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Course Overview
Polymer Design and Synthesis
Reaction Types and Processes
Introduction to Step Growth
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Sections 1-1 to 1-4.
"Examples of Common Functional Groups Used in Step Growth Polymerization" Handout.
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Step Growth Polymerization |
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Molecular Weight (MW) Control
Molecular Weight Distribution (MWD) in Equilibrium Step Condensation Polymerizations
Interchange Reactions: Effects on Processing and Product
Application Example: Common Polyesters
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Sections 2-1a, 2-4ab, 2-2abcd, especially 2-2ab. |
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Step Growth Polymerization
Types of Monomers
Kinetics and Equilibrium Considerations
Closed vs. Open Systems
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Sections 2-6ab, 2-7abc, and 2-8defg.
Edlund, U., and A.-C. Albertsson. "Polyesters Based on Diacid Monomers." Advanced Drug Delivery Reviews 55 (2003): 585-609.
Ikada, Y., and Hideto Tsuji. "Biodegradable Polyesters for Medical and Ecological Applications." Macromolecular Rapid Communications 21, no. 3 (2000): 117-132.
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Common Processing Approaches
Near-equilibrium vs. Far from Equilibrium
Homogeneous Solution and Bulk Polymerization
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Section 2-8ab.
Erdmann, L., and K. E. Uhrich. "Synthesis and Degradation Characteristics of Salicylic Acid-Derived Poly(anhydride-esters)." Biomaterials 21 (2000): 1941-1946.
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Interfacial Polymerizations
Application Examples: Polyamides
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Section 2-8c.
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.
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Other Polymers of Interest Obtained by Step-Growth
Polyaramids
Polyimides
Segmented and Block Copolymers from Step Condensation Methods
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Sections 2-8defg and 2-13bc. |
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Crosslinking and Branching
Network Formation and Gelation
Carothers Equation: Pn Approach
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Sections 2-9 and 2-10a. |
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Network Formation
Statistical Approach: Pw Approach
A Word on MWD for Nonlinear Polymerizations
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Sections 2-10b, 2-11, and 2-12. |
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Step-by-Step Approaches I: Polypeptide Synthesis: Examples from Biology
Step-by-Step Approaches II: Dendrimers, Traditional Convergent and Divergent Routes
New "one-pot" Approaches to Hyperbranced Species
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Section 9-13.
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.
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.
van Hest, Jan C. M., and David A. Tirrell. "Protein-Based Materials, Toward a New Level of Structural Control." Chem Commun (2001): 1897-1904.
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Free Radical Chain Polymerization |
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Introduction to Radical Polymerization |
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Radical Polymerization
Homogeneous Reaction Rate Kinetics
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Sections 3-1a and 3-3ab. |
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Free Radical Kinetic Chain Length
MWD
Chain Transfer
Energetics
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Sections 3-5ab, 3-6a, and 3-6c. |
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Thermodynamics of Free Radical Polymerizations
Ceiling T's
Tromsdorff Effect
Instantaneous Pn
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Sections 3-9bc and 3-10. |
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Processing Approaches: Emulsion Polymerization Processes |
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. |
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Processing Approaches: Suspension (Bead) Polymerization Processes
Polyvinyl Chloride Via Precipitation Polymerization
Polyethylene Via Radical Polymerization
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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. |
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Ziegler-Natta Catalysis
Stereochemistry of Polymers
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Sections 6-1, 6-2ad, 6-3ab, especially 6-3b-4. |
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Stereoregular Polymerizations |
Sections 8-1, 8-4abc, and 8-4fg. |
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Radical Copolymerization: Alternating to Block Copolymers |
Hlatky, G. G. Page 246 in "Metallocene Catalysts for Olefin Polymerization: Annual Review for 1996." Coordination Chemistry Reviews 181, no. 1 (1999): 243-296.
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.
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Ionic Polymerization |
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Metallocene Chemistry
Introduction to New Developments from Brookhart, et al.
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Sections 5-1 and 5-3. |
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Introduction to Anionic Polymerization
Monomers Applicable to Anionic Methods
Kinetics of "Nonliving" Anionic Polymerization
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Section 5-3e. |
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Living Anionic Polymerization
Effects of Initiator and Solvent
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Anionic Block Copolymerization |
Section 5-4abcd. |
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Anionic Ring Opening Polymerization
End Group Functionalization
Telechelic Oligomers and Novel Architectures Using Coupling Techniques
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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. |
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Introduction to Cationic Polymerization, Monomers, Kinetics
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Sections 5-2a1, 5-2a2, and 5-2b.
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.
Hamley, I. W. "Nanotechnology with Soft Materials." Angew Chem Int Ed 42 (2003): 1692-1712.
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"Living" Cationic Polymerizations
Examples of Cationic Polymerization, Isobutyl Rubber Synthesis, Polyvinyl Ethers
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Anionic Ring Opening Polymerization
Cationic Ring Opening Polymerization
Other Ring Opening Polymerizations
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Polysiloxanes, Lactams, etc. |
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Polymer Functionalization and Modification |
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Introduction to Polymer Functionalization: Motivations, Yield, Crystallinity, Solubility Issues
Common Functionalization Approaches |
Sections 9-1a to 9-1k. |
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Functionalization Case Studies: Biomaterials Systems, Liquid Crystal (LC) Polymers |
Sections 9-4, 9-5, and 9-6. |
Less Traditional Approaches to Polymer Synthesis |
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Surface Functionalization of Polymers
Graft Copolymerization
Approaches to Making Comb and Graft Architectures
Grafting onto Existing Polymer Surfaces
Surface Engineering Using Graft Copolymers
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Section 9-8. |
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"Living" Free Radical Approaches: Stable Free Radical Polymerization
Atom Transfer Radical Polymerization (ATRP)
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ATRP
RAFT and Other New Methods
Ring Opening Metathesis Polymerization (ROMP)
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Coca, Simion, and Krzystof Matyjaszewski. "Block Copolymers by Transformation of 'Living' Carbocationic into 'Living' Radical Polymerization." Macromolecules 30 (1997): 2808-2810.
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.
Patten, Timothy E., and Krzystof Matyjaszewski. "Atom Transfer Radical Polymerization and Synthesis of Polymeric Materials." Advanced Materials 10, no. 12 (1998): 901-915.
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.
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ROMP
Oxidative Coupling
Electrochemical Polymerizations
Case Study: Electro-active Polymers
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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.
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.
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Inorganic Polymer Synthesis |
Manners, Ian. "Poly (ferrocenylsilanes): Novel Organometallic Plastics." Chem Commun (1999): 857-865.
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.
Additional Reading
Photorefractive Polymers
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.
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.
Polyphosphazenes
Gleria, M., and R. De Jaeger. "Polyphosphazenes: A Review." New Aspects in Phosphorus Chemistry V Topics in Current Chemistry 250 (2005): 165-251.
Polysilanes
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.
Tachibana, H., and Y. Tokura. "Optical-Properties of Polysilanes and Related Materials." Synthetic Metals 71, nos. 1-3 (April 1, 1995): 2005-2008.
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Macromolecular Systems Via Secondary Bonding: Use of H-bonding and Ionic Charge to Build Structures
Concept of Self-Assembly - From Primary Structure to Complex Structure
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Additional Reading
Hydrogen Bonding in Polymeric Structures
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.
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.
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.
2-Dimensional Polymers
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.
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.
Electrochemical Polymerization
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.
Self-Assembly of Viruses and Liquid Crystalline Polymers
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.
———. "Bioinspired Supramolecular Liquid Crystals." Philosophical Transactions of the Royal Society A-Mathematical Physical and Engineering Sciences 364, no. 1847 (October 15, 2006): 2709-2719.
Multilayer Assembly
Hammond, P. T. "Form and Function in Multilayer Assembly: New Applications at the Nanoscale." Advanced Materials 16, no. 15 (August 3, 2004): 1271-1293.
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