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A list of topics by session is included in the calendar below.
Description
In this Chemical Engineering graduate level course, basic methods in the synthesis of polymers are addressed and discussed, including the various types of polymerizations and their applications toward both common and new promising polymer products. This class presents the most common synthetic methods used in polymerization, the basic differences in the kinetics of these methods, the final end-products obtained, and the synthetic processing techniques that might be used for various applications.
New and developing approaches to polymerization such as atom transfer free radical and "living" free radical methods are addressed using literature references and class discussion. Throughout the course, general materials and engineering design concepts are introduced, as well as the manipulation of polymer structure and processing to obtain desired properties. In the class, we emphasize the use of chemistry as a tool for the development of new materials or the modification of existing polymer systems. For this reason, the course covers functionalization of polymers, including polymer surface modification for applications requiring improved adhesive, frictional, or reactive properties. The use of self-assembly in the formation of macromolecular structures using hydrogen bonding, ionic bonding, and other non-covalent bonds is discussed at the end of the course by means of examples from the literature and classroom discussion. A design project is introduced at the middle of the term as a means of engaging students in their own research interests.
Prerequisites
This course assumes knowledge of organic chemistry (5.12 and 5.13) and thermodynamics and kinetics (5.60).
Texts
Odian, George. Principles of Polymerization. 4th ed. Hoboken, NJ: Wiley-Interscience, 2004. ISBN: 9780471274001.
Supplementary Handouts will be used frequently and will be handed out in lecture as needed during the course.
Grading
There will be three hour-long exams, open book and notes. Each exam will be worth 25% of the class credit. There will be occasional problem sets, which will be worth a total of 5% credit. A final design project paper will be due at the end of the term, worth 20% credit. The details of the design project can be found in projects.
Grading criteria.
| ACTIVITIES |
PERCENTAGES |
| Problem Sets |
5% |
| Design Project |
20% |
| Exam 1 |
25% |
| Exam 2 |
25% |
| Exam 3 |
25% |
Calendar
Calendar table.
| SES # |
TOPICS |
KEY DATES |
| 1 |
Course Overview
Polymer Design and Synthesis
Reaction Types and Processes
Introduction to Step Growth
|
|
| 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
|
|
| 3 |
Step Growth Polymerization
Types of Monomers
Kinetics and Equilibrium Considerations
Closed vs. Open Systems
|
|
| 4 |
Common Processing Approaches
Near-equilibrium vs. Far from Equilibrium
Homogeneous Solution and Bulk Polymerization
|
|
| 5 |
Interfacial Polymerizations
Application Examples: Polyamides
|
Problem set 1 out |
| 6 |
Other Polymers of Interest Obtained by Step-Growth
Polyaramids
Polyimides
Segmented and Block Copolymers from Step Condensation Methods
|
|
| 7 |
Crosslinking and Branching
Network Formation and Gelation
Carothers Equation: Pn Approach
|
|
| 8 |
Network Formation
Statistical Approach: Pw Approach
A Word on MWD for Nonlinear Polymerizations
|
|
| 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
|
Problem set 1 due
|
|
Exam 1 (Step Growth): Lectures 1-9 (Two Days After Ses #9) |
|
| Free Radical Chain Polymerization |
| 10 |
Introduction to Radical Polymerization |
|
| 11 |
Radical Polymerization
Homogeneous Reaction Rate Kinetics
|
|
| 12 |
Free Radical Kinetic Chain Length
MWD
Chain Transfer
Energetics
|
Problem set 2 out
Exam 2 practice problems out
|
| 13 |
Thermodynamics of Free Radical Polymerizations
Ceiling T's
Tromsdorff Effect
Instantaneous Pn
|
|
| 14 |
Processing Approaches: Emulsion Polymerization Processes |
|
| 15 |
Processing Approaches: Suspension (Bead) Polymerization Processes
Polyvinyl Chloride Via Precipitation Polymerization
Polyethylene Via Radical Polymerization
|
|
| 16 |
Ziegler-Natta Catalysis
Stereochemistry of Polymers
|
Problem set 2 due |
| 17 |
Stereoregular Polymerizations |
|
| 18 |
Radical Copolymerization: Alternating to Block Copolymers |
|
|
Exam 2 (Free-Radical Chain): Lectures 12-18 (Two Days After Ses #18) |
|
| Ionic Polymerization |
| 19 |
Metallocene Chemistry
Introduction to New Developments from Brookhart, et al.
|
Design project: project description distributed
|
| 20 |
Introduction to Anionic Polymerization
Monomers Applicable to Anionic Methods
Kinetics of "Nonliving" Anionic Polymerization
|
|
| 21 |
Living Anionic Polymerization
Effects of Initiator and Solvent
|
|
| 22 |
Anionic Block Copolymerization |
Problem set 3 out |
| 23 |
Anionic Ring Opening Polymerization
End Group Functionalization
Telechelic Oligomers and Novel Architectures Using Coupling Techniques
|
|
| 24 |
Introduction to Cationic Polymerization, Monomers, Kinetics
|
|
| 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
|
Problem set 3 due |
| 27 |
Polysiloxanes, Lactams, etc. |
|
|
Exam 3 (Ionic): Lectures 20-27 (Three Days After Ses #27) |
|
| Polymer Functionalization and Modification |
| 28 |
Introduction to Polymer Functionalization: Motivations, Yield, Crystallinity, Solubility Issues
Common Functionalization Approaches
|
|
| 29 |
Functionalization Case Studies: Biomaterials Systems, Liquid Crystal (LC) Polymers |
|
| 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
|
|
| 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)
|
|
| 33 |
ROMP
Oxidative Coupling
Electrochemical Polymerizations
Case Study: Electro-active Polymers
|
|
| 34 |
Inorganic Polymer Synthesis |
|
| 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
|
Design project due |