开环聚合.ppt

* Ring - Opening Polymerization 1 Thermodynamic of ring-opening polymerization 1.1 General aspect n -R-Z- -[-R-Z-]- n comparison with polycondensation/addition polymerization and step/chain polymerization 1) polymerization rate (kinetic) equation similar to that of addition and chain polymerization 2) molecular weight of polymer ~ t curve similar to that of polycondensation and step 3) equilibrium of polymerization and depolymerization types of ring monomers: cyclic alkane -(-CH2-)- n=3, 4, 5… cyclic ether -(CH2-)-O- n=2, 3, 4… n=2 ethylene oxide propylene oxide n=3 oxetane n=4 tetrahydrofuran acetals trioxane amides -(-CH2-)-C-NH n=5 caprolactam n n O O CH3 O O O O O O n O n esters -(-CH2-)-C-O n=5 caprolacton O=C-O anhydride (CH2-)-C=O amines -(-CH2-)-NH siloxanes -(-Si(CH3)2-O-)- n=3, 4, 5… n=4 octamethyl cyclotetrasiloxane (D4) n n n ?G=?H-T?S ?H is affected by: 1) angle strain 2) conformational strain 3) transannular strain 4) steric effect of side group ? ring-opening polymerization: Tc (THF, 1,3-dioxalane) Tf (S8, Se8) [M]e 1.2 Homocyclic compounds 1.2.1 Factors affecting ?H 1.2.1.1 Angle strain measure: distortion, strain per CH2, strain energy, ?H, ?G 1) distortion of bond angles = (normal valency angle - actual angle between bonds) for 4-member ring, = (109o28? - 90o)=9o44? 2) strain energy per CH2 = heat of combusion of CH2 in cycloalkane - that of CH2 (659 kJ/mol) for 4-member ring, = 686.7 - 659 = 27.7 kJ/mol 3) strain energy of cycloalkane = n ? strain energy per CH2 for 4-member ring, = 4 ? 27.7 = 110.8 kJ/mol 4) enthalpy of polymerization calorimetrically ?H for 4-member ring, -CH2-CH2-CH2-CH2- + ?Hls 1 2 1 2 for cycloalkane 3 60 24o44? 697.6 38.6 115.6 115.8 113.1 69 92.5 4 90 9o44? 686.7