Grignard metathesis method

SCHEME 9.3 The Grignard metathesis method for the synthesis of regjoregular HT-PATs. 

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...

Stefan MC, Javier AE, Osaka I, McCullough RD (2009) Grignard metathesis method (GRIM) toward a universal method for the synthesis of conjugated polymers. Macromolecules 42 30-32... 

R.S. Loewe, S.M. Khersonsky, and R.D. McCullough, A simple method to prepare head-to-tail coupled, regioregular poly(3-alkylthiophenes) using Grignard metathesis, Adv. Mater., 11 250-253, 1999. 

R. S. Loewe, S. M. Khersonsky, R. D. McCullough, A Simple Method to Prepare Head-to-Tail Coupled, Regioregulcu Poly(3-Alkylthiophenes) Using Grignard Metathesis. Adv. Mater. 1999,11,250-253. 

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. 

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. 

Grignard metathesis (GRIM) method, 9-8 Grignard, 9-2, 9-8 GRIM methods, 9-3 Group representations of PGP s, 22-3... 

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... 

A Grignard metathesis (GRIM) method gave an HT PAT [poly (3-dodecylthiophene)], with regioregularity >99.9%. Here, a 2,5-dibromo-3-aUcylthiophene is treated with CH3MgBr in the presence of Ni(dppp)Cl2 as catalyst, as shown in Scheme 7. 

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... 

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