This chemistry and technology of hydrogenation of diene elastomers have substantially grown during the past decade. New applications of hydrogenated elastomers have emerged. Homogeneous hydrogenation has several advantages over heterogeneous hydrogenation because of its higher selectivity, faster rate and cleaner end products. However, separation of catalysts and recycle/reuse of expensive metals still poses problems. The preferred alternative for the hydrogenation of elastomers in solution is the use of Zeigler type catalyst which are less expensive than the noble metal catalysts like Rh, Pd etc. However, such catalysts are not effective when strongly coordinating groups are present in the elastomer. One approach would be to use transition metals, which have less tendency to coordinate with polar monomers in the elastomer. Research is also warranted in the use of less expensive metals for elastomer hydrogenation (Ni, Co, Ru). Use of large quantities of solvent (to keep the solution viscosity low) is another significant cost center in elastomer hydrogenation. Novel agitator systems/reactor configuration to handle higher concentration of rubber in solution, yet provide adequate heat and mass transfer in gas-liquid hydrogenation reaction, needs to be explored. Hydrogenation of diene elastomers in the latex form using water soluble catalyst appear to be hold great promise at the present time since many diene elastomers (like SBR, CR and NBR etc.) are commercially produced directly in the form of latex. Creative exploitation of biphasic catalysts for hydrogenation is expected to gain momentum since early results look promising. This would require greater fundamental understanding of the aqueous-organic interphase in a latex process and the mechanism of transport of catalytic reagent across this interphase. More studies are needed to achieve homogeneous chemical reaction inside of each individual latex particles.

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We previously reported that the polyamide 3a derived from bis(5-carboxy-1,3-phenylene)-32-crown-10 (BCP32C10, 1a) and 4,4‘-oxydianiline (ODA, 2) was completely insoluble and attributed this to the formation of mechanical cross-links via self-threading of the crown ether moieties by the amide backbone through hydrogen bonding. Moreover, polycondensation of 1a with bis[4-(m-aminophenoxy)phenyl]phenylphosphine oxide (m-BAPPO, 4) produced polyaramide 5a that, like its analogue 3a, was insoluble in all solvents examined, including H2SO4. In the present work bis(5-carboxy-1,3-phenylene)−(3x+2)-crown-x ethers [BCP(3x+2)Cx] with 26-membered (BCP32C10, 1b), 20-membered (BCP20C6, 1c) and 14-membered (BCP14C4, 1d) rings were utilized to investigate further the proposed topological branching via in situ threading during polymerization. Condensation of BCP26C8 (1b) with ODA (2) and m-BAPPO (4) gave two new poly(amide crown ether)s, 3b and 5b, which were soluble in dipolar aprotic solvents. However, the GPC traces of aramides 3b and 5b exhibited bimodal behavior indicative of two distinct molecular weight fractions, one very high, DPn > 800! Similarly the aramide 3c formed by condensation of BCP20C6 (1c) and ODA (2) displayed a bimodal GPC curve. As a reference system BCP14C4 (1d) was prepared and polymerized with ODA; the resultant aramide 3d displayed a monomodal GPC trace and relatively narrow molecular weight distribution. Mass spectrometric studies show that cyclic aramides (lactams) form in the larger crown ether-based systems 3b and 5b. Model aramide 6 from isophthalic acid and ODA also contains cyclic polymers, as expected from Kricheldorf's recent results, but has a “normal” molecular weight distribution. Mass spectrometric examination of aramides 3c and 3d does not indicate any cyclic polymer formation. Inasmuch as lactam formation by itself does not necessarily produce branching or cross-linking, e.g., 6, we conclude that threading of the crown ether moieties is the key step, leading to polypseudorotaxane, polyrotaxane and polycatenane structures to an extent dependent upon the their cavity size and the propensity for cyclization of the polymer backbone.

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