Abstract
The effect of poly(dimethylsiloxane) (PDMS) or polypropylene glycol (PPG) linear chain and polyoctahedral oligosilsesquioxanes (POSS) cubic nanoparticles on surface and gas transport properties of poly(dimethylsiloxane-urethane) PDMS-PU or poly(propylene glycol-urethane) (PPG-PU) hybrid membranes were studied. PDMS-PU or PPG-PU hybrid membranes were prepared using PDMS-diol or PPG-diol as a chain extender and diisocyanate with POSS-amine macromonomer as a crosslinker. The macromer synthesized was characterized using FT-IR, 1H-, 13C- and 29Si-NMR spectroscopic methods. The hybrid membranes were characterized by CP-MAS 29Si-NMR, DSC, contact angle, WAXD, AFM and density measurements. The glass transition temperature (Tg) of the hybrid membranes were determined by differential scanning calorimetry (DSC) and were found to be in the range of 176–189°C. The surface free energy was reduced by increasing the POSS-amine crosslinker content of the membranes. The AFM measurement showed phase separation of POSS-amine molecule and PDMS with the urethane matrix on the surfaces. The XRD profiles confirm that the membranes were highly amorphous in nature. The decrease in permeability was observed by increasing the concentration of POSS-amine incorporated hybrid membranes. The selectivities of O2/N2 and CO2/N2 gas pairs increased with an increase in the POSS concentration. This suggests that the selectivities were dependent mainly on the presence of urethane and ester functional groups in the crosslinker.
Similar content being viewed by others
Abbreviations
- PA :
-
Permeability coefficient
- NA :
-
Steady state flux
- ΔPA :
-
Pressure difference
- d:
-
Thickness of the membranes
- α A/B :
-
Selectivity of gas A to B
- ρ film :
-
Density of the film
- m air :
-
Weight of polymer in air
- m liquid :
-
Weight of polymer in liquid
- ρ liquid :
-
Density of the liquid
- γ LV :
-
Interfacial tension at liquid/air interface
- γ dL :
-
Dispersion factors of membrane for liquid
- γ dS :
-
Dispersion factors of membrane for solid
- γ pL :
-
Polar factors of liquid
- γ pS :
-
Polar factors of solid
- γ SV :
-
Total surface energy of membrane
- θ:
-
Contact angle between the sample and liquid/air interface.
- Φ f :
-
Volume fraction of nanofiller in the membrane
- DA :
-
Diffusion coefficient
- SA :
-
Sorption coefficient
- Pc :
-
Permeability of composite
- Pm :
-
Permeability of pure polymer matrices
References
Sridhar S, Smitha M, Aminabhavi TM (2007) Separation of carbon dioxide from natural gas mixtures through polymeric membranes—a review. Sep Purif Rev 36:113
Sairam M, Nataraj SK, Aminabhavi TM (2006) Polyaniline membranes for separation and purification of gases, liquids, and electrolyte solutions. Sep Purif Rev 35:249
Robeson LM (1991) Correlation of separation factor versus permeability for polymeric membranes. J Membr Sci 62:165
Robeson LM, Burgoyne WF, Langsam M, Savoca AC, Tien CF (1994) High performance polymers for membrane separation. Polymer 35:4970
Sridhar S, Aminabhavi TM, Mayor SJ, Ramakrishna M (2007) Permeation of carbon dioxide and methane gases through novel silver-incorporated thin film composite pebax membranes. Ind Eng Chem Res 46:8144–8151
Sridhar S, Suryamurali R, Smitha B, Aminabhavi TM (2007) Development of crosslinked poly(ether-block-amide) membrane for CO2/CH4 separation. Colloids Surf A Physicochem Eng Asp 297:267
Yave W, Peinemann K-V, Shishatskiy S, Khotimskiy V, Chirkova M, Matson S, Litvinova E, Lecerf N (2007) Synthesis, characterization, and membrane properties of poly(1-trimethylgermyl-1-propyne) and its nanocomposite with TiO2. Macromolecules 40:8991
Moaddeb M, Koros WJ (1997) Gas transport properties of thin polymer membranes in the presence of silicon dioxide particles. J Membr Sci 125:143
Park HB, Kim JK, Nam SY, Lee YM (2003) Imide-siloxane block copolymer/silica hybrid membranes: preparation, characterization and gas separation properties. J Membr Sci 220:59
Patel NP, Miller AC, Spontak RJ (2003) Highly CO2-permeable and selective polymer nanocomposite membranes. Adv Mater 15:729
Merkel TC, Freeman BD, Spontak RJ, He Z, Pinnau I, Meakin P, Hill AJ (2003) Sorption, transport and structural evidence for enhanced free volume in poly(4-methyl-2-entyne)/fumed silica nanocomposite membranes. Chem Mater 15:109
Qiu J, Zheng JM, Pienemann KV (2006) Gas transport properties in a novel poly(trimethylsilylpropyne) composite membrane with nanosized organic filler Trimethylsilylglucose. Macromolecules 39:4093
Ni Y, Zheng Z (2007) Supramolecular inclusion complexation of polyhedral oligomeric silsesquioxane capped poly(ε-caprolactone) with α -cyclodextrin. J Polym Sci A Polym Chem 45:1247
Markovic E, Markovic MG, Clarke S, Matisons J, Hussain M, Simon GP (2007) Poly(ethylene glycol)-octafunctionalized polyhedral oligomeric silsesquioxane: Synthesis and thermal analysis. Macromolecules 40:2694
Ashworth AJ, Brisdon BJ, England R, Reddy BSR, Zafar I (1991) The permselectivity of polyorganosiloxanes containing ester functionalities. J Membr Sci 56:217
Achalpurkar MP, Kharul UK, Lohokare HR, Karadkar PB (2007) Gas permeation in amine functionalized silicon rubber membranes. Sep Purif Technol 57:304
Raghu AV, Gadaginamath GS, Priya M, Seema P, Jeong HM, Aminabhavi TM (2008) Synthesis and characterization of novel polyurethanes based on N1,N4-Bis[(4-hydroxyphenyl)methylene]succinohydrazide hard segment. J Appl Polym Sci 110:2315
Raghu AV, Anita G, Barigaddi YM, Gadaginamath GS, Aminabhavi TM (2007) Synthesis and characterization of novel polyurethanes based on 2,6-Bis(4-hydroxybenzylidene) cyclohexanone hard segments. J Appl Polym Sci 104:81
Hasegawa I (1993) Co-hydrolysis products of tetraethoxysilane and methyltriethoxysilane in the presence of tetramethylammonium ions. J Sol-Gel Sci Technol 1:57
Madhavan K, Reddy BSR (2006) Poly(dimethylsiloxane-urethane) membranes: effect of hard segment in urethane on gas transport properties. J Membr Sci 283:357
Madhavan K, Reddy BSR (2009) Synthesis and characterization of polyurethane hybrids: influence of Poly(dimethylsiloxane) linear chain and silsesquioxane cubic structure on thermal and mechanical properties of polyurethane hybrids. J Appl Polym Sci 113:4052
Soh MS, Yap AUJ, Sellinger A (2007) Methacrylate and epoxy functionalized nanocomposites based on silsesquioxane cores for use in dental applications. Eur Polym J 43:315
Ríos-Dominguez H, Ruiz-Treviño FA, Contreras-Reyes R, González-Montiel A (2006) Syntheses and evaluation of gas transport properties in polystyrene–POSS membranes. J Membr Sci 271:94
Liang K, Li G, Yoghiani H, Koo JH, Pittman CU Jr (2006) Cyanate ester/polyhedral oligomeric silsesquioxane (POSS) nanocomposites: Synthesis and characterization. Chem Mater 18:301
Adamso AW (1960) Physical chemistry of surfaces. Interscience Pub. Inc., New York
Madhavan K, Reddy BSR (2009) Structure–gas transport property relationships of poly(dimethylsiloxane–urethane) nanocomposite membranes. J Membr Sci 342:291
Chen RS, Chang CJ, Chang YH (2005) Study on siloxane-modified polyurethane dispersions from various polydimethylsiloxane. J Polym Sci A Polym Chem 43:3482
Lee YJ, Kuo SW, Huang WJ, Lee HY, Chang FC (2004) Miscibility, specific interactions, and self-assembly behavior of phenolic/polyhedral oligomeric silsesquioxane hybrids. J Polym Sci A Polym Chem 42:1127
Park HB, Kim CK, Lee YM (2002) Gas separation properties of polysiloxane/polyether mixed soft segment urethane urea membranes. J Membr Sci 204:257
Merkel TC, Bondar VI, Nagai K, Freeman BD, Pinnau I (2000) Gas sorption, diffusion, and permeation in Poly(dimethylsiloxane). J Polym Sci B Polym Phys 38:415
Iyer P, Iyer G, Coleman M (2010) Gas transport properties of polyimide–POSS nanocomposites. J Membr Sci 358:26
Acknowledgements
K. Madhavan thanks CSIR, New Delhi for the Senior Research Fellowship and D. Gnanasekaran thanks the department of Science and Technology, New Delhi for JRF (No. SR/S1/PC-33/2006).
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Madhavan, K., Gnanasekaran, D. & Reddy, B.S.R. Poly(dimethylsiloxane-urethane) membranes: effect of linear siloxane chain and caged silsesquioxane on gas transport properties. J Polym Res 18, 1851–1861 (2011). https://doi.org/10.1007/s10965-011-9592-8
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10965-011-9592-8