1. Types of Vinyl Polymerization MethodAdvantagesDisadvantages Bulk (Neat)Simple equipment Rapid reaction Pure polymer isolated Heat buildup Gel effect Branched or crosslinked product SolutionGood mixing Ready for application Lower mol. Wt. Low R poly Solvent Recovery Suspension (Pearl) Low viscosity Direct bead formation Removal of additives EmulsionHigh R poly Low Temperatures High Mol. Wt. High surface area latex Removal of additives Coagulation needed Latex stability Inverse EmulsionWater in oil latex formed Inversion promotes dissolution in water

2. Fate of Initiator Radicals Radical reactions Recombination in solvent cage Chain initiation, R i = 2 f kd [I] Efficiency factor, f = 0.1 - 0.9 Reaction with polymer radicals (k t )--primary termination Reaction with initiator (MIH) Hydrogen abstraction from polymer chains (chain transfer to polymer) Reaction with solvent or inhibitor

3. Radical Initiators Azo Initiators

4. Decomposition of Azo Initiators 2- bond cleavage to liberate nitrogen Cage Recombination ---Side reaction- irreversible coupling of succinonitrile radicals, efficiency decreases at high conversion

5. Peroxy Initiators High temperature initiators Moderate temperature initiators

6. Peroxy Initiators Low temperature initiators, 35-60 C 3-bond cleavage process?  -cleavage to carbon centered radical

7. Redox Initiation 0-5 C in water 0-5 C in organic/aqueous phase

8. Decomposition of Peroxy Initiators 1-bond cleavage process If R = aryl, acyl radical initiates = alkyl, CO2 lost before initiation occurs

9. Reaction of benzoyloxy radicals with styrene

10. Chain Transfer Hydrogen transfer to growing polymer chain Reinitiation of growing chain using transferred radical

11. Effect of Chain Transfer on R p and DP Relative rate constants Type of effectEffect on R p Effect on DP k p.>> k tr k a ~ k p NormalNoneDecrease k p << k tr k a ~ k p TelomerizationNoneLarge decrease k p >> k tr k a < k p RetardationDecrease k p << k tr k a << k p InhibitionLarge decrease

12. Control by Chain Transfer Chain transfer depends upon nature and concentration of chain transfer agent. Where Ctr is the chain transfer constant that includes the rate constants for hydrogen abstraction and re-initiation of a new chain Ctr is specific for a given monomer at a given temperature

13. Common Chain Transfer Agents Transfer agentStyrene, Ctr x 10 4 Vinyl Acetate Ctr x 10 4 Toluene0.12521.6 Di-n- butyldisulfide 2410,000 Carbon tetrabromide 22,000390,000 n-butyl mercaptan 210,000480,000

14. Additional Chain Transfer Processes Chain transfer to monomer, Ctr x 10 4 –Ethylene, 0.4- 4.0; Styrene, 0.3-0.6 Chain transfer to polymer--branching Polyethylene Vinyl acetate Vinyl chloride Vinyl acetate, 1.75-2.8 Vinyl chloride, 10.8-16 Allyl systems, 50-100

15. Transfer to Polymer Polyethylene branching Long branches Short branches

16. Inhibition of Radical Polymerization Must stop oxygen- and carbon centered radicals Carbon centered radicals stopped by addition Oxygen centered radicals stopped by hydrogen transfer Radicals generated by auto oxidation May be metal catalyzed

17. Critical Inhibitor Properties An inhibitor should not add to, abstract from or otherwise reach with monomer or solvent Inhibitors should not undergo self reaction or unimolecular decomposition Inhibitors must react rapidly with the propagating and/or initiator derived radicals to terminate polymer chains

18. Trapping Oxygen Centered Radicals

19. Trapping carbon centered radicals Carbon centered radicals stopped by addition to oxygen or carbon

20. Typical Inhibitors

21. Stable Radical Inhibitors