高分子化学（浙江大学） polymer2-3 Measurement of rate coefficients.pptVIP

* Polymerization heat Steric effect: -?H? Resonance effect: -?H ? Styrene(69.9) butadiene(72.8) acrylonitrile (72.4) negative substitute: -?H? vinyl chloride(95.8) vinylidene fluoride(129.7) tetrafluoroethylene(154.8) H bond solvent: -?H ? acrylic acid(66.9) methacrylic acid(42.3) - * monomer - ?H? (kJ/mol) - ?S? (J/mol.K) ethylene 95.0 100.4 propylene 85.8 116.3 butylene-1 79.5 112.1 isobutylene 51.5 119.7 isoprene 72.8 85.8 butadiene 73 89.0 styrene 69.9 104.6 ?-methylstyrene 35.1 103.8 tetrafluroethylene 155.6 112.1 vinylchloride 95.6 - methly methacrylate 56.5 117.2 acrylic acid 66.9 acrylamide 82.0 Data of ?H? and ?S ? for some monomers (25?C) * Ceiling Temperature (聚合上限温度) [M]=1.0 * * For example: ΔH° ΔS° [M] at 70 oC kJ/mol J/(molK) MMA 56 118 4.36×10-3 Styrene 73 104 2.09×10-6 ?-Methylstyrene 45 148 7.60 equil. monomer concentration equilibrium monomer concentration * 11. Controlled/Living Radical Polymerization * Disadvantages of tradition radical Polymerization Slow and continuous initiation prevents synthesis of well-defined polymers with degrees of polymerization predetermined by the ratio of concentrations of the converted monomer to the introduced initiator, with controlled topologies (stars, combs) and compositions (blocks, grafts, gradients). The typical lifetime of a propagating chain is very short, in the range of 1 s. Molecular weight distribution is broad. Poor control on the regio- and stereoselectivity * Features of Living Polymerization No termination reaction! Linear kinetic plot in semilogarithmic coordinates (ln([M]0/[M] ) vs. time), if the reaction is first-order with respect to the monomer concentration. Linear evolution of MW with conversion. MW is predicted by ?[M]/[I]0 Polydispersity (Mw/Mn) should be close to unity End-functionality of polymer chain Block polymer can be prepared by continuous polymerization of second monomer *