高分子合成化学英文课件.pptVIP

* * * * * * * * * * * * Polymer Synthesis CHEM 421 A Brief Review What is living polymerization? What are the major criteria for living polymerization? No termination No chain transfer Living polymerization is a good tool for the preparation of block copolymers. Block copolymers can be prepared by sequential addition of monomers. C Mn A PDI B Time ln[M]0/[M]t Rankings of Anions… How to characterize the reactivity of a propagating anion? Propagating Anions pKa of conjugate acid of prop.chain end 42 25 25 20 Propagating Anions pKa of conjugate acid of prop.chain end 16-18 10-12 11-13 Initiators Monomer pKa Useful Initiator Styrenes.dienes 42 RLi, NH2-, Ar - Acrylates 25 RMgX, DPHL Acrylonitriles 25 RO -, C5H5- Vinyl ketones, Aldehydes 20 RO - Cyclic oxides 16-18 RO - Siloxanes(-D3) 10-12 HO -, RO - Cyano acrylates 11-13 H2O, HO -, RO - Nitroalkenes 10 KHCO3, H2O most nucleophilic Least nucleophilic Reactivity Super glue Microstructure of Dienes Four different microstructures in polyisoprene cis-1,4 favored in hydrocarbon solvents trans 1-4 isomer cis 1-4 isomer (natural rubber) 1-2 isomer 3-4 isomer Can MMA be polymerized via living process ? 3) 2) 1) Side reactions PMMA via Living Pzn PMMA homopolymer Can not use BuLi directly Make new initiator (use 1,1-diphenylethylene) 1,1-diphenyl hexyl lithium (DPHL) Sterically hindered resonant stabilization PMMA via Living Pzn Block Copolymers Definition: Macromolecules consisting of homogenous segments made from different monomers (usually two or three different monomers). Ex. A-A-A-A-A-A-B-B-B-B-B-B Some Basic Diblock Copolymer Architectures Linear Graft Ex: PS-g-PI Ex. PS-b-PI Star Microphase Separation Most polymers are immiscible Thermoplastic Elastomer Common Elastomer SBS (PS-PB-PS) Poly(cis-1,4-butadiene) Physical crosslinking Can process it repeatedly Thermal reversibility Chemical rosslinking Can’t process it repeatedly Thermal irreversibility heating cooling Sulfur Crosslinking Block