# Syllabus

## Course Meeting Times

Lectures: 3 sessions / week, 1 hour / session

## 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