Polyoctenamer

Polyoctenamer trans-ocX.en.e mbber) is manufactured in Europe by Hbls AG at 12,000 t/yr under the trade name Vestenamer. Components for the manufacture of polydicyclopentadiene (PDCPD), a Hquid mol ding resin, are produced by Hercules in the United States (13,600 t/yr), by Teijin in Japan (3000 t/yr), and by Shell in Europe, under the trade name Metton they are also produced by Goodrich in the United States and Japan under the trade name Telene. 

Unsubstituted monocyclic mono-olefins, e.g. cyclopentene and cyclo-octene, which yield polypentenamers and polyoctenamers respectively. 

Rather more success has been achieved by trans-polyoctenamer, which was introduced by Hiils in 1980 under the name Vestenamer. The two initial grades had trans -contents of approx. 80 and approx. 62%. The polymers have a low molecular weight, and above the T, which increases with increasing transcontent once the latter exceeds 30% and is about 60°C with the high trans-grades, the polymer on its own has a very low melt viscosity. Below the melting... 

Polynorbomene (PNR), polyoctenamer and hydrogenated nitrile rubber (HNBR)—this chapter... 

Another example is the metathesis of cyclooctene, which produces poly-octenylene, an elastomor known as trans-polyoctenamer ... 

The data of Table II indicate that the etch rates for CB and its "homologues"—TP, CO (or TO), and EPM—tend to increase monotonically with a decrease in vinylene (-CH=CH-) unsaturation. The elastomeric EPM was chosen instead of crystalline polyethylene as a model for the fully saturated CB to avoid a morphology factor in etch rates, as was observed with crystalline TB. The difference in etch rates for the partially crystalline TO and the elastomeric CO (ratio of about 1.2 1.0) is attributable more to a morphology difference between these polyoctenamers than to the difference in their cis/trans content. Cis/trans content had likewise no perceptible effect on etch rates in the vinyl-containing polybutadienes (see Table I) if there was a small effect, it was certainly masked by the dominant effect of the vinyl groups. 

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. 

GRAFTING OF HINDERED AMINES GROUPS ON EPDM AND POLYOCTENAMER VIA PHOTO-HYDROPEROXIDATION... 

In the present work, we performed the hydroperoxidation of unsaturated polymers as EPDM or polyoctenamer by using singlet oxygen photo-generated at 365 nm by anthracene / O2. The resulting hydroperoxidized polymer (POOH) was then decomposed by UV irradiation (X > 300 nm) in the presence of unsaturated monomers or nitroxyl radicals. The efficiency of these new grafted polymers as new photo- and thermo-stabilizers will be finally demonstrated. 

EPDM with different contents of 5-ethylidene-2-norbornene (VISTALON 7500 (VIST), EXXON, 0.7 mol. kg 1 POLYSAR 585, (POLY) HOECHST, 1.0 mol. kg 1) and polyoctenamer (VESTENAMER, (VEST) HULS, 9.1 mol. kg 1) were first precipitated from toluene solutions to remove possible additives. 

The exact position of nitrate bands (at 1274 and 1276 cm 1 for EPDM and polyoctenamer respectively) is consistent with the selective formation of secondary hydroperoxides (a)15. 

Figure 4. IR characterization of graftings on polyoctenamer (film thickness = 100 p.m) (reproduced with permission from reference 10)...

Hydroperoxidation was also successful in the case of toluene solutions of both EPDM and polyoctenamer. Some differences in the course of the reaction were however revealed, -the consumption of anthracene is much slower as in the case of the film and additional introduction of anthracene is not necessaty to reach high hydroperoxide contents ... 

Photoageing at X>300 nm. The good photoprotective effect of polyoctenamer (VEST) grafted with PPA and St-NO has been reported elsewhere13. 

Finally, all the additives prepared by hydroperoxide intermediates increase dramatically the life time (both in photo and thermal ageing) of elastomers such as EPDM(ENB) and polyoctenamer whose the original stabilities are well known to be very low. 

Copolymers of ethylene (E) or propylene (P) with acrylic acid (AA) or methacrylic acid (MA) were obtained from SP2 (USA) and used as received (EAA, PAA, PEAA, PMA). Copolymers of ethylene and vinyl alcohol (EVOH) were prepared by hydrolysis (NaOH 0,5M in methanol, reflux, 48 h), of commercial ethylene-vinyl acetate copolymers (EVA, Elf-Atochem) containing 5, 9, 14, and 18 w% of acetate. Hydroperoxides of EPDM based on 5-ethylidene-2-norbornene (0.7 mol Kg 1, Exxon) and polyoctenamer (Vestenamer, VEST, Hiils) resulted from a reaction of polymer films with singlet oxygen. 

Moreover, the treatment of polyoctenamer film with hydrogen bromide gas was also tested. The yield was poor in these conditions it is why the reaction was finally performed in a chloroform solution of the polymer (see exp. part). 

Low Voltage Mass Spectrometry. The nominal parent mass numbers of the various components in the low molecular weight extractable fractions obtained from polyoctenamer and poly-1,5-octadienamer are listed in Table I. Quantitative estimation of the relative amounts of individual components were not carried out owing to experimental difficulties. The large variation in the volatilities of the various oligomers limits this procedure to the determination of molecular weights of the oligomers. 

Figure 6. Comparison of cyclooctene extractable macrocyclics obtained by catalyst treatment of high molecular weight polyoctenamer with extractable macrocyclics obtained during cyclooctene polymerization...

Figure 8. NMR spectra of polyoctenamer, extractable macrocyclic fraction from polyoctenamer and polyoctenamer obtained by polymerization of the extractable macrocyclic fraction...

---