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991.
Three methods to block the methanol transport through proton-conducting polymer membranes while maintaining the proton conductivity unchanged have been conducted; 1) selective layer formation on the surface of the membrane, 2) prearation of nanoclay composite membrane providing tortuous pathway of methanol, 3) control and fixation of the proton transport channels. The methanol permeability through the membranes decreased significantly at the expense of the small decrease in the proton conductivity. It is thus concluded that both the structure and the fixation of the proton transport channels are crucial in optimizinging proton conducting membranes for direct methanol fuel cells. 相似文献
992.
993.
Ansa‐zirconocene diamide complex rac‐(EBI)Zr(NMe2)2 [rac‐1, EBI = ethylene‐1,2‐bis(1‐indenyl)] reacted with AlR3 (R = Me, Et, iBu) or Al(iBu2)H and then with [CPh3][B(C6F5)4] (2) in toluene in order to perform propylene polymerization by cationic alkylzirconium species, which are in situ generated during polymerization. Through the sequential NMR‐scale reactions of rac‐1 with AlR3 or Al(iBu2)H and then with 2, rac‐1 was demonstrated to be transformed to the active alkyzirconium cations via alkylated intermediates of rac‐1. The cationic species generated by using AlMe3, AlEt3, and Al(iBu2)H as alkylating reagents tend to become heterodinuclear complex; however, those by using bulky Al(iBu)3 become base‐free [rac‐(EBI)Zr(iBu)]+ cations. The activity of propylene polymerization by rac‐1/AlR3/2 catalyst was deeply influenced by various parameters such as the amount and the type of AlR3, metallocene concentration, [Al]/[2] ratio, and polymerization temperature. Generally the catalytic systems using bulky alkylaluminum like Al(iBu)3 and Al(iBu)2H show higher activity but lower stereoregularity than those using less bulky AlMe3 and AlEt3. The alkylating reagent Al(iBu)3 is not a transfer agent as good as AlMe3 or AlEt3. The polymerization activities show maximum around [Al]/[2] ratio of 1.0 and increase monotonously with polymerization temperature. The overall activation energy of both rac‐1/Al(iBu)3/2 and rac‐1/Al(iBu)2H catalysts is 6.0 kcal/mol. As the polymerization temperature increases, the stereoregularity of the resulting polymer decreases markedly, which is demonstrated by the decrease of [mmmm] pentad value and by the increase of the amount of polymer soluble in low boiling solvent. The physical properties of polymers produced in this study were investigated by using 13C‐NMR, differential scanning calorimetry (DSC), viscometry, and gel permeation chromatography (GPC). © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1523–1539, 1999 相似文献
994.
Lee Soon Park Tae Hyung Lee Soo Chang Lee 《Journal of polymer science. Part A, Polymer chemistry》1999,37(14):2311-2317
Copolymerizations of p-dichlorobenzene (DCB)/4-bromophenyl ether (BPE), DCB/4,4′-dibromobiphenyl (DBB), and DBB/BPE pairs with sodium sulfide under high temperature (270–290°C) utilizing N-methyl-2-pyrrolidinone (NMP) as solvent were carried out to give C(DCB/BPE), C(DCB/DBB), and C(DBB/BPE) copolymers, respectively. The reactivity of dihaloaromatic monomers toward thiolate anion in the polycondensation reaction followed the order DBB > DCB > BPE. The reactivity gap between DBB and DCB toward thiolate anion seemed to be smaller than that between BPE and DCB, resulting in both high yield and high molecular weight in the C(DCB/DBB) copolymers compared to C(DCB/BPE) copolymers. The copolymerization of DBB/BPE pair with sodium sulfide, which has larger reactivity gap than the DCB/DBB or DCB/BPE pair, gave mixtures of PBS and PPSE homopolymers especially in the range of 50–80 mol % BPE in the feed. The C(DCB/DBB) and C(DCB/BPE) copolymers, however, exhibited random copolymer character in all comonomer ratios in the feed as evidenced by copolymer composition and DSC data. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2311–2317, 1999 相似文献
995.
Seung‐Yeop Kwak Soo Gyung Jung Young Seo Yoon Dae Woo Ihm 《Journal of Polymer Science.Polymer Physics》1999,37(13):1429-1440
In the present article, some new events on the surface morphology of the aromatic polyamide thin‐film‐composite (TFC) membranes were demonstrated in conjunction with their inherent chemical nature. In addition, the detailed, quantitative understanding of the microscopic surface features was shown to be essential in controlling the water permeability and eventually developing the high performance membranes. The surface roughness and the surface area were mainly affected by the existence or nonexistence of the crosslinking and/or the free amide groups not pertinent to the formation of the hydrogen bonding, which in turn contributed to the water permeability. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1429–1440, 1999 相似文献
996.
Soo Young Park Joong Hwan Yang Soon Hong Yuk Mu Shik Jhon 《Journal of Polymer Science.Polymer Physics》1999,37(13):1407-1411
Terpolymers composed of N‐n‐propylacrylamide (NPAAm), butyl methacrylate (BMA), and N,N‐diethylaminoethyl methacrylate (DEAEMA) were prepared in an attempt to investigate the temperature‐induced phase transition and its mechanism. Poly(NPAAm) showed the lower critical solution temperature (LCST) around 24°C in water. With the incorporation of DEAEMA with NPAAm, the LCST change was characterized by an initial increase. However, the LCST was shifted to the lower temperature at the later stage. This might be explained in terms of hydrophilic/hydrophobic contribution of DEAEMA to the LCST. The swelling behavior of copolymer gel in the various solvents and spin‐lattice relaxation time (T1) study by NMR strongly suggested the hydrophilic/hydrophobic contribution of DEAEMA to the LCST depending on the local environment. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1407–1411, 1999 相似文献
997.
Soo‐Gyun Roh Ki‐Min Park Gil‐Jae Park Shigeru Sakamoto Kentaro Yamaguchi Kimoon Kim 《Angewandte Chemie (International ed. in English)》1999,38(5):637-641
Like with a string of pearls , four molecular “beads” are threaded on a molecular rectangle to form a molecular necklace. This rectangular species is synthesized from two L‐shaped, preorganized pseudorotaxanes with two molecular beads each (cucurbituril, schematically symbolized by the barrels), held together by Cu2+ ions [Eq. (1)]. 相似文献
998.
Jungahn Kim Keon Hyeong Kim Jae Cheol Cho Soonjong Kwak Kwang Ung Kim Won Ho Jo Hye Sung Yoon Dong Soo Lim 《Journal of polymer science. Part A, Polymer chemistry》1998,36(11):1733-1741
The catalytic activities in syndiospecific polymerization of styrene in hydrocarbon using homogeneous Ti-based catalysts in the presence of methylaluminoxane (MAO) were investigated through UV/visible spectroscopic analysis. A strong UV absorption band of CpTiCl3, itself, incipiently appeared at λmax = 400 nm in toluene, followed by a bathochromic shift with its remarkable decrease by the addition of MAO. The absorption band intensity at λmax = 400 nm arising from delocalization of π-electrons on the cyclopentadienyl ring decreased by methylation in the presence of MAO with regard to the mechanism for production of an active center (“cation-like”), for example, the change of the ionic nature. The intensity decrease at λmax = 400 nm was suppressed over 2000 of the [Al]/[Ti] ratio. In the case of Ti(OC4H9)4 having a σ-ligand, new and broad UV absorption bands were developed at λmax = 340 nm and 410 nm in the presence of MAO in contrast with the CpTiCl3/MAO system. Comparison between the relative absorption intensities at λmax = 340 nm and 410 nm led to the determination of a maximum catalytic activity of Ti(OC4H9)4 in the presence of MAO related to the polymerization yield. The maximum polymerization yield was observed with regard to the relative maximum value of the absorption intensity at λmax = 410 nm with the [Al]/[Ti] ratio (500). From observation for polymorphism of the final products via differential scanning calorimetric analysis (DSC), the thermally unstable β-form seemed to be produced by the CpTiCl3/MAO system independent of the MAO concentration, the Ti(OC4H9)4/MAO system produced a thermally stable α-form in the low MAO concentration (up to 100 of the [Al]/[Ti] ratio), and a mixture of α- and/or β-forms over 200 of the [Al]/[Ti] ratio under our experimental conditions. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1733–1741, 1998 相似文献
999.
Pseudoelement Compounds. XII. [1] On the Characterization of 1,1,2,3,3-Pentacyanopropenide in Unidentate and Bidentate Function. Syntheses of Complexes of the Type [MX(PPh3)n] (M = CuI, AgI; X = NCC{C(CN)2}2; n = 2, 3) 1,1,2,3,3-Pentacyanopropenide is characterized as unidentate and bidentate ligand. For that reason compounds of the types [MX(PPh3)3] ( 6 ) and [MX(PPh3)2]2 ( 8 ) (M = CuI, AgI) are synthesized. In the complexes 6 the ionic ligand is coordinated unidentately through an end-on nitrile group of a C(CN)2 unit and in the dimeric complexes 8 bidentately bridging through the N atoms of a C(CN)2 moiety too. The compounds are characterized by 13C NMR, 31P NMR and IR spectroscopy. The crystal structure of [AgX(PPh3)3] is presented and the structural parameters of the anion in this complex and in [CuX(PPh3)2]2 [X = NCC{C(CN)2}2] are compared. 相似文献
1000.
Youngsoo Park Jaeyoung Ko Tae-Kwang Ahn Soonja Choe 《Journal of Polymer Science.Polymer Physics》1997,35(5):807-815
The influence of moisture absorption on the primary (glass) transition (Ta or Tg) and the low temperature relaxations of semiaromatic amorphous polyamides synthesized by isomeric aliphatic diamine and metha or para oriented phthalicdiacids has been investigated by means of differential scanning calorimeter (DSC) and dynamic mechanical thermal analyser (DMTA). The glass transition of semiaromatic polyamides was lowered due to the water absorption, and the β and the γ relaxations were as well. From the observed Tg and the difference in the heat capacity, the calculated Tg depression per 1 wt % water content was 12.3 K and the result was in good agreement with the experimental data. The depression of the glass transition may be expressed by the same manner as the plasticization of nylon 6 by water. The depressed β relaxation observed in the specimen containing a few percent of moisture was splitted into two transitions due to the reduction of water content, of which one was the elevation of the Tβ and another was the simultaneous appearance of the Tγ, and then the single Tγ solely was observed for the completely dried specimen. The Tγ seemed to be merged into or not to be observed by the large and broad Tβ transition when the sample was governed by a few percent of water, then it was emerged from the Tβ due to water desorption. Thus, the Tβ is believed to arise from the intermolecular hydrogen bonding between water molecules or between water and amide groups in wet polyamides. In addition, the γ relaxation originated from the peptide groups is attributable to the inter- and intramolecular hydrogen bonding between amide groups. © 1997 John Wiley & Sons, Inc. J Polyn Sci B: Polym Phys 35: 807–815, 1997 相似文献