Dicyclopentadienes ring-opening metathesis polymerization

Ring-Opening Metathesis Polymerization. Several new titanacyclobutanes have been shown to initiate living ring-opening metathesis polymerization (ROMP) systems. These have been used to make diblock and triblock copolymers of norbomene [498-66-8] (N) and its derivatives (eg, dicyclopentadiene [77-73-6] (D)) (Fig. 2) (41). 

D. Schaubroeck, S. Brughmans, C. Vercaemst, J. Schaubroeck and F. Verpoort, Qualitative FT-Raman investigation of the ring opening metathesis polymerization of dicyclopentadiene, J. Mol. Catal. A Chem., 254, 180-185 (2006). 

Figure 1.7 Ring opening metathesis polymerization of dicyclopentadiene using transition metal catalysts...

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

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. 

Figure 5.46. Ring-opening metathesis polymerization (ROMP) of dicyclopentadiene catalyzed by Grubbs catalyst.

Matyjaszewski et al. demonstrated that living ring opening metathesis polymerization (ROMP) could also be combined with ATRP to produce novel block copolymers [292]. ROMP of norbornene (NB) and dicyclopentadiene (CPD) were performed using an Mo-alkylidene complex, followed by reaction with p-(bro-momethyl) benzaldehyde to generate a benzyl bromide terminated polymer capable of being used as a macroinitiator for ATRP (Scheme 41). 

Well-defined diblock and triblock copolymers (pdi = 1.08-1.14) were first prepared by ring-opening metathesis polymerization by sequential monomer addition of norbor-nene, dicyclopentadiene and benzonorbor-... 

Free-radical chemistry is the most widely used but not the only one. Frontal curing of epoxy resins has been studied (14-18). Begishev et al. studied anionic polymerization of e-caprolactam (19). Frontal Ring-Opening Metathesis Polymerization (FROMP) has been successfully achieved with dicyclopentadiene (20) and applied to making IPNs (21). Mariani et al. have achieved FP with urethane chemistry (22). 

TABLE 4. Ring opening metathesis polymerization of dicyclopentadiene (DCPD) with the carbyne tungsten (VI) complexes Cl3(dme)WsC Bu (A), ( BuO)3WsC Bu (B), Np3W=C Bu (C) as catalysts reaction time 24 h, pa = polymerization activity [mmol DCPD mmol catalyst h ] (calculated from the turnover of monomer after 1 h), GPC Polystyrene standard solvent THE, temperature 25°C. 

Ring-opening metathesis polymerization of dicyclopentadiene (DCPD) can take place by two different pathways in the first, the reaction occurs with opening of the norbornene unit leading to linear polydicyclopentadiene while in the second both the norbornene and cyclopentene rings are successively opened forming a cross-linked polymer (Scheme 1) [1-3]. Due to substantial differences in reactivity of the double... 

Hayano, S. Kurakata, H. Uchida, D. Sakamoto, M. Kishi, N. Matsumoto, H. Tsunogae, Y. Igarashi, I. Stereospecific ring-opening metathesis polymerization of ewrfo-dicyclopentadiene by Schrock-Hoveyda catalyst and novel Mo- and W-based complexes. Development of crystalline hydrogenated poly(e rfo-dicyclopentadiene). Chem. Lett. 2003, 32, 670-671. 

Frontal polyurethane polymerization [13-15], frontal atom transfer radical polymerization [16], and frontal ring-opening metathesis polymerization (ROMP) [17] all suffer from short pot lives that is, bulk polymerization occurs in less than an hour. In some cases, the only way to avoid even faster bulk polymerization is to cool the reagents. For example, with frontal ring-opening metathesis polymerization of dicyclopentadiene with a Grubbs catalyst, the starting materials had to be frozen to prevent rapid bulk polymerization [17]. 

Y., and Pojman, ).A. (2001) Frontal ring-opening metathesis polymerization of dicyclopentadiene. Macromckcules,... 

Abstract Several routes to access ruthenium (Ru)-vinylidene complexes are described, the majority of which employ alkynes and a Ru source as the starting materials. The successful application of Ru-vinylidenes as efficient pre-catalysts for the synthesis of carbocyclic and heterocyclic compoimds by ring-closing metathesis (RCM) of a, -dienes, and in the synthesis of polymers by ring-opening metathesis polymerization (ROMP) of cyclooctene, norbomene, 5-substituted norbomene, and dicyclopentadiene is fully illustrated. Relevant aspects concerning the activity and selectivity of this type of Ru complexes in metathesis reactions are highlighted. 

Mariani et first demonstrated that FP could be achieved with the ring-opening metathesis polymerization (ROMP) of dicyclopentadiene. In a typical run, a glass test tube already containing suitable amounts of solid Grubbs catalyst (GC) and PPh3 was filled with liquid dicyclopentadiene at 35 °C. After the reagents dissolved, the reaction mixture was cooled to 27 ° C in order to permit solidification of the solution. 

Fig. 8 Ring-opening metathesis polymerization of Dilulin and dicyclopentadiene [48] (reproduced with kind permission from Elsevier— License no. 3891281355385)...

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