1,2-Decadiene

One of the butadiene dimeri2ation products, COD, is commercially manufactured and used as an intermediate in a process called FEAST to produce linear a,C0-dienes (153). COD or cyclooctene [931-87-3], obtained from partial hydrogenation, is metathesi2ed with ethylene to produce 1,5-hexadiene [592-42-7] or 1,9-decadiene [1647-16-1], respectively. Many variations to make other diolefins have been demonstrated. Huls AG also metathesi2ed cyclooctene with itself to produce an elastomer useful in mbber blending (154). The cycHc cis,trans,trans-tn.en.e described above can be hydrogenated and oxidi2ed to manufacture dodecanedioic acid [693-23-2]. The product was used in the past for the production of the specialty nylon-6,12, Qiana (155,156). 

Figure 8.3 Wagener s ADMET of 1,9-decadiene using Schrock s [W] catalyst.

Kinetic studies using 1,9-decadiene and 1,5-hexadiene in comparison widi catalyst 14 and catalyst 12 demonstrate an order-of-magnitude difference in their rates of polymerization, widi 14 being the faster of the two.12 Furdier, this study shows diat different products are produced when die two catalysts are reacted widi 1,5-hexadiene. Catalyst 14 generates principally lineal" polymer with the small amount of cyclics normally observed in step condensation chemistry, while 12 produces only small amounts of linear oligomers widi die major product being cyclics such as 1,5-cyclooctadiene.12 Catalyst 12, a late transition metal benzylidene (carbene), has vastly different steric and electronic factors compared to catalyst 14, an early transition metal alkylidene. Since die results were observed after extended reaction time periods and no catalyst quenching or kinetic product isolation was performed, this anomaly is attributed to mechanistic differences between diese two catalysts under identical reaction conditions. 

The following steps are performed in an argon atmosphere glovebox. In a 50-mL round-bottom flask equipped with a Teflon magnetic stirbar, 2.03 g (14.7 mmol) of previously distilled and degassed 1,9-decadiene (9) (Aldrich) and 27.6 mg (3.61 x 10 2 mmol) of Schrock s catalyst (14) (400 1) are combined. In a matter of seconds, the catalyst is dissolved into the monomer and a vigorous evolution of ethylene is observed. The flask is sealed with a Teflon vacuum adapter and removed from the box. The polymerization vessel is immediately connected to the vacuum line, placed into an oil bath, and stirred at 30°C. Intermittent vacuum... 

Figure 8.8 ADMET polymerization of (a) 1,9-decadiene and (b) 6-methyl-1,10-undecadiene.

ADMET polymers are easily characterized using common analysis techniques, including nuclear magnetic resonance ( H and 13C NMR), infrared (IR) spectra, elemental analysis, gel permeation chromatography (GPC), vapor pressure osmometry (VPO), membrane osmometry (MO), thermal gravimetric analysis (TGA), and differential scanning calorimetry (DSC). The preparation of poly(l-octenylene) (10) via the metathesis of 1,9-decadiene (9) is an excellent model polymerization to study ADMET, since the monomer is readily available and the polymer is well known.21 The NMR characterization data (Fig. 8.9) for the hydrogenated versions of poly(l-octenylene) illustrate the clean and selective nature of ADMET. 

Figure 8 The air-stable 77-conjugated organoboron segmented block copolymer (8) obtained by the hydroboration polymerization of allyl-telechelic polyisobutylene, 1,9-decadiene, and tripylborane. (Adapted from ref. 28.)...

Representative data illustrating the influence of Lewis base functional groups in the ADMET reaction are shown in Table 1. When molybdenum catalysts are used to polymerize ether or thioether dienes, little change in reaction rate is observed as compared with the standard, 1,9-decadiene, which possesses no heteroatoms in its structure. When a sulfur atom is three carbons atoms away from the alkene site, the reaction rate is reduced approximately one order of magnitude otherwise, the kinetics are all essentially unaffected [20a]. 

FEAST (further exploitation of advanced shell technology), another Shell process142-144 commercialized in 1986, utilizes a highly active promoted rhenium-on-alumina catalyst (100°C, 2 atm) to synthesize 1,5-hexadiene from 1,5-cyclo-octadiene [Eq. (12.30)] and 1,9-decadiene from cyclooctene [Eq. (12.31)] ... 

The synthesis of polyoctenamer has been commercialized by Huels.150 In contrast with the transformation of cyclooctene to 1,9-decadiene [Eq. (12.31)], homogeneous catalyst compositions, such as WClg + EtAlCl2, are used to promote ring-opening metathesis polymerization of cyclooctene. A polymer of narrow molecular-weight distribution with high trans content (55-85%) called Vestenamer is produced and used as blend component in different rubbers and thermoplastics. 

The proposed idea that metal alkyhdene complexes are be able to catalyze olefin metathesis was confirmed in 1980 [8] and consolidated in 1986 by Schrock with the development of the first well-characterized, highly active, neutral tungsten (Cl, Fig. 3) [9] and molybdenum (C2) [10] alkylidene complexes. These complexes were able to catalyze both the metathesis of different olefins and the ROMP of functionalized norbomene to polynorbomene with low polydispersities [11]. Moreover, these catalysts were used by Wagener and coworkers to perform the first quantitative ADMET polymerization [12] and copolymerization [13] of 1,5-hexadiene and 1,9-decadiene. However, the low stability of these catalysts in... 

Tab. 4.13 n-Decane-, 1 -hexadecene-, and 1,9-decadiene-water partition coefficients (molar concentrations) for various solutes at 25 °C. (Reprinted from Tab. 1 of ref. 49 with permission from Bertelsmann-Springer)... 

Metathetical polycondensation of acyclic dienes has not been successful with conventional catalysts used for the ring-opening metathesis polymerisation of cycloolefins, which is due to the fact that Lewis acids are usually present, and produce deleterious side reactions [13,16,17]. Only Lewis acid-free, well-defined catalysts have been successfully applied for acyclic diene metathesis polycondensation the key success has been to choose catalysts that obviate other pathways not involving the metathesis mechanism [18-20]. It was Wagener et al. [16,21] who first were able to convert an acyclic a, co-diene (1,9-decadiene), by using an acid-free metal alkylidene catalyst, to a high molecular weight... 

CM of 1,9-decadiene with an excess of trialkoxy- and trisiloxy-substituted vinylsilanes results in the formation of , -l,10-bis(silyl)deca-l,9-dienes (Eq.37) [67],... 

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