the reaction of the dissociated isocyanate groups. Some of the isocyanate groups would have first reacted with moisture in the atmosphere to yield amino groups, which underwent further reaction with other isocyanate groups, resulting in the formation of urea bonds. We presume that only polymer chains in the same layer were crosslinked by the reaction of the isocyanate groups, resulting in the formation of a layered polymer network structure. Reactions between the layers did not occur because of the wide layer spacing.