Poly ring-opening metathesis

Ring-opening metathesis polymerization (ROMP) of 1,4-cyelooctadiene was used to prepare poly(l,4-B) terminated with halo end groups.647 This was then used as a macroinitiator of ATRP with heterogeneous Cu bpy catalysts to form PS- >/ti /r-poly(l,4-B)-WoeA -PS and PMMA-Moc.T-poly(l,4-B)-Wof A-PMMA. 

We have reported the first example of a ring-opening metathesis polymerization in C02 [144,145]. In this work, bicyclo[2.2.1]hept-2-ene (norbornene) was polymerized in C02 and C02/methanol mixtures using a Ru(H20)6(tos)2 initiator (see Scheme 6). These reactions were carried out at 65 °C and pressure was varied from 60 to 345 bar they resulted in poly(norbornene) with similar conversions and molecular weights as those obtained in other solvent systems. JH NMR spectroscopy of the poly(norbornene) showed that the product from a polymerization in pure methanol had the same structure as the product from the polymerization in pure C02. More interestingly, it was shown that the cis/trans ratio of the polymer microstructure can be controlled by the addition of a methanol cosolvent to the polymerization medium (see Fig. 12). The poly(norbornene) prepared in pure methanol or in methanol/C02 mixtures had a very high trans-vinylene content, while the polymer prepared in pure C02 had very high ds-vinylene content. These results can be explained by the solvent effects on relative populations of the two different possible metal... 

V.P. Conticello, D.L. Gin, and R.H. Grubbs, Ring-opening metathesis polymerization of substituted bicyclo[2.2.2]octadienes a new precursor route to poly(p-phenylene vinylene), J. Am. Chem. Soc., 114 9708-9710, 1992. 

Curable poly(dicyclopentadiene), (V), was prepared by Konze et al. (4) using ring-opening metathesis polymerization with tungsten oxychloride and diallyldimethylsilane. 

Ruthenium-catalysed Ring-Opening Metathesis Polymerization (ROMP) 29 526 529 (Equation 10) and Pd(tppms)3-catalysed synthesis of water soluble poly-(p-phenylene) derivatives (Equation ll).530 The latter is a special example of a Suzuki coupling (see earlier). 

Polymers of monocyclic olefins (cyclopentene, cyclooctene) produced by ring-opening metathesis are linear elastomers. Their properties are somewhat similar to those of poly eri-1,4-hn i.idiene). Polymers of dicy-clopentadiene produced with the same catalysts are heavily cross-linked resins displaying high toughness and tensile strength as well as excellent impact strength at low temperatures. 

Partially substituted derivatives of polyacetylene are synthesized via the ring-opening metathesis polymerization (ROMP) of cyclooctatetraene (COT) and its derivatives. Certain poly-COT derivatives afford soluble, highly conjugated poly acetylenes. These materials exhibit large third-order optical nonlinearities and low scattering losses. 

The ring-opening metathesis polymerization of dicyclopentadiene was monitored by ultrasonic spectroscopy.16 The thermoset poly(dicyclopentadiene) is formed by ringopening and cross-linking in a reaction injection molding system. A reaction cell with a plastic window was constructed for use with pulse echo ultrasonic spectroscopy. Realtime measurements of density, longitudinal velocity, acoustic modulus and attenuation were monitored. Reaction kinetics were successfully determined and monitored using this technique. 

Rhenium complex (37) has been used in the ring-opening metathesis polymerization of strained alkenes such as norbornene.37 The alkenes of the polymer backbone are predominantly Z, the polymer exhibiting high molecular weight and poly-dispersity. 

Recently, Dai, Su, and coworkers synthesized the block copolymer of polythiophene and polypyridine from the vinyl-terminated polythiophene (Scheme 102) [336]. Meijer and coworkers used an allyl-terminated polythiophene to synthesize a block copolymer of poly(3-hexylthiophene) and polyethylene the ring-opening metathesis polymerization of cyclooctene in the presence of the allyl-terminated polythiophene was followed by hydrogenation (Scheme 103) [337]. 

Norbornene polymerization was initiated selectively on the surface of SWCNTs via a specifically adsorbed pyrene-linked ring-opening metathesis polymerization initiator (Fig. 1.20). The adsorption of the organic precursor was followed by cross-metathesis with a ruthenium alkylidene, resulting in a homogeneous noncovalent poly (norbornene) (PNBE) coating [249]. 

The products of the ring-opening metathesis polymerisation of cycloolefins, poly(l-alkenylene)s, are known as polyalkenamers according to the nomenclat-... 

Acyclic a, co-diene metathesis is a method for the synthesis of poly(l-alkeny-lene)s, which are also available from the ring-opening metathesis polymerisation of cycloolefins [13-15]. 

Ring-opening metathesis polymerization (ROMP) has been used to make precursor polymers to PAVs as shown in Scheme 6.10 for the synthesis of poly (naphthalene vinylene)s 43 by Grubbs and coworkers [55, 56], ROMP has also... 

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