GRIM method

R.S. Loewe, P.C. Ewbank, J. Liu, L. Zhai, and R.D. McCullough, Regioregular, head-to-tail coupled poly(3-alkylthiophenes) made easy but the GRIM method investigation of the reaction and the origin of regioselectivity, Macromolecules, 34 4324-4333, 2001. 

Scheme 7.15 Polymerization of l,4-dibromo-2,5-dihexyloxybenzene using the GRIM method.

Subsequently, several examples have been reported of fully conjugated diblock copolymers synthesized by Kumada polycondensations (Scheme 7.20). Typically, the monomers are prepared by the modified GRIM method, as this affords a greater control over the polymerization [149]. Yokozawa reported a detailed investigation into the block copolymer containing a hydrophobic and a hydrophilic... 

Table 9.1 is a quick reference to the large number of side-chain functionalized PTs that have been synthesized to date. All of these have been covered throughout the chapter. The primary methods of synthesis used have been designated as Method A (McCullough), Method B (Rieke), Method C (GRIM), Method D (Stille), Method E (FeCl3), and Method F (derivatization). Please refer to the previous section for the general schemes of these synthesizes. 

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

Scheme 2.6 Proposed mechanism of end-capping of regioregular poly(3-alkylthiophene) synthesized by Crig-nard metathesis (GRIM) method...

Terminal ring functionalization has been explored as a route to block copolymer synthesis. The Stille coupling approach affords Br and RsSn termini on an isolable product. Iraqi and Barker isolated a low-A/ fraction (DP 14) then homo-cross-coupled to increase Af (DP ra 28), thus demonstrating telechelic utility [43]. The nature of the nickel-initiated cross-coupling polymerization (GRIM method) allows chain extension from the quasi-living end until the reaction is terminated. Controlled blocks of HT-PHT with HT-PDDT were prepared by changing the monomer [63]. 

Method A (McCullough), Method B (RIeke), Method C (GRIM), Method D (Stille), Method E (FeCIs), Method F (Suzuki) Method C (post-functionallzation) Method H (Ullmann). 

Figure 2.10 MALDI-TOF mass spectrum of regioregular poly(3-hexylthiophene) synthesized by the GRIM method (M = 5476 g mol Mw = 5930 g/mol PDi = 1.08)...

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