Synthesis, Characterization, and Gas Permeation Properties

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47 Chapter 1 diffusion coefficient. These findings are consistent with those observed in various substituted polyacetylenes. 12 It is noteworthy that the increase in the diffusion coefficients upon silylation was more pronounced than the decrease in the solubility coefficients, thus leading to the net effect of enhanced permeability. Furthermore, these results indicate the significance of silyl groups to enhance the gas permeability by increasing the gas diffusion coefficients of the polymer membranes. Conclusions The present study is concerned with the synthesis of novel silyl ethers of ethyl cellulose (2a–f). It was demonstrated that halosilanes served as excellent silylating agents, in the presence of imidazole, accomplishing the complete silylation of ethyl cellulose even at room temperature without any chain degradation of the starting material. All of the silylated polymers (2a–f) displayed good solubility in common organic solvents, fair thermal stability, and adequate membrane-forming ability. Membranes of 2a–f exhibited higher gas permeability than that of 1 due to the increased diffusion coefficients resulting from the introduction of silyl moieties in ethyl cellulose. Although silylation could not affect a very large increase in gas flux, probably due to the very small extent of hydroxy groups (0.31 per anhydroglucose unit) available for derivatization yet good separation performance for CO2/N2 and CO2/CH4 was discerned. References and Notes 1. (a) Pinnau, I.; Freeman, B. D. Advanced Materials for Membrane Separations; ACS Symposium Series 876; American Chemical Society: Washington, DC, 2004. (b) Nagai, K.; Masuda, T.; Nakagawa, T.; Freeman, B. D.; Pinnau, I. Prog. Polym. Sci. 2001, 26, 721–798. (c) Nunes, S. P.; Peinemann, K.-V. Membrane Technology in the Chemical Industry; Wiley: New York, 2001. (d) Koros, W. J.; Mahajan, R. J. Membr. Sci. 2000, 175, 181–196. (e) Aoki, T. Prog. Polym. Sci. 1999, 24, 951–993. (f) Maier, G. Angew. Chem. Int. Ed. 1998, 37, 2961–2974. 2. (a) Alentiev, A. Y.; Shantarovich, V. P.; Merkel, T. C.; Bondar, V. I.; Freeman, B.
Silylation of Ethyl Cellulose D.; Yampolskii, Yu. P. Macromolecules 2002, 35, 9513–9522. (b) Freeman, B. D.; Pinnau, I. Trends Polym. Sci. 1997, 5, 167–173. (c) Langsam, M. Plastics Engineering 1996, 36, 697–741. (d) Chung, I. J.; Lee, K. R.; Hwang, S. T. J. Membr. Sci. 1995, 105, 177–185. (e) Henis, J. M. S. Commercial and Practical Aspects of Gas Separation Membranes; CRC Press: Boca Raton, FL, 1994. (f) Koros, W. J. In Membrane Separation Systems: Recent Developments and Future Directions, Baker, R. W., Cuasler, E. L., Eykamp, W., Koros, W. J., Riley, R. L., Strathmann, H., Eds.; Noyes Data Corporation: Park Ridge, NJ, 1991; pp 189–241. (g) Spillman, R. W. Chem. Eng. Prog. 1989, 85, 41–62. 3. (a) Sakaguchi, T.; Shiotsuki, M.; Masuda, T. Macromolecules 2004, 37, 4104–4108. (b) Sakaguchi, T.; Kwak, G.; Masuda, T. Polymer 2002, 43, 3937–3942. (c) Morisato, A.; Pinnau, I. J. Membr. Sci. 1996, 121, 243–250. (d) Tsuchihara, K.; Masuda, T.; Higashimura, T. Macromolecules 1992, 25, 5816–5820. (e) Hayakawa, Y.; Nishida, M.; Aoki, T.; Muramatsu, H. J. Polym. Sci., Part A: Polym. Chem. 1992, 30, 873–877. 4. (a) Nagai, K.; Kanehashi, S.; Tabei, S.; Nakagawa, T. J. Membr. Sci. 2005, 251, 101–110. (b) Starannikova, L.; Khodzhaeva, V.; Yampoľskii, Y. J. Membr. Sci. 2004, 244, 183–191. (c) Hill, A. J.; Pas, S. J.; Bastow, T. J.; Burgar, M. I.; Nagai, K.; Toy, L. G.; Freeman, B. D. J. Membr. Sci. 2004, 243, 37–44. (d) Bi, J. J.; Wang, C. L.; Kobayashi, Y.; Ogasawara, K.; Yamasaki, A. J. Appl. Polym. Sci. 2003, 87, 497–501. (e) Madkour, T. M. Polymer 2000, 41, 7489–7497. 5. (a) Sakaguchi, T.; Yumoto, K.; Shiotsuki, M.; Sanda, F.; Yoshikawa, M.; Masuda, T. Macromolecules 2005, 38, 2704–2709. (b) Raharjo, R. D.; Lee, H. J.; Freeman, B. D.; Sakaguchi, T.; Masuda, T. Polymer 2005, 46, 6316–6324. (c) Kouzai, H.; Masuda, T.; Higashimura, T. J. Polym. Sci., Part A: Polym. Chem. 1994, 32, 2523–2530. (d) Tsuchihara, K.; Masuda, T.; Higashimura, T. J. Polym. Sci., Part A: Polym. Chem. 1993, 31, 547–552. 6. (a) Crowley, M. M.; Schroeder, B.; Fredersdorf, A.; Obara, S.; Talarico, M.; Kucera, S.; McGinity, J. W. Int. J. Pharm. 2004, 269, 509–522. (b) Li, X.-G.; Kresse, I.; Xu, Z.-K.; Springer, J. Polymer 2001, 42, 6801–6810. (c) Klemm, D.; Philipp, B.; Heinze, T.; Heinze, U.; Wagenknecht, W. Comprehensive Cellulose Chemistry; Wiley-VCH: Weinheim, 1998; Vol. 2. 7. (a) Li, X.-G.; Huang, M.-R.; Hu, L.; Lin, G.; Yang, P.-C. Eur. Polym. J. 1999, 35, 157–166. (b) He, Y.; Yang, J.; Li, H.; Huang, P. Polymer 1998, 39, 3393–3397. (c) Li, X.-G.; Huang, M.-R. J. Appl. Polym. Sci. 1997, 66, 2139–2147. (d) Houde, A. Y.; Stern, S. A. J. Membr. Sci. 1997, 127, 171–183. (e) Suto, S.; Niimi, T.; Sugiura, T. J. Appl. Polym. Sci. 1996, 61, 1621–1630. (f) Houde, A. Y.; Stern, S. A. J. Membr. Sci. 1994, 92, 95–101. 48
Page 1 and 2: Synthesis, Characterization, and Ga
Page 3 and 4: Table of Contents General Introduct
Page 5 and 6: General Introduction cellulose deri
Page 7 and 8: General Introduction biogenetically
Page 9 and 10: General Introduction chemistry offe
Page 11 and 12: General Introduction solution-diffu
Page 13 and 14: General Introduction A simplified t
Page 15 and 16: General Introduction been observed
Page 17 and 18: polymers. 41,46 General Introductio
Page 19 and 20: General Introduction Keeping in vie
Page 21 and 22: General Introduction the derivatize
Page 23 and 24: General Introduction strategy (G1-a
Page 25 and 26: General Introduction In conclusion,
Page 27 and 28: General Introduction 5. (a) Kobayas
Page 29 and 30: General Introduction 15. (a) Goetma
Page 31 and 32: General Introduction American Chemi
Page 33 and 34: General Introduction Macromolecules
Page 35 and 36: Silylation of Ethyl Cellulose Intro
Page 37 and 38: Silylation of Ethyl Cellulose milli
Page 39 and 40: Silylation of Ethyl Cellulose chlor
Page 41 and 42: Silylation of Ethyl Cellulose Resul
Page 43 and 44: Silylation of Ethyl Cellulose Solub
Page 45 and 46: Silylation of Ethyl Cellulose 1.034
Page 47 and 48: Silylation of Ethyl Cellulose poly(
Page 49: Silylation of Ethyl Cellulose the r
Page 53 and 54: Chapter 2 51 Chapter 2 Synthesis, C
Page 55 and 56: 53 Chapter 2 are few and far betwee
Page 57 and 58: 55 Chapter 2 constant volume/variab
Page 59 and 60: 57 Chapter 2 Membrane Density. Memb
Page 61 and 62: 59 Chapter 2 IR spectrum of 1 (Figu
Page 63 and 64: 61 Chapter 2 1,3-bis(trifluoromethy
Page 65 and 66: 63 Chapter 2 The increase in the po
Page 67 and 68: 65 Chapter 2 other fluorinated poly
Page 69 and 70: 67 Chapter 2 of the gas permeabilit
Page 71 and 72: 69 Chapter 2 Gas Diffusivity and So
Page 73 and 74: 71 Chapter 2 mobility of the perflu
Page 75 and 76: 73 Chapter 2 1325-1329. (b) Hamza,
Page 77 and 78: Chapter 3 75 Chapter 3 Synthesis an
Page 79 and 80: 77 Chapter 3 cost, and above all ap
Page 81 and 82: 79 Chapter 3 molecular weights (Mn
Page 83 and 84: 81 Chapter 3 1.99-2.07 (m, 2H, (CH3
Page 85 and 86: 83 Chapter 3 25 °C, ppm): 11.9, 13
Page 87 and 88: 85 Chapter 3 38.1, 44.7, 46.8, 47.9
Page 89 and 90: 87 Chapter 3 CH2CH2C(=O)O), 2.50-4.
Page 91 and 92: 89 Chapter 3 1091, 1053, 853, 806,
Page 93 and 94: 91 Chapter 3 dendrons (G1-a-ІІ-G1
Page 95 and 96: 93 Chapter 3 (DMAP) as a base, as s
Page 97 and 98: Figure 3. FTIR spectra of 1, 2c, an
Page 99 and 100: 97 Chapter 3 (partly soluble) and 3
Page 101 and 102:
99 Chapter 3 increased polarity of
Page 103 and 104:
101 Chapter 3 that of 1, and approx
Page 105 and 106:
103 Chapter 3 derivatization per th
Page 107 and 108:
105 Chapter 3 (2a-c) were in the or
Page 109 and 110:
107 Chapter 3 2709-2719. (b) Schenn
Page 111 and 112:
109 Chapter 3 17. van Krevelen, D.
Page 113 and 114:
Chapter 4 111 Chapter 4 Synthesis,
Page 115 and 116:
113 Chapter 4 Since, no significant
Page 117 and 118:
115 Chapter 4 Materials. Ethyl cell
Page 119 and 120:
DStotal = DSEt + DSCarb (for 1a and
Page 121 and 122:
119 Chapter 4 Figure 2. 1 H NMR spe
Page 123 and 124:
121 Chapter 4 ruling out the possib
Page 125 and 126:
123 Chapter 4 t-butyl moiety. A str
Page 127 and 128:
125 Chapter 4 reported to lead to t
Page 129 and 130:
127 Chapter 4 Table 4. Gas Permeabi
Page 131 and 132:
129 Chapter 4 augmentation in eithe
Page 133 and 134:
131 Chapter 4 indicate the signific
Page 135 and 136:
133 Chapter 4 M.-R. J. Appl. Polym.
Page 137 and 138:
Chapter 5 135 Chapter5 Synthesis an
Page 139 and 140:
137 Chapter5 acid- and peptide-cont
Page 141 and 142:
139 Chapter5 Specific rotations ([
Page 143 and 144:
141 Chapter5 1.66 (brs, 1.1H, NHCH(
Page 145 and 146:
143 Chapter5 as shown in Scheme 1,
Page 147 and 148:
145 Chapter5 in Table 1. The molecu
Page 149 and 150:
147 Chapter5 almost same pattern of
Page 151 and 152:
Conclusions Table 3. Thermal Proper
Page 153 and 154:
151 Chapter5 W.; Jing, X. J. Polym.
Page 155 and 156:
Chapter 5 Synthesis and Properties
Page 157 and 158:
Acknowledgments While submitting th
Page 159:
Synthesis, Characterization, and Ga
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