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10.569

Synthesis of Polymers

3-0-6 units · Graduate

Studies synthesis of polymeric materials, emphasizing interrelationships of chemical pathways, process conditions, and microarchitecture of molecules produced. Chemical pathways include traditional approaches such as anionic, radical condensation, and ring-opening polymerizations. New techniques, including stable free radicals and atom transfer free radicals, new catalytic approaches to well-defined architectures, and polymer functionalization in bulk and at surfaces. Process conditions include bulk, solution, emulsion, suspension, gas phase, and batch vs continuous fluidized bed. Microarchitecture includes tacticity, molecular-weight distribution, sequence distributions in copolymers, errors in chains such as branches, head-to-head addition, and peroxide incorporation.

Fall 2006

Studies synthesis of polymeric materials, emphasizing interrelationships of chemical pathways, process conditions, and microarchitecture of molecules produced. Chemical pathways include traditional approaches such as anionic polymerization, radical condensation, and ring-opening polymerizations. Other techniques are discussed, including stable free radical polymerizations and atom transfer free radical polymerizations (ARTP), catalytic approaches to well-defined architectures, and polymer functionalization in bulk and at surfaces. Process conditions include bulk, solution, emulsion, suspension, gas phase, and batch vs. continuous fluidized bed. Microarchitecture includes tacticity, molecular-weight distribution, sequence distributions in copolymers, errors in chains such as branches, head-to-head addition, and peroxide incorporation. ##### Acknowledgements The instructor would like to thank Karen Shu and Karen Daniel for their work in preparing material for this course site.

Readings

  • Odian, George. Principles of Polymerization. 4th ed. Hoboken, NJ: Wiley-Interscience, 2004. ISBN: 9780471274001.
    Required
  • Edlund, U., and A.-C. Albertsson. “Polyesters Based on Diacid Monomers.” Advanced Drug Delivery Reviews 55 (2003): 585-609.
    Listed reading
  • Ikada, Y., and Hideto Tsuji. “Biodegradable Polyesters for Medical and Ecological Applications.” Macromolecular Rapid Communications 21, no. 3 (2000): 117-132.
    Listed reading
  • Erdmann, L., and K. E. Uhrich. “Synthesis and Degradation Characteristics of Salicylic Acid-Derived Poly(anhydride-esters).” Biomaterials 21 (2000): 1941-1946.
    Listed reading
  • Anderson, Daniel G., David M. Lynn, and Robert Langer. “Semi-Automated Synthesis and Screening of a Large Library of Degradable Cationic Polymers for Gene Delivery.” Angew Chem Int Ed 42 (2003): 3153-3158.
    Listed reading
  • Fréchet, Jean M. “Dendrimers and Other Dendritic Macromolecules: From Building Blocks to Functional Assemblies in Nanoscience and Nanotechnology.” J Polym Sci Part A: Polym Chem 41 (2003): 3713-3725.
    Listed reading
  • Tomalia, Donald A., and Jean M. Fréchet. “Discovery of Dendrimers and Dendritic Polymers: A Brief Historical Perspective.” J Polym Sci Part A: Polym Chem 40 (2002): 2719-2728.
    Listed reading
  • van Hest, Jan C. M., and David A. Tirrell. “Protein-Based Materials, Toward a New Level of Structural Control.” Chem Commun (2001): 1897-1904.
    Listed reading
  • SES #: 14 · TOPICS: Processing Approaches: Emulsion Polymerization Processes · READINGS: Rempp, P., and Edward W. Merrill. “Emulsion and Suspension Polymerization.” Chapter 12 in Polymer Synthesis . 2nd Revised ed. New York, NY: Hüthig and Wepf, 1991. ISBN: 9783857391149.
    Reading assignment
  • Rempp, P., and Edward W. Merrill. “Emulsion and Suspension Polymerization.” Chapter 12 in Polymer Synthesis . 2nd Revised ed. New York, NY: Hüthig and Wepf, 1991. ISBN: 9783857391149.
    Listed reading
  • SES #: 17 · TOPICS: Stereoregular Polymerizations · READINGS: Sections 8-1, 8-4abc, and 8-4fg.
    Reading assignment
  • Hlatky, G. G. Page 246 in “Metallocene Catalysts for Olefin Polymerization: Annual Review for 1996.” Coordination Chemistry Reviews 181, no. 1 (1999): 243-296.
    Listed reading
  • Yanjarappa, M. J., and S. Sivaram. Pages 1350-1353, 1356, and 1364 in “Recent Developments in the Synthesis of Functional Poly(Olefin)s.” Prog Polym Sci 27, no. 7 (2002): 1347-1398.
    Listed reading
  • SES #: 22 · TOPICS: Anionic Block Copolymerization · READINGS: Section 5-4abcd.
    Reading assignment
  • Lazzari, Massimo, and M. Arturo López-Quintela. Pages 1583-1589 in “Block Copolymers as a Tool for Nanomaterial Fabrication.” Adv Mater 15, no. 19 (October 2, 2003): 1583-1594.
    Listed reading
  • Cheng, J. Y., C. A. Ross, E. L. Thomas, H. I. Smith, and G. J. Vancso. “Fabrication of Nanostructures with Long-Range Order Using Block Copolymer Lithography.” Appl Phys Lett 81, no. 19 (November 4, 2002): 3657-3659.
    Listed reading
  • Hamley, I. W. “Nanotechnology with Soft Materials.” Angew Chem Int Ed 42 (2003): 1692-1712.
    Listed reading
  • SES #: 29 · TOPICS: Functionalization Case Studies: Biomaterials Systems, Liquid Crystal (LC) Polymers · READINGS: Sections 9-4, 9-5, and 9-6.
    Reading assignment
  • Coca, Simion, and Krzystof Matyjaszewski. “Block Copolymers by Transformation of ‘Living’ Carbocationic into ‘Living’ Radical Polymerization.” Macromolecules 30 (1997): 2808-2810.
    Listed reading
  • Davis, Kelly A., and Krzystof Matyjaszewski. Pages 1-13 in “Statistical, Gradient, Block, and Graft Copolymers by Controlled/Living Radical Polymerizations.” Advances in Polymer Science 159 (2002): 1-169.
    Listed reading
  • Patten, Timothy E., and Krzystof Matyjaszewski. “Atom Transfer Radical Polymerization and Synthesis of Polymeric Materials.” Advanced Materials 10, no. 12 (1998): 901-915.
    Listed reading
  • Pyun, Jeffrey, Shijun Jia, Tomasz Kowalewski, and Krzystof Matyjaszewski. “Synthesis and Surface Attachment of ABC Triblock Copolymers Containing Glassy and Rubbery Segments.” Macromol Chem Phys 205 (2004): 411-417.
    Listed reading
  • Grubbs, R. H., R. H. Friend, E. W. Meijer, R. W. Richards, and N. R. Cameron. “Jim Feast: A Career in Polymer Science.” Polymer 46, no. 5 (February 14, 2005): 1427-1438.
    Listed reading
  • Saunders, R. S., R. E. Cohen, and R. R. Schrock. “Synthesis and Characterization of Diblock Copolymer Films Containing Self-Assembled Polyacetylene Structures.” Macromolecules 24, no. 20: 5599-5605.
    Listed reading
  • Manners, Ian. “Poly (ferrocenylsilanes): Novel Organometallic Plastics.” Chem Commun (1999): 857-865.
    Listed reading
  • Wang, Xiao-Song, André Arsenault, Geoffrey A. Ozin, Mitchell A. Winnik, and Ian Manners. “Shell Cross-Linked Cylinders of Polyisoprene-b-ferrocenyldimethylsilane: Formation of Magnetic Ceramic Replicas and Microfluidic Channel Alignment and Patterning.” J Am Chem Soc 125 (2003): 12686-12687.
    Listed reading
  • Yu, L. P. “Lessons Learned From Research on Photorefractive Polymers and Molecular Materials.” Journal of Polymer Science Part A-Polymer Chemistry 39, no. 15 (August 1, 2001): 2557-2564.
    Listed reading
  • Bao, Z. N., and L. P. Yu. “Recent Progress in the Synthesis and Applications of Porphyrin-Containing Polymers as Electronic and Photonic Materials.” Trends in Polymer Science 3, no. 5 (May 1995): 159-164.
    Listed reading
  • Gleria, M., and R. De Jaeger. “Polyphosphazenes: A Review.” New Aspects in Phosphorus Chemistry V Topics in Current Chemistry 250 (2005): 165-251.
    Listed reading
  • Fujlki, M., J. R. Koe, K. Terao, T. Sato, A. Teramoto, and J. Watanabe. “Optically Active Polysilanes. Ten Years of Progress and New Polymer Twist for Nanoscience and Nanotechnology.” Polymer Journal 35, no. 4 (2003): 297-344.
    Listed reading
  • Tachibana, H., and Y. Tokura. “Optical-Properties of Polysilanes and Related Materials.” Synthetic Metals 71, nos. 1-3 (April 1, 1995): 2005-2008.
    Listed reading
  • Kato, T., H. Kihara, S. Ujiie, T. Uryu, and J. M. J. Fréchet. “Structures and Properties of Supramolecular Liquid-Crystalline Side-Chain Polymers Built Through Intermolecular Hydrogen Bonds.” Macromolecules 29, no. 27 (December 30, 1996): 8734-8739.
    Listed reading
  • Alexander, C., C. P. Jariwala, C. M. Lee, and A. C. Griffin. “Self-Assembly of Main-Chain Liquid-Crystalline Polymers via Heteromeric Hydrogen Bonding.” Macromolecular Symposia 77 (January 1994): 283-294.
    Listed reading
  • Muller, M., A. Dardin, U. Seidel, V. Balsamo, B. Ivan, H. W. Spiess, and R. Stadler. “Junction Dynamics in Telechelic Hydrogen Bonded Polyisobutylene Networks.” Macromolecules 29, no. 7 (March 25, 1996): 2577-2583.
    Listed reading
  • Stupp, S. I., S. Son, H. C. Lin, and L. S. Li. “Synthesis of 2-Dimensional Polymers.” Science 259, no. 5091 (January 1, 1993): 59-63.
    Listed reading
  • Stupp, S. I., S. Son, L. S. Li, H. C. Lin, and M. Keser. “Bulk Synthesis of 2-Dimensional Polymers - The Molecular Recognition Approach.” Journal of the American Chemical Society 117, no. 19 (May 17, 1995): 5212-5227.
    Listed reading
  • Okahata, Y., and G. Enna. “Permeability-Controllable Membranes. 7. Electrochemical Responsive Gate Membranes of a Multibilayer Film Containing a Viologen Group as Redox Sites.” Journal of Physical Chemistry 92, no. 15 (July 28, 1988): 4546-4551.
    Listed reading
  • Percec, V. “Self-Assembly of Viruses as Models for the Design of New Macromolecular and Supramolecular Architectures.” Journal of Macromolecular Science-Pure and Applied Chemistry A33, no. 10 (1996): 1479-1496.
    Listed reading
  • ———. “Bioinspired Supramolecular Liquid Crystals.” Philosophical Transactions of the Royal Society A-Mathematical Physical and Engineering Sciences 364, no. 1847 (October 15, 2006): 2709-2719.
    Listed reading
  • Hammond, P. T. “Form and Function in Multilayer Assembly: New Applications at the Nanoscale.” Advanced Materials 16, no. 15 (August 3, 2004): 1271-1293.
    Listed reading
  • Odian, George. Principles of Polymerization . 4th ed. Hoboken, NJ: Wiley-Interscience, 2004. ISBN: 9780471274001.
    Listed reading

Prerequisites & course information

Prereq: 5.12 G (Fall) 3-0-6 units

Sources