BLOCK GRAFT COPOLYMERS

1 BLOCK & GRAFT COPOLYMERS Cao học Hóa Lý Tổng hợp & Biến tính polymer Hà Thúc Huy 2 General Synthetic Strategies AB diblock copolymers: • (a) sequential addition of monomers • (b) coupling of two appropriately end- functionalized chains. 3 ABA triblock copolymers : (a) three-step sequential addition of monomers (b) two-step sequential addition of monomers followed by a coupling reaction with a suitable difunctional linking agent (c) use of a difunctional initiator and a two-step sequential addition of monomers. 4 Synthesis of Block Copolymers by Anionic Polymerization 5 The less reactive monomer should be polymerized first • Preparation of ABA triblock copolymer by anionic living polymerization In non polar solvent (e.g., benzene), styrene is less reactive 6 7 8 ??? EX : Hajduk DA, Takenouchi H, Hillmyer MA, Bates FS, Vigild ME, Almdal K (1997) Macromolecules 30:3788 9 EX : P2VP-b-PEO-b-P2VP 10 EX : P4VP-b-PBd-b-P4VP difunctional initiator m-diisopropenylbenzene Erukhimovich I, Dobrynin AV (1994) Macromol Symp 81:253 [...]... 1,3-Cyclohexadiene  CHD Ko MJ, Kim SH, Jo WH (2001) Macromol Theory Simul 10:381 13 Synthesis of Block Copolymers by Controlled Radical Polymerization • Synthesis of Block Copolymers by Nitroxide-Mediated Radical Polymerization, NMP PS-b-PI 14 Fukunaga K, Hashimoto T, Elbs H, Krausch G (2003) Macromolecules 36:2852 Synthesis of Block Copolymers by Atom Transfer Radical Polymerization, ATRP 2-bromo-2-methylpropionic... 36:7707 21 Synthesis of Non-Linear Block Copolymers a Use of multifunctional initiators: b Use of multifunctional linking agents: c Use of difunctional monomers: 22 {polycaprolactone-bpoly[4-(2-hydroxyethyl)caprolactone]}4 Krishnamoorti R, Modi MA, Tse MF, Wang H-C (2000) Macromolecules 33:3810 23 (PEO-b-PS)n, n = 3, 4 star -block copolymers 24 25 26 27 28 29 EX : Grafting - onto 30 Synthesis of Macromonomers... 2-bromo-2-methylpropionic acid 4methoxyphenyl ester 1,4-(2’-bromo-2’-methylpropionate)benzene 15 Synthesis of Block Copolymers by Reversible Addition-Fragmentation Chain Transfer Radical Polymerization, RAFT 16 17 Mogi Y, Mori K, Matsushita Y, Noda I (1992) Macromolecules 25:5412 Synthesis of Block Copolymers by Combinations of Different Polymerization Techniques 18 EX : PTHF-b-PS-b-PTHF 19 EX : PLLA-b-PS-b-PMMA . 1 BLOCK & GRAFT COPOLYMERS Cao học Hóa Lý Tổng hợp & Biến tính polymer Hà Thúc Huy 2 General Synthetic Strategies AB diblock copolymers: • (a) sequential. Jo WH (2001) Macromol Theory Simul 10:381 14 Synthesis of Block Copolymers by Controlled Radical Polymerization • Synthesis of Block Copolymers by Nitroxide-Mediated Radical Polymerization,. of Block Copolymers by Atom Transfer Radical Polymerization, ATRP 1,4-(2’-bromo-2’-methyl- propionate)benzene 2-bromo-2-methylpropionic acid 4- methoxyphenyl ester 16 Synthesis of Block Copolymers