Grignard metathesis polymerization

Keywords Donor-acceptor block copolymers Grignard metathesis polymerization... 

A variant of metathesis is the Grignard metathesis polymerization. The polymerization of substituted thiophenes proeeeds hy a living chain-growth mechanism. Thiophene modified MEH-PPV can be synthesized from a precursor monomer with Grignard reagents. The procedure is shown in Figure 3.6. 

M. G. Alemseghed, S. Gowrisanker, J. Servello, M. C. Stefan, Synthesis of Di-Block Copolymers Containing Regioregular Poly(3-Hexylthiophene) and Poly(Tetrahydrofuran) by a Combination of Grignard Metathesis and Cationic Polymerizations. Macromol. Chem. Phys. 2009,210,2007-2014. 

L. Miozzo, N. Battaglini, D. Braga, L. Kergoat, C. Susptee, A. Yassar, Synthesis and Characterization of All-Conjugated Copolymers of 3-Hexyl-Thiophene and EDOT by Grignard Metathesis Polymerization. /. Polym. Sci. PartPolym. Chem. 2012, 50, 534-541. 

M. Jeffries-EL, G. Sauv6, R. D. McCullough, In-Situ End-Group Functionalization of Regioregular Poly(3-Alkylthiophene) Using the Grignard Metathesis Polymerization Method. Adv. Mater. 2004,16,1017-1019. 

Grignard metathesis polymerization allows the preparation of poly (3-hexylthiophene)-based... 

Jelfiies-EI, M., G. Sauve, and R.D. McCullough. 2004. In-situ end group functionalization of regioregular poly(3-alkylthiophene) using the Grignard metathesis polymerization method. Adv Mater 16 (12) 1017-1019. 

Alemseghed, M.G., Gowrisanker, S., Servello, (., and Stefan, M.C. (2009) Synthesis of di-block copolymers containing regioregular poly(3-hexylthiophene) and poly (tetrahydrofuran) by a combination of Grignard metathesis and cationic polymerizations. Macromol. Chem. Phys., 210, 2007-2014. 

J. (2009) All-polymer photovoltaic devices of poly(3-(4-n-octyl)-phenylthiophene) from Grignard metathesis (GRIM) polymerization./. Am. Chem. Soc., 131, 14160-14161. 

Figure 2.4 Dependence of molecular weights and polydispersities on conversion for 2-bromo-5-chloromagnesium-3-hexylthiophene Grignard metathesis polymerization at variable Ni(dppp)Cl2 concentrations [M]q = 0.07 mol THE 23-25°C. Reprinted with permission from M. C. lovu, E. E. Sheina, R. R. Gil and R. D. McCullough. Experimental evidence for the quasi- living nature of the Grignard metathesis method for the synthesis of regioregular poly(3-alkylthiophenes). Macromolecules 38(21), 8649-8656 (2005). Copyright 2005 American Chemical Society...

M. C. lovu and R. D. McCullough. Quasi-living Grignard metathesis polymerization for the synthesis of regioregular poly(3-alkylthiophene)s. Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.) 47(1), 242-243 (2006). 

Mentioned below are broadly eleven ways of synthesizing these polymers Method A Electrochemical Polymerization Method B Solution Polymerization Method C In situ Chemical Oxidative Polymerization Method D Dispersion Polymerization Method E Vapor-Phase Polymerization Method F SoUd-State Polymerization Method G Solvent-Free Chemical Polymerization Method H Grignard Metathesis (GRIM) Polymerization Method I Direct C-H Arylation Polymerization Method J Stille Polymerization Method K Yamamoto Polymerization... 

One of the most highly researched conjugated polymers is poly(3-aIkylthiophene) (underivatized polythiophene is insoluble). In a synthetic method developed by McCullough [94, 96] and further modified by Yokozawa [95, 97], Kumada catalyst-transfer polycondensation (KCTP), also commonly known as Grignard metathesis polymerization... 

Huang L, Wu S, Qu Y, Geng Y, Wang F. Grignard metathesis chain-growth polymerization for polyfluorenes. Macromolecules 2008 41 8944-8947. 

Scheme 8 Chain-growth mechanism of Grignard metathesis polymerization proposed by the McCullough group [110]. Reprinted with permissions from Sheina et al. [110]. Copyright (2004) American Chemical Society...

Stefan MC, Bhatt MP, Sista P, Magurudeniya HD (2012) Grignard metathesis (GRIM) polymerization for the synthesis of conjugated block copolymers containing regioregular poly(3-hexylthiophene). Polym Chem 3 1693-1701... 

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