Linear non‐conjugated dienes from biomass as termonomers in EPDM synthesis, 3. Conventional versus metallocene catalysis

Abstract

The synthesis in the presence of the ruc-EtInd,ZrC1,/MAO catalytic system of new EPDM terpolymers based on linear non-conjugated dienes issued from biomass, 3,7-dimethylocta-l,6-diene (3,7-DMO) and 5,7-dimethylocta-1,6-diene (5,7-DMO), is described. 5,7-DMO can be readily incorporated in ethylene/propylene (ER) chains, while 3,7-DMO does not react in the presence of the metallocene catalyst. The reactivity of these linear dienes is compared with that of 2-ethylidenebicyclo[2.2.l]hept-5-ene (ENB), the preferred termonomer for the industrial synthesis of EPDMs. With the metallocene catalyst, the reactivity of 5,7-DMO is close to that of ENB, suggesting that 5,7-DMO is a good candidate for the synthesis of a new EPDM. A comparison with the conventional catalysis based on vanadium systems shows that the advantages of the metallocene catalysis consist in higher catalyst activities and higher incorporation rates of the termonomers in the polymer without any noticeable side reaction. The structural and physico-chemical characteristics of the various terpolymers, investigated by NMR, SEC and DSC, also underline that the use of metallocenes allows one to prepare EPDM based on linear dienes, with an homogeneous chemical composition and a controlled structure.

Functionalisation of Polyolefins: Grafting of Phenol Groups on Olefin/5,7‐Dimethylocta‐1,6‐diene Copolymers

“…In previous works we have investigated the copolymerization of 5,7-DMO with ethylene [15,16] and its terpolymerisation with ethylene and propylene, [17][18][19] in the presence of various metallocene catalytic systems. High Full Paper: The grafting of phenol groups on ethylene/5,7-dimethylocta-1,6-diene copolymers and on ethylene/propylene/5,7-dimethylocta-1,6-diene terpolymers was performed, using two different modification procedures.…”

Transition Metal Complexes as Catalysts for the Homo- and Copolymerisation of Olefins and Non-Conjugated Dienes

“…These results are consistent with the reported ability of the Et(Ind) 2 ZrCl 2 /MAO system to copolymerise and/or terpolymerise 5,7-DMO with propylene [5] and ethylene. [7] Although the constrained geometry catalyst (2) shows a lower overall activity than Cp 2 ZrCl 2 at the same polymerisation temperature, similar 5,7-DMO incorporation levels in polyethylene are obtained for much lower diene concentrations in the feed (Table 2). It is expected that the relatively low polymerisation activity observed for the CGC catalyst will be significantly increased when using higher polymerisation temperatures.…”

[(η5-C5Me4)SiMe2(NtertBu)]TiCl2 as Pre-Catalyst for the Copolymerisation of Ethylene with 5,7-Dimethylocta-1,6-diene and with 3,7-Dimethylocta-1,6-diene

“…Previous attempts to terpolymerise 3,7-DMO with ethylene and propylene using rac-EtInd 2 ZrCl 2 did not show the presence of the diene in the polymer chains. [21] Indeed, the CGC catalyst presents a wider aperture, which makes it especially suitable for the incorporation of bulky monomers.…”