Polymer Chemistry

Aug 8, 2025

Overview

This lecture introduces the basics of polymers, covering their types, methods of polymerization, structural variations, and how these factors influence polymer properties and uses.

Introduction to Polymers

  • Polymers are large molecules made from repeated smaller units called monomers.
  • Biological polymers include DNA, RNA, and proteins; synthetic examples are plastics like polyethylene and polystyrene.
  • Teflon (PTFE) and Kevlar are notable polymers discovered accidentally.

Types and Naming of Polymers

  • Addition polymers are made by repeatedly joining the same monomers, named by adding "poly" to the monomer's name (e.g., polystyrene).
  • Copolymers are formed from more than one type of monomer (e.g., ABS in Lego bricks).
  • Repeat units in structures are indicated with brackets and an "n" for the number of repetitions.

Polymerization Mechanisms

  • Addition (chain growth) polymerization can occur via radical, cationic, or anionic mechanisms.
  • Free radical polymerization starts with a radical initiator and ends by random chain termination.
  • Cationic polymerization uses a cationic initiator and ends through chain transfer reactions.
  • Anionic polymerization requires anions and monomers that stabilize negative charges, with termination via proton transfer.

Condensation (Step-Growth) Polymers

  • Condensation polymerization involves monomers joining and releasing a small molecule, often water or HCl.
  • Examples include Kevlar and polycarbonates (Lexan), which can lose molecules other than water during formation.
  • No termination step is required; reaction stops when reactants are depleted or conditions change.

Polymer Structure and Morphology

  • Polyethylene exists as high-density (HDPE, linear, strong) and low-density (LDPE, branched, flexible) forms.
  • Structure affects properties: linear polymers pack closely and are stronger; branched ones are softer.
  • Polymer strands can be crystalline (ordered) or amorphous (disordered); real samples may have both.

Thermal Properties of Polymers

  • Glass transition temperature (Tg) is when a polymer becomes soft and rubbery.
  • Polymers with Tg above room temperature are hard and brittle (e.g., polystyrene).
  • Tg affects performance; for example, brittle O-rings below Tg contributed to the Challenger disaster.

Key Terms & Definitions

  • Polymer — Large molecule of repeating smaller units (monomers).
  • Monomer — Small molecule that bonds to form a polymer.
  • Addition Polymer — Polymer formed by linking identical monomers without byproducts.
  • Copolymers — Polymers made from more than one type of monomer.
  • Radical Polymerization — Chain reaction started by a molecule with an unpaired electron.
  • Condensation Polymerization — Polymerization involving loss of a small molecule (often water or HCl).
  • Repeat Unit — The molecular segment that repeats in a polymer chain.
  • Crystalline Polymer — Polymers with ordered, tightly packed regions.
  • Amorphous Polymer — Polymers with disordered, tangled regions.
  • Glass Transition Temperature (Tg) — Temperature where a polymer becomes soft and rubbery.

Action Items / Next Steps

  • Review polymerization mechanisms and practice drawing repeat units.
  • Prepare for next lecture on benzene, aromatic compounds, and NMR analysis.
  • Complete any assigned readings on polymer structures and applications.