Synthesis of Polymers

Readings

The readings consist of sections from the primary text, journal articles, and handouts. The readings should be completed before attending lecture. The sections given below come from the course required text.

Required Text

Odian, George. Principles of Polymerization. 4th ed. Hoboken, NJ: Wiley-Interscience, 2004. ISBN: 9780471274001.

Readings

SES #	TOPICS	READINGS
1	Course Overview Polymer Design and Synthesis Reaction Types and Processes Introduction to Step Growth	Sections 1-1 to 1-4. “Examples of Common Functional Groups Used in Step Growth Polymerization” Handout.
Step Growth Polymerization
2	Molecular Weight (MW) Control Molecular Weight Distribution (MWD) in Equilibrium Step Condensation Polymerizations Interchange Reactions: Effects on Processing and Product Application Example: Common Polyesters	Sections 2-1a, 2-4ab, 2-2abcd, especially 2-2ab.
3	Step Growth Polymerization Types of Monomers Kinetics and Equilibrium Considerations Closed vs. Open Systems	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.
4	Common Processing Approaches Near-equilibrium vs. Far from Equilibrium Homogeneous Solution and Bulk Polymerization	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.
5	Interfacial Polymerizations Application Examples: Polyamides	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.
6	Other Polymers of Interest Obtained by Step-Growth Polyaramids Polyimides Segmented and Block Copolymers from Step Condensation Methods	Sections 2-8defg and 2-13bc.
7	Crosslinking and Branching Network Formation and Gelation Carothers Equation: Pn Approach	Sections 2-9 and 2-10a.
8	Network Formation Statistical Approach: Pw Approach A Word on MWD for Nonlinear Polymerizations	Sections 2-10b, 2-11, and 2-12.
9	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	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.
Free Radical Chain Polymerization
10	Introduction to Radical Polymerization
11	Radical Polymerization Homogeneous Reaction Rate Kinetics	Sections 3-1a and 3-3ab.
12	Free Radical Kinetic Chain Length MWD Chain Transfer Energetics	Sections 3-5ab, 3-6a, and 3-6c.
13	Thermodynamics of Free Radical Polymerizations Ceiling T’s Tromsdorff Effect Instantaneous Pn	Sections 3-9bc and 3-10.
14	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.
15	Processing Approaches: Suspension (Bead) Polymerization Processes Polyvinyl Chloride Via Precipitation Polymerization Polyethylene Via Radical Polymerization	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.
16	Ziegler-Natta Catalysis Stereochemistry of Polymers	Sections 6-1, 6-2ad, 6-3ab, especially 6-3b-4.
17	Stereoregular Polymerizations	Sections 8-1, 8-4abc, and 8-4fg.
18	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.
Ionic Polymerization
19	Metallocene Chemistry Introduction to New Developments from Brookhart, et al.	Sections 5-1 and 5-3.
20	Introduction to Anionic Polymerization Monomers Applicable to Anionic Methods Kinetics of “Nonliving” Anionic Polymerization	Section 5-3e.
21	Living Anionic Polymerization Effects of Initiator and Solvent
22	Anionic Block Copolymerization	Section 5-4abcd.
23	Anionic Ring Opening Polymerization End Group Functionalization Telechelic Oligomers and Novel Architectures Using Coupling Techniques	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.
24	Introduction to Cationic Polymerization, Monomers, Kinetics	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.
25	“Living” Cationic Polymerizations Examples of Cationic Polymerization, Isobutyl Rubber Synthesis, Polyvinyl Ethers
26	Anionic Ring Opening Polymerization Cationic Ring Opening Polymerization Other Ring Opening Polymerizations
27	Polysiloxanes, Lactams, etc.
Polymer Functionalization and Modification
28	Introduction to Polymer Functionalization: Motivations, Yield, Crystallinity, Solubility Issues Common Functionalization Approaches	Sections 9-1a to 9-1k.
29	Functionalization Case Studies: Biomaterials Systems, Liquid Crystal (LC) Polymers	Sections 9-4, 9-5, and 9-6.
Less Traditional Approaches to Polymer Synthesis
30	Surface Functionalization of Polymers Graft Copolymerization Approaches to Making Comb and Graft Architectures Grafting onto Existing Polymer Surfaces Surface Engineering Using Graft Copolymers	Section 9-8.
31	“Living” Free Radical Approaches: Stable Free Radical Polymerization Atom Transfer Radical Polymerization (ATRP)
32	ATRP RAFT and Other New Methods Ring Opening Metathesis Polymerization (ROMP)	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.
33	ROMP Oxidative Coupling Electrochemical Polymerizations Case Study: Electro-active Polymers	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.
34	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.
35	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	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.