1. Chemistry 367L/392N Paul J Flory 1910-1985 Macromolecular Chemistry Wallace H. Carothers 1896-1937

2. Chemistry 367L/392N Nomenclature Methods Source name (more common use) – based on monomer name (polystyrene) IUPAC, constitutional repeating unit – used in both source and structure names…messy! Abbreviations and acronyms – PMMA [poly(methyl methacrylate)]…also common Trade names – marketing and technological literature

3. Chemistry 367L/392N Examples 1. Poly(1-acetoxyethylene) - structure 2. Poly(vinyl acetate) - source 1. Poly(but-1-ene-1,4-diyl) 2. Polybutadienea 1. Poly(1-cyanoethylene) 2. Polyacrylonitrile 1. Poly(methylene) 2. Polyethene; polyethylene 1. Poly[(2,5-dioxotetrahydrofuran- 3,4-diyl)(1-phenylethylene)] 2. Poly(maleic anhydride-alt-styrene)

4. Chemistry 367L/392N Industrial Influence: Trade Names PVC poly (vinylidene chloride) Saran wrap PVC poly (vinyl chloride) Pipe and records PET poly (ethylene teraphthalate) Coke bottles, Dacron Polystyrene Cups and packaging Delrin Bushings and engineering parts Lexan Bullet proof glass Teflon Non stick pans PVDF speakers and microphones Kevlar bullet proof vests Nylon Rope and fiber

5. Chemistry 367L/392N Common Abbreviations Selected examples ABS (acrylonitrile butadiene styrene) LLDPE(linear low density polyethylene) PA66 [polyamide (Nylon) 66] PC (polycarbonate) PET [poly(ethylene terephthalate)] PMMA [poly(methyl methacrylate)] PS (polystyrene) PVC[poly(vinyl chloride)] TP (thermoplastic elastomer polyolefin) PVF2 [poly(vinlylidine fluoride)] (www.plasticsusa.com/tradename.html)

6. Chemistry 367L/392N Class Names Polyolefin Polyester Polyamide Polycarbonate Polyurethane Naming “classes” of polymers

7. Chemistry 367L/392N Poly(ethylene-alt-carbon monoxide) Poly(1-oxopropanediyl) Poly(vinyl alcohol) Poly(1-methyl-1-phenylethylene) Name ‘em or draw ‘em

8. Chemistry 367L/392N Wallace Hume Carothers 1896-1937 Carothers, W.H., J. Am. Chem. Soc. 1929, 51, 2548-58J. Am. Chem. Soc

9. Chemistry 367L/392N Carothers Paper

10. Chemistry 367L/392N Addition polymer Polystyrene ( )n)n

11. Chemistry 367L/392N Addition Polymer Polyvinylchloride

12. Chemistry 367L/392N Condensation Polymer Dacron H 2 O +

13. Chemistry 367L/392N Condensation Polymer ( )n)n Nylon 6,6 H 2 O +

14. Chemistry 367L/392N

15. Carothers Definition Addition CO 2 H HO 2 C HO OH O O O HO O H + ( ( Condensation - H 2 O NCO NCO HO OH OCN H N O O O N H O Ar + Condensation? O OO O O O Condensation? Addition? Problems with Carothers Definition

16. Chemistry 367L/392N Another Problem from ω-hydroxycarboxylic acid Polyester from lactone

17. Chemistry 367L/392N Paul J Flory 1910-1985 The Nobel Prize in Chemistry 1974 "for his fundamental achievements, both theoretical and experimental, in the physical chemistry of the macromolecules"

18. Chemistry 367L/392N Flory Clears Things Up Polymer Structure is distinct from Polymerization Process. ProcessStructure Addition Similar connections Ring-opening No by-products Same composition (monomer = polymer) Condensation New functional groups Release of small molecules Degradation gives different composition

19. Chemistry 367L/392N Basic Types of Polymerization Mechanisms Chain-growth Step-growth Ring-opening

20. Chemistry 367L/392N Chain growth system The characteristic of a chain polymer is that polymer growth takes place by monomer reacting only with the reactive centers. Monomer does not react with monomer and the different-sized species such as dimer, trimer, and n-mer do not react with each other. The polymerization ceases when the active center is destroyed by termination reaction(s).

21. Chemistry 367L/392N A condensation takes place between two polyfunctional molecules to produce one larger polyfunctional molecule with the possible elimination of a small molecule such as water. The reaction continues until one of the reagents is used up. Step Growth system

22. Chemistry 367L/392N The chain growth vs. step growth Step Chain