10.569 | Fall 2006 | Graduate

Synthesis of Polymers

Lecture Notes

These notes are preliminary and may contain errors.

SES # TOPICS LECTURE NOTES
1

Course Overview

Polymer Design and Synthesis

Reaction Types and Processes

Introduction to Step Growth

(PDF)
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

(PDF)
3

Step Growth Polymerization

Types of Monomers

Kinetics and Equilibrium Considerations

Closed vs. Open Systems

(PDF)
4

Common Processing Approaches

Near-equilibrium vs. Far from Equilibrium

Homogeneous Solution and Bulk Polymerization

(PDF)
5

Interfacial Polymerizations

Application Examples: Polyamides

(PDF)
6

Other Polymers of Interest Obtained by Step-Growth

Polyaramids

Polyimides

Segmented and Block Copolymers from Step Condensation Methods

(PDF)
7

Crosslinking and Branching

Network Formation and Gelation

Carothers Equation: Pn Approach

(PDF)
8

Network Formation

Statistical Approach: Pw Approach

A Word on MWD for Nonlinear Polymerizations

(PDF)
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

(PDF)
Free Radical Chain Polymerization
10 Introduction to Radical Polymerization (PDF)
11

Radical Polymerization

Homogeneous Reaction Rate Kinetics

(PDF)
12

Free Radical Kinetic Chain Length

MWD

Chain Transfer

Energetics

(PDF)
13

Thermodynamics of Free Radical Polymerizations

Ceiling T’s

Tromsdorff Effect

Instantaneous Pn

(PDF)
14 Processing Approaches: Emulsion Polymerization Processes (PDF)
15

Processing Approaches: Suspension (Bead) Polymerization Processes

Polyvinyl Chloride Via Precipitation Polymerization

Polyethylene Via Radical Polymerization

(PDF)
16

Ziegler-Natta Catalysis

Stereochemistry of Polymers

(PDF)
17 Stereoregular Polymerizations (PDF)
18 Radical Copolymerization: Alternating to Block Copolymers (PDF)
Ionic Polymerization
19

Metallocene Chemistry

Introduction to New Developments from Brookhart, et al.

(PDF)
20

Introduction to Anionic Polymerization

Monomers Applicable to Anionic Methods

Kinetics of “Nonliving” Anionic Polymerization

(PDF)
21

Living Anionic Polymerization

Effects of Initiator and Solvent

(PDF)
22 Anionic Block Copolymerization (PDF)
23

Anionic Ring Opening Polymerization

End Group Functionalization

Telechelic Oligomers and Novel Architectures Using Coupling Techniques

(PDF)
24

Introduction to Cationic Polymerization

Monomers

Kinetics

(PDF)
25

“Living” Cationic Polymerizations

Examples of Cationic Polymerization

Isobutyl Rubber Synthesis

Polyvinyl Ethers

(PDF)
26

Anionic Ring Opening Polymerization

Cationic Ring Opening Polymerization

Other Ring Opening Polymerizations

(PDF)
27 Polysiloxanes, Lactams, etc. (PDF)
Polymer Functionalization and Modification
28

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

Common Functionalization Approaches

(PDF)
29 Functionalization Case Studies: Biomaterials Systems, Liquid Crystal (LC) Polymers (PDF)
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

(PDF)
31

“Living” Free Radical Approaches: Stable Free Radical Polymerization

Atom Transfer Radical Polymerization (ATRP)

(PDF)
32

ATRP

RAFT and Other New Methods

Ring Opening Metathesis Polymerization (ROMP)

(PDF)
33

ROMP

Oxidative Coupling

Electrochemical

Polymerizations

Case Study: Electro-active Polymers

(PDF)
34 Inorganic Polymer Synthesis (PDF)
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

(PDF)

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