Synthesis of polymers

Lectures: 3 sessions / week, 1 hour / session

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.

This course assumes knowledge of organic chemistry (5.12 and 5.13) and thermodynamics and kinetics (5.60).

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.

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.

Course Overview

Polymer Design and Synthesis

Reaction Types and Processes

Introduction to Step Growth

Molecular Weight (MW) Control

Molecular Weight Distribution (MWD) in Equilibrium Step Condensation Polymerizations

Interchange Reactions: Effects on Processing and Product

Application Example: Common Polyesters

Step Growth Polymerization

Types of Monomers

Kinetics and Equilibrium Considerations

Closed vs. Open Systems

Common Processing Approaches

Near-equilibrium vs. Far from Equilibrium

Homogeneous Solution and Bulk Polymerization

Interfacial Polymerizations

Application Examples: Polyamides

Other Polymers of Interest Obtained by Step-Growth

Polyaramids

Polyimides

Segmented and Block Copolymers from Step Condensation Methods

Crosslinking and Branching

Network Formation and Gelation

Carothers Equation: Pn Approach

Network Formation

Statistical Approach: Pw Approach

A Word on MWD for Nonlinear Polymerizations

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

Radical Polymerization

Homogeneous Reaction Rate Kinetics

Free Radical Kinetic Chain Length

MWD

Chain Transfer

Energetics

Problem set 2 out

Exam 2 practice problems out

Thermodynamics of Free Radical Polymerizations

Ceiling T's

Tromsdorff Effect

Instantaneous Pn

Processing Approaches: Suspension (Bead) Polymerization Processes

Polyvinyl Chloride Via Precipitation Polymerization

Polyethylene Via Radical Polymerization

Ziegler-Natta Catalysis

Stereochemistry of Polymers

Metallocene Chemistry

Introduction to New Developments from Brookhart, et al.

Design project: project description distributed

Introduction to Anionic Polymerization

Monomers Applicable to Anionic Methods

Kinetics of "Nonliving" Anionic Polymerization

Living Anionic Polymerization

Effects of Initiator and Solvent

Anionic Ring Opening Polymerization

End Group Functionalization

Telechelic Oligomers and Novel Architectures Using Coupling Techniques

Introduction to Cationic Polymerization, Monomers, Kinetics

"Living" Cationic Polymerizations

Examples of Cationic Polymerization, Isobutyl Rubber Synthesis, Polyvinyl Ethers

Anionic Ring Opening Polymerization

Cationic Ring Opening Polymerization

Other Ring Opening Polymerizations

Introduction to Polymer Functionalization: Motivations, Yield, Crystallinity, Solubility Issues

Common Functionalization Approaches

Surface Functionalization of Polymers

Graft Copolymerization

Approaches to Making Comb and Graft Architectures

Grafting onto Existing Polymer Surfaces

Surface Engineering Using Graft Copolymers

"Living" Free Radical Approaches: Stable Free Radical Polymerization, Atom Transfer Radical Polymerization (ATRP)

ATRP

RAFT and Other New Methods

Ring Opening Metathesis Polymerization (ROMP)

ROMP

Oxidative Coupling

Electrochemical Polymerizations

Case Study: Electro-active Polymers

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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