Entropically driven ring-opening metathesis polymerization (ED-ROMP) of macrocyclic olefin-containing oligoamides

Acyclic diene metathesis (ADMET) polymerization of allyl undec-10-enoate and some related esters

“…We suggest that with the diallyl esters an intermediate analogous to 6 is formed and that this is sufficiently stable to suppress polymerization. A similar effect has also been observed when a,x-divinyl amides are treated with catalyst 1 [33]. One possible explanation for the polymerization of allyl undece-10-enoate (7) is that it is achieved indirectly via Table 2 Percentages of head-to-tail, head-to-head and tail-tail linkages in polymers 15-18 a The set of eight signals for the in-chain olefinic C-atoms were assigned on the basis of the following.…”

“…The signal for the Z-isomer will usually appear at a shift value about 0.5 ppm lower than the Eisomer (see Ref. [33]). Usually the latter will be the main isomer present.…”

“…f Major mass peaks were observed due to the species indicated. g By 1 H NMR spectroscopy (see Ref [33]. for an example) the DPs of the polymers were as follows: 14, 60; 15, 64; 16, 80; 17, 46; 18, 82. h By 1 H NMR spectroscopy the DPs of the oligomers from the various monomers were as follows: 4, 4; 19, 3; 20, 6. i 50 mol% of each monomer was used.…”

Unsaturated PA X,20 from Renewable Resources via Metathesis and Catalytic Amidation

“…Tastard et al described the indirect polymerization of a variety of amide containing a,v-dienes by first performing a ring-closing metathesis (RCM) reaction at high dilution in chloroform or THF with 1 mol-% of the Grubbs second generation catalyst to obtain an amide containing macrocycle in moderate to good yields. [15] These macrocyles were then further polymerized by an entropically driven ROMP (ED-ROMP) using 0.5 mol-% of the same catalyst, to give the final polyamides (including PA 8,20). The properties of the resulting polymers were not described.…”

“…Moreover, the direct ADMET polymerization of amide containing a,v-dienes was investigated in this study revealing that only oligomers were formed with 1% of the Grubbs second generation catalyst after 4 d of reaction time. [15] Moreover, many different types of long chain PAs obtained by conventional melt polycondensation are described in the literature. For instance, the long chain diacids octadec-9-enedioic acid, [16] icosanedioic acid, [17,18] 1,18-octadecane diacid, [19] and 1,16-hexadecane diacid [20] were polymerized with various aliphatic diamines, ranging from 2 to 12 methylene units.…”