Learn Polymers

Step-growth Polymer Synthesis and Properties

This site has an enormous range of structures for monomers and polymers, synthesis and compositions of polymers, plus mechanisms and applications including both homopolymers and copolymers. We will look at basic principles and properties that overlap and interact, especially when the interaction is synergistic in developing ultitmate properties. A major component of this course will be development of a broad understanding of step-growth polymer syntheses and structures as they relate to properties needed for commercial applications.

Detailed Syllabus

General Considerations

  • Historical: New science reaching maturity?
  • Unique molecular dimensionality
  • Hydrocarbon homologs: high MW effect
  • Consequences: summation, entanglements, timescale
  • Levels of organization
  • Molecular, microscopic, macroscopic
  • Polyolefin examples: branching, crosslinking
  • Synthetic variables: LD, HD, LLD
  • Processing: uHMW to spectra fibers
  • PP thermoplastic elastomer via metallocenes
  • Types of Intermolecular forces
  • Table of types and enthalpies
  • Plot of limiting Tm’s
  • Molecular engineering: controlling symmetry, packing, rigidity, intermolecular forces, crosslinking
  • Polymer synthesis: enthalpy versus entropy
  • Overall free energy versus temperature
  • Entropic control and ceiling temperature

Polyesters: Concepts and General Methods

  • Mechanisms, kinetics, catalyst effects
  • The tetrahedral intermediate: key for many acid reactions
  • Carothers equations: stoichiometry, conversion and MW control
  • Star, branched and crosslinked systems (A-B versus AA-BB)

Polyesters: Examples

  • Polycaprolactone: condensation versus ring-opening
  • PET, PBT and PEN: commercial polyesters
  • Polyglycolide/polylactide
    • Peptide analogs for biomedical applications
    • Ring-opening mechanism
    • Condensation route via phase-transfer (SN2)
  • Arylates: AB and AA-BB
    • Acetate route: rationale and mechanism
    • Acid chloride solution path
    • Thermotropic liquid crystals
  • Unsaturated polyester and fiberglass: synthesis, cure, properties
  • Polycarbonates: Introduction to carbonic acid polymers
    • PC via solution, melt and macrocycle
      • macrocycle synthesis via PTC
      • general advantages of ROMP
    • Properties and applications: Tg enhancement

Aliphatic Polyethers

  • Poly(ethylene glycol) versus poly(ethylene oxide)
  • Poly(propylene oxide) and pluronics
  • Polyoxetanes and pentaerythritol
  • Poly(tetrahydrofuran)
  • Polythioethylene
  • Poly(s8) and thiokols: ring-opening thermodynamics, PTC & condensation
  • Aryl polyethers via benzylic halides

Polyamides and Nylons: Monomers and Polymers

  • Nylon 6 and Nylon 6,6: ROMP, strike, interfacial methods
  • Nylon 11, Nylon 12, and Nylon 13,13: "hydrophobic" nylons
  • Nylon 6-T and Nylon 12-T: mixed aliphatic-aromatic
  • More Carothers equation applications
  • Aramids: Kevlar and Nomex
  • Acid chlorides versus in situ activation
  • Lyotropic liquid crystals
  • AB aramids and mixed systems
  • Carbonyl atom polymerization

Order in Nylons: Crystallinity, H-bonding and Orientation

  • Nylon crystal types and solid-state NMR
  • Psuedohexagonal phase via copolymerization

Urethanes and Ureas

  • Isocyanate syntheses and reactions
  • Hard-soft thermoplastic elastomers
  • Reaction injection molding (RIM) and RRIM
  • "New" foam technology

Polyimides

  • Monomer and Polymer Syntheses
  • Soluble/Thermoplastic versus amic-acid processing
  • Reactive oligomers: nadeimide versus acetylene
  • Fluorine property modifiers
  • Torlon Poly(amide-imide)

Engineering Resins via Nucleophilic Aromatic Substitution

  • NAS versus EAS: mechanisms, characteristics
  • PPS versus PPO and Iodine-mediated PPS
  • Poly(ether-imide): ultem
  • Neopentyl glycol imide
  • PEEK, PES versus PEK, PEKK
  • Adamantyl-substituted resins

Metal-Catalyzed Coupling Polymerizations

  • PPO as prototype: red-ox polymerization
  • Polyaniline, polythiophene, polypyrrole: conducting polymers
  • Polyacetylenes: coupling versus addition reactions
  • Diacetylene and polydiacetylenes: single-crystal polymerizations
  • Polyphenylenes: meta versus para effect
  • Polyphenylenevinylenes: electrolumenescence

Polybenzazoles: PBI, PBT and PBO

  • Polybenzimidazole: space and fire
  • Polybenzothiazole and polybenzoxazole
    • General monomer syntheses
    • Traditional two-stage polymerization
    • Lyotropic processing in PPA
    • Properties and commercial considerations
    • Carbonyl atom polymerizations