Ring opening metathesis polymerization Subject

Numerous friends and colleagues in the field of metathesis (the soldiers to whom we dedicate this book) have encouraged us to believe that a new book incorporating these recent developments would be both timely and welcome. We felt, however, that the book should still outline the historical development of the subject and not just be a supplement to the original book. This has necessarily meant some compression of earlier material and some restriction of discussion. The title has been expanded to include the words Metathesis Polymerization , which embraces not only ring-opening metathesis polymerization (ROMP), but also the metathesis condensation reactions of acyclic dienes (ADMET) and the addition reactions of acetylenes. The division of the material and the subjects of the chapters follow the same pattern as before. The literature has been covered up to mid-1996. 

PLA-functionalized polyoxanorbomenes with one or two exo-FLA chains as well as two endo-, exo-chains were prepared using Sn(Oct)2 as a catalyst in the presence of mono- or dialcohol derivatives of oxanorbomenes [73]. These macromonomers are then subjected to ring-opening metathesis polymerization (ROMP) to yield graft copolymers (Figure 4.8). 

Polymers 48a and 48b were also subjected to ring-opening metathesis polymerization reactions to produce crosslinked polymers 50a and 50b. Scheme 21 shows the structure of these polynorbomene networks. These polymers were insoluble in all organic solvents tested. 

This facile solution for catalyst immobilisation follows a more complex approach reported by Mayr et al. [246], This research group attached the imidazolium salt to a nor-bomene unit that was then subjected to a ring opening metathesis polymerisation (ROMP) reaction to form the polymeric NHC precursor (see Figure 4.77). The ROMP reaction had to be carried out with a molybdenum based Schrock catalyst because the ruthenium based Grubbs catalyst did not provide an endgroup that could be quantitatively capped with a suitable final endgroup. 

Polymerization by means of metathesis is a subject spanning more than 30 years now, with the first reactions being focused upon ring-opening metathesis chemistry. Ring opening polymerizations to produce elastic polymers are known and in fact used commercially today (Figure 1). 

Part 2 includes chapters on specific classes of cyclic monomers and their polymerization mechanisms and kinetics, their main (co)polymer architectures and related products, as well as current and future applications. Hence, siloxane-con-taining and sulfur-nitrogen-phosphorus-containing polymers are described in Chapters 3 and 4, respectively, while the polymerization of cyclic depsipeptides, ureas and urethanes, of polyethers and polyoxazolines, and of polyamides are detailed in Chapters 5, 6 and 7, respectively. Chapters 9, 10, 11 and 12 include details of polyesters prepared from either P-lactones, from dilactones, from larger lactones and from polycarbonates, while the polymerization of cycloalkanes is described in Chapter 13. It should be noted that, slightly out of place . Chapter 8 covers the subject of ring-opening metathesis polymerizahon. 

Norbomene, or bicyclo[2.2.1]hept-2-ene, is one of the better-known monomers that can be subjected to ring-opening polymerization by metathesis catalysts. This monomer, or its derivatives, produces polymers with both a ring and a site of unsaturation in the main chain repeat unit. 

---