Copolymerization 1,5-cyclooctadiene

The gas chromatographic analysis of the unreacted monomers in the experiments from Table II discloses a constant C5/C8 ratio comparing the starting comonomer composition to the final composition. This means that monomer conversion is the same for 1,5-cyclooctadiene and cyclopentene in the copolymerization so that copolymer compositions are equal to the charge ratios. This result is consistent with the product analysis by 13C NMR spectroscopy where the copolymer composition is nearly identical to the starting comonomer composition. 13C NMR is used to determine the composition of the cyclopentene/1,5-cyclooctadiene copolymers as part of a detailed study of their microstructure (52). The areas of peaks at 29-30 ppm (the pp carbon from cyclopentene units) and at 27.5 ppm (the four ap carbons from the 1,5-cyclooctadiene) are used to obtain the mole fractions of the two comonomers (53, 54, 55). 13C NMR studies and copolymer composition determinations are described by Ivin (51, 56, 57) for various systems. 

The Diels-Alder adduct of 1,5-cyclooctadiene with hexachlorocyclo-pentadiene was homopolymerized or copolymerized (113) with cyclic olefins using tungsten halide salts with either organoaluminum or organo-tin cocatalyst to give thermally stable flame- and oil-resistant polymers. 

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... 

Poly(l,4-butadiene) segments prepared by the ruthenium-mediated ROMP of 1,5-cyclooctadiene can be incorporated into the ABA-type block copolymers with styrene (B-106) and MMA (B-107).397 The synthetic method is based on the copper-catalyzed radical polymerizations of styrene and MMA from the telechelic poly(butadiene) obtained by a bifunctional chain-transfer agent such as bis(allyl chloride) or bis-(2-bromopropionate) during the ROMP process. A more direct route to similar block copolymers is based on the use of a ruthenium carbene complex with a C—Br bond such as Ru-13 as described above.67 The complex induced simultaneous or tandem block copolymerizations of MMA and 1,5-cyclooctadiene to give B-108, which can be hydrogenated into B-109, in one pot, catalyzed by the ruthenium residue from Ru-13. 

Cycloaddition copolymerization of diynes (Equation 44, product 46) such as 3,11-tetradecadiyne, 3,9-dodecadiyne, 1,3- or 1,4-di(2-hexynyl)benzene with CO2 was successfully carried out in the presence of zero-valent nickel catalyst [NiCOD)2 2P( -C8Hi )3] prepared from bis(l,5-cyclooctadiene)nickel and tri-n-octylphosphine ligand Synthesis of soluble ladder-type polymers (47) was carried out by cycloaddition copolymerization of 1,7-cyclotridecadiyne (48) and CO2 (equation 45). 

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). 

Copolymerization of Sulfur Dioxide with 1,5-Cyclooctadiene—General Method [52]... 

TABLE XII Representative Copolymerizations of Sulfiir Dioxide and IjS-Cyclooctadiene"... 

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. 

Palladium(II) complexes (77a-c) have been prepared from (cod)Pd(Me)Cl (cod = cyclooctadiene-1,5) and pyridinylphosphoranimines (76a-c). Treatment with AgBp4 in MeCN solution affords the corresponding cationic complexes (78a-c), of which (78b) shows the highest catalytic activity in copolymerizations of norbornene with CO or ethylene. ... 

Other copolymers with interesting mechanical properties have been reported in the literature. Haynes et al. copolymerized PLA with perfluoro-polyether (PFPE) and observed an increase of the elongation at break up to 300% with 5% of PFPE. Another alternative was described by Pitet et al./ who synthesized ABA triblock copolymers from 1,5-cyclooctadiene (COD) and D,L-lactide. The triblocks were considerably tougher than PDLA, especially for poly-COD low midblock contents. An elongation at break of 180% was obtained for a triblock containing 0.76 volume fraction of PLA. 

The so-called palm tree-like copolymers consist in an arrangement of nB blocks with one A block of much larger size in a heteroarmed star architecture [8]. These architectures were obtained by sequential copolymerization of norbornenyl-PS macromonomers with a molecular comonomer, namely cyclooctadiene (COD), Scheme 6. Dumbbell-shaped copolymers can be viewed as double stars that are linked through a linear block. They are obtained upon using palm tree-like copolymers to trigger the polymerization of a new amount of PS macromonomers. Scheme 6. 

The monomer cis, cis-1, 5-cyclooctadiene, in contrast to 1,3-cyclooctadiene, thermally copolymerize with Heating a 1 2 (MA 1,5-... 

Copolymerization of 1,5-cyclooctadiene with cyclooctatetraene will form random copolymers (61), displaying interesting electrical and optical properties ... 

By controlling the ratios of 1,5-cyclooctadiene to cyclooctatetraene, products with varying conjugation length and electrical properties will be produced. When 1,5-cyclooctadiene is copolymerized with hexa-chlorocyclopentadiene [41b], elastomeric copolymers (62), having improved chemical resistance, can be obtained ... 

Analogous copolymers are obtained from 1,5-cyclooctadiene and other ,j8-unsaturated diacids, diesters, or half-acid esters 17). Sulfuryl chloride copolymerizes with 1,5-cyclooctadiene to yield polymers of moderately high molecular weight ( 5). Radical or ultraviolet initiation is effective. The polymers [38], being sulfonyl chloride-terminated, polymerize with diamines to higher molecular weight polymers 48). 

Cyclooctadiene is reported to yield a different type of product in a similar copolymerization. The polymer [56] was produced at room temperature in acetone with lithium nitrate (149). Its inherent viscosity was 0.80. Oxygen as the initiator in sulfolane gives polymer with an inherent viscosity of 1.94. High polymer was also obtained from dicyclopentadiene in this polymerization (149). A transannular sulfonyl bridge was postulated to exist in its structure. 

---