Synthesis, Characterization, and Gas Permeation Properties

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88 Dendronization of Ethyl Cellulose solid, 1 H NMR (400 MHz, CDCl3, 25 ºC, ppm): 0.845 (brs, 7.44H, CH3CH2), 1.12 (brs, 8.07H, OCH2CH3), 1.43 (brs, 4.96H, CH3CH2), 1.55–1.64 (m, 3.72H, C(=O)NHCH2CH2CH2), 1.86 (brs, 1.24H, (CH3CH2)2CH), 2.15 (brs, 1.24H, C(=O)CH2CH2C(=O)), 2.47–4.59 (m, (12.4H, OCH2CH3, OCH, OCH2) and (9.92H, C(=O)CH2CH2C(=O), C(=O)NHCH2CH2CH2)), 6.55 (brs, 0.62H, C(=O)NH), 6.65 (brs, 1.24H, C(=O)NH); IR (ATR, cm -1 ): 3300 (νNH), 3090, 2960, 2928, 2873, 1744 (νCO), 1638, 1540, 1455, 1378, 1276, 1231, 1091, 1058, 920, 856, 804; anal. calcd for (C28.12H50.8N2.8O8.1)n (557.65)n: C, 60.57; H, 9.19; N, 7.01; O, 23.23, found: C, 60.02; H, 9.28; N, 7.59; O, 23.11. 3b. This derivative was prepared by following the same procedure as for 2a using G2-b-ІІ (7.1 g, 6.10 mmol) instead of G1-a-ІІ. Yield 96%, light peach-colored solid, 1 H NMR (400 MHz, CDCl3, 25 ºC, ppm): 0.85 (brs, 7.44H, CH3CH2), 1.11–1.36 (m, (8.07H, OCH2CH3) and (9.92H, CH3CH2CH2)), 1.51–1.65 (m, 3.72H, C(=O)NHCH2CH2CH2), 1.82 (brs, 1.24H, (CH3CH2CH2)2CH), 2.07 (brs, 1.24H, C(=O)CH2CH2C(=O)), 2.47–4.59 (m, (12.4H, OCH2CH3, OCH, OCH2) and (9.92H, C(=O)CH2CH2C(=Om), C(=O)NHCH2CH2CH2)), 6.73 (brs, 0.62H, C(=O)NH), 6.99 (brs, 1.24H, C(=O)NH); IR (ATR, cm -1 ): 3292 (νNH), 3075, 2972, 2929, 2871, 1739 (νCO), 1635, 1542, 1441, 1378, 1257, 1221, 1091, 1053, 879, 802, 710; anal. calcd for (C30.6H55.8N2.8O8.1)n (592.43)n: C, 62.04; H, 9.49; N, 6.60; O, 21.87, found: C, 62.58; H, 9.11; N, 7.09; O, 21.22. 3c. This derivative was prepared by following the same procedure as for 2a using G2-c-ІІ (7.1 g, 6.10 mmol) instead of G1-a-ІІ. Yield 90%, light yellow solid, 1 H NMR (400 MHz, CDCl3, 25 ºC, ppm): 0.83 (brs, 7.44H, CH3CH2), 1.12 (brs, 8.07H, OCH2CH3), 1.22 (brs, 4.96H, CH3CH2CH2CH2), 1.38 (brs, 2.48H, CH3CH2CH2CH2), 1.55 (brs, 2.48H, CH3CH2), 1.63 (brs, 3.72H, C(=O)NHCH2CH2CH2), 1.83 (brs, 1.24H, (CH3CH2CH2CH2)(CH3CH2)CH), 1.95 (brs, 1.24H, C(=O)CH2CH2C(=O)), 2.44–4.61 (m, (12.4H, OCH2CH3, OCH, OCH2) and (9.92H, C(=O)NHCH2CH2CH2)), 6.60 (brs, 0.62H, C(=O)NH), 6.95 (brs, 1.24H, C(=O)NH); IR (ATR, cm -1 ): 3294 (νNH), 3080, 2958, 2929, 2872, 1732 (νCO), 1636, 1545, 1456, 1379, 1232, 1123,
89 Chapter 3 1091, 1053, 853, 806, 707; anal. calcd for (C30.6H55.8N2.8O8.1)n (592.43)n: C, 62.04; H, 9.49; N, 6.60; O, 21.87, found: C, 61.45; H, 9.16; N, 7.13; O, 22.26. Determination of the Degree of Substitution. The degree of substitution with ethyl group (DSEt) of the starting material, 1, was determined by 1 H NMR measurement, which also provided a clear indication of the incorporation of the dendritic moieties into ethyl cellulose. However, the overlapping of the peaks arising due to the methyl protons of the dendritic moiety and those of ethyl cellulose did not allow the exact estimation of the degree of esterification (DSEst) which was determined by the elemental analysis (%N content) of the polymers (2a–c, 3a–c). The total degree of substitution (DStotal) of 2a–c and 3a–c was calculated by the following equation: DStotal = DSEt + DSEst Membrane Fabrication. Membranes (thickness ca. 40–80 μm) of polymers 1 and 2a–c were fabricated by casting their chloroform solution (concentration ca. 0.50–1.0 wt%) onto a Petri dish. The dish was covered with a glass vessel to retard the rate of solvent evaporation (3–5 days). Membrane Density. Membrane densities (ρ) were determined by hydrostatic weighing using a Mettler Toledo balance (model AG204, Switzerland) and a density determination kit. 15 This method makes use of a liquid with known density (ρ0), and membrane density (ρ) is calculated by the following equation: ρ = ρ0 MA/(MA– ML) where MA is the weight of membrane in air and ML is that in the auxiliary liquid. Aqueous NaNO3 solution was used as an auxiliary liquid to measure the density of the polymer membranes. Fractional Free Volume (FFV) of Polymer Membranes. FFV (cm 3 of free
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Synthesis, Characterization, and Ga
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Table of Contents General Introduct
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General Introduction cellulose deri
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General Introduction biogenetically
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General Introduction chemistry offe
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General Introduction solution-diffu
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General Introduction A simplified t
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General Introduction been observed
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polymers. 41,46 General Introductio
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General Introduction Keeping in vie
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General Introduction the derivatize
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General Introduction strategy (G1-a
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General Introduction In conclusion,
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General Introduction 5. (a) Kobayas
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General Introduction 15. (a) Goetma
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General Introduction American Chemi
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General Introduction Macromolecules
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Silylation of Ethyl Cellulose Intro
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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 and 50: Silylation of Ethyl Cellulose the r
Page 51 and 52: Silylation of Ethyl Cellulose D.; Y
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: 87 Chapter 3 CH2CH2C(=O)O), 2.50-4.
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
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139 Chapter5 Specific rotations ([
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141 Chapter5 1.66 (brs, 1.1H, NHCH(
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143 Chapter5 as shown in Scheme 1,
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145 Chapter5 in Table 1. The molecu
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147 Chapter5 almost same pattern of
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Conclusions Table 3. Thermal Proper
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151 Chapter5 W.; Jing, X. J. Polym.
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Chapter 5 Synthesis and Properties
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Acknowledgments While submitting th
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Synthesis, Characterization, and Ga
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