Cyclooctene copolymerization

Conversions of about 80% were obtained within a few minutes at 90°C. The polymer could also be cleaved by cross-metathesis with an excess of 4-octene which gave, as the main product, 9-tridecenyl-7-undecenoate, thus confirming the structure assignment as indicated in Eq. (62). The unsaturated lactone was also copolymerized with cyclooctene, 1,5-cy-clooctadiene, and cyclopentene under the previously stated conditions to afford linear copolymers which were high molecular weight, unsaturated, rubbery polyesters (110). 

The ROMP of cyclooctene-5-methacrylate and its copolymerization with cyclooctadiene is catalysed by 19 in the presence of p-methoxyphenol as radical inhibitor. The double... 

Alternating polymers can be produced by taking advantage of the functional group tolerance, high activity, and chemoselectivity of 3. Copolymerization of cycloalkenes such as cyclooctene or cyclopentene with diacrylates affords regular alternating polymers (Eq. 15) [32]. Based on the different reactivity of the two monomers (class 1 and class 2, respectively) the more... 

Ruthenium complex (4a) provided a new general route to alternating copolymerization utilizing cyclooctene and diacrylates via olefin metathesis (equation 65). Nuclear magnetic resonance (NMR) studies demonstrated that under the reaction conditions cyclic monomers like cyclooctene... 

Jeon et al. have recently reported on ring-opening metathesis copolymerizations of cyclooctene and the PGSS-norbornylene monomer performed with Grubbs s catalyst. Random copolymers were then formed and fully charac-... 

The ROMP of cyclooctene-5-methacrylate and its copolymerization with cyclooctadiene is catalyzed by Ru(=CHCH=CPh2)(Cl)2(PCy3)2 in the presence of p-methoxyphenol as radical inhibitor. The double bonds in the methacrylate groups are inert towards metathesis. After chain transfer with ethyl vinyl ether to release the polymer from the ruthenium centre, it can be cross-linked by radical polymerization through the methacrylate side-chains (Maughon 1995). 

High efficiency of the cross-metathesis of 1,9-decadiene and ROM/CM of cyclooctene with vinylsilanes points to a possibility of effective runs of the ADMET copolymerization of 1,9-decadiene [40] and tandem ROM/CM polymerization of cyclooctadiene [20], in both cases with divinylsilicon compounds. The reactions have proceeded according to Eq. 11, yielding polymeric material isolated and analyzed by GPC and NMR methods. 

Metathesis of 1,9-decadiene and cyclooctene with trialkoxy- and trisiloxy-substituted vinylsilanes in the presence of Grubbs catalyst, carried out in appropriate conditions, leads to the formation of bis(silyl)diene with a high yield. Similar processes performed with divinyl-substituted siloxane lead to the formation of silicon-containing polymers (via ADMET copolymerization and tandem ROM/CD polymerization), thus opening a new convenient route to synthesis of unsaturated organosilicon copolymers. 

Yong and S wager [181] reported ring-opening metathesis copolymerizations of calixarene containing monomers with cyclooctene and norbomene to yield high molecular weight transparent elastic polymers. 

The proof that the C=C bond was itself being broken in these reactions was provided by isotopic labelling studies, first by Calderon in 1967 for the exchange reaction of but-2-ene [7,8], eq. (2), then by Boelhouwer (1968) for the reaction of propene [9], eq.(3), and later by DallAsta in 1971 for the ring-opening copolymerization of [1- C]cyclopentene with unlabelled cyclooctene [10]. 

Kaminsky and Spiehl also investigated the copolymerization of ethylene with cyclohexene, cycloheptene, and cyclooctene using the isoselective zirconocene rac-Et(Ind)2ZrCl2 under similar conditions to those used for ethylene/CPE copolymerization.Ethylene copolymerization with... 

As mentioned above, Calderon recognized in 1972 that metathesis polymerization and metathesis of acyclic olefins are two aspects of the same reaction [10]. As early as 1968 he had identified the double bonds as the reactive centers in the metathesis of acyclic olefins. Apart from the educts the metathesis reaction of dg-2-butene with 2-butene yielded only d4-2-butene, so he could exclude the cleavage of any single bond [39,40]. Dali Asta and Motroni drew an analogous conclusion for ROMP by copolymerization of 1- C-cyclopentene and cyclooctene (3). After ozonolytic degradation of the polymers the complete radioactivity was found in the C5-fraction, showing the exclusive cleavage of the double bonds (pathway (3b)) [41,42]. 

Scheme 5.11 Alternating copolymerization of cyclooctene and norbornene with an unsymmetric ruthenium catalyst.

Cycloheptene and cyclooctene can be copolymerized with ethene, though copolymer yields are about 25% of that obtained with cyclopentene [28]. Copolymers with up to 4.5 mol% of cycloheptene and 1 mol% of cyclooctene could be produced using rac-[Et(fiid)2]ZrCl2/MAO (I-l) as catalyst. Alternating copolymers of cycloheptene and cyclooctene using a constrained geometry catalyst with a benzindenyl ligand were obtained by Lavoie and Waymouth [36]. 

Copolymerization. Copolymers could be prepared from the mixtures of the norbornene derivatives. They could also be copolymerized with cycloolefins without polar group such as cyclopentene or cyclooctene. The formation of the copolymer was confirmed by elemental analysis, ir spectrum, thin layer chromatography(TLC) and differencial scanning calorimetry(DSC). 

Cyclobutene/ cyclopentene/ " methylenecyclopentene/ cyclohexene/ " cycloheptene/ cyclooctene/ bicyclo[2.2.1]hepta-2-ene (norbornene)/ " " and some derivatives of norbornene " are also known to copolymerize with MA to give noncrystalline equimolar copolymers. 

Relatively few data are published concerning the polymerization of cyclobutene, cyclopentene, cyclohexene, or cyclooctene and their substituted derivatives in the presence of cationic initiators [1], Cyclopentene and cyclohexene proved to be unreactive toward AICI3 at low temperatures (—20°C) in ethyl chloride, but they give dimers, trimers, and tetramers as well as higher polymers with BF3 and hydrogen fluoride [9, 10]. On the other hand, copolymerization of cyclohexene with styrene and a-methylstyrene in the presence of AICI3... 

The reactivity of various cycloolefins in copolymerization reactions with ethylene and 2-butene has been examined using V(acac)3/Et2AlCl and VCl4/Hex3Al as the catalysts [21]. It was observed that, while the catalyst system has little effect on the relative reactivity of the cycloolefin, the nature of the cyclic and acychc monomer proved to be quite determinant for reaction kinetics and stereospecificity. In this respect, cyclopentene and cycloheptene displayed high reactivity compared to cyclohexene and cyclooctene, while cis-2-butene was more reactive than tra 5-2-butene. These observations were rationalized by considering steric factors induced by monomers rather than catalyst activity and specificity. 

Similar copolymers (56) and (57) have been reported in the copolymerization reactions of cyclopentene with cyclooctene [35] and of cyclooctene with cyclodode-cene [36] in the presence of the foregoing catalytic systems ... 

Finally, copolymers containing polyethylene backbone and polystyryl grafts, (124), have been manufactured by ring-opening metathesis copolymerization of cycloalkenes like cyclooctene with co-norbornenyl macromonomers in the presence of the molybdenum carbene initiator Mo(NAr)(CHrBu)(OC(CH3)(CF3)2)2 [92] [Eq. (56)]. 

Thom-Cs yi, E., Kramer, P, and Hammer, J. (1994) Ring-opening copolymerization of [2.2] paracyclophane-1,9-diene (PCPDE) and cyclooctene (COE) a route to soluble products with p-phenylenevinylene sequences. Journal of Molecular Catalysis, 90,15. 

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