review Finish the following reactions: BF+ HO CI HC=C Sncl4+RCI
BF3 + H2 O SnCl 4+ RCl Finish the following reactions: H2 C C CH3 CH3
§42 Anionic polymerizationction (1)History 1877, Wurtz, bases, epoxy ethane 1914, Na, Bd, Ip, st 1940, Ellis, BuLi, ethylene 1952, Higginson, styrene, KNH2, kinetic study 1956, Szwarc, sodium naphthalene, St, living polymerization conception 60s, commercial SDs products were available 90s, study on the living polymerization of polar monomers (2) Carbanion
§4.2 Anionic polymerization 1、Introduction 1877，Wurtz, bases, epoxy ethane 1914, Na, Bd, Ip, St 1940, Ellis, BuLi, ethylene 1952，Higginson, styrene, KNH2 , kinetic study 1956，Szwarc, sodium naphthalene, St, living polymerization conception 60's, commercial SDS products were available 90‘s, study on the living polymerization of polar monomers (1) History (2) Carbanion
2. Monomer (1)Olefin with polar substituent For example CH H.=CH C=CH HC-C C=N C-O o O--CH Acrylonitrile Nitroethene Methyl methacrylate
2. Monomer (1) Olefin with polar substituent H2 C CH C N H2 C CH N O O H2 C C C O CH3 O CH3 Acrylonitrile Nitroethene Methyl methacrylate For example
(2)Conjugated diene CH HC=CH HC=C styrene a-Me-Styrene H2C=CH-CH=CH2 C-CH-C=C butadiene Isoprene
(2) Conjugated diene H2 C CH H2 C C CH3 H2 C CH CH CH2 H2 C CH C CH2 CH3 styrene a-Me-styrene butadiene isoprene
(3)Reactivity of monomer (Substituting constant: o) Group a H2C=C(CN)2>H2=C-COOC2 Hs >H2C-CH CN NO2 (1.256) (1.150) (0.778) Group b: H2 C=CHCN >H2C=C-CH3>H2c=CH-C-CH CN o (0.66) (0.49) 0.502) HC=CH HC=C-CH 3 Group c: COOCH3 COOCH3 (0.385) (0.215) CH H2C-CH H C=C Group d: Hc三cH-cH=cH (-0.01) (-0.161)
(3) Reactivity of monomer (Substituting constant: s) Group A: Group B: H2 C C(CN) 2 H2 C C CN COOC2 H5 H2 C CH NO2 (1.256) > (1.150) (0.778) > H2 C CHCN H2 C C CN CH3 H2 C CH C O CH3 (0.66) > (0.49) (0.502) > Group C: H2 C CH COOCH3 H2 C C CH3 COOCH3 (0.385) > (0.215) Group D: H2 C CH CH CH2 H2 C CH (- 0.01) H2 C C CH3 (- 0.161)