Linear non‐conjugated dienes from biomass as termonomers in EPDM synthesis, 1. Study of their reactivity in homo‐, co‐ and terpolymerizations

Abstract

This paper deals with the use of 3,7-dimethylocta-l,6-diene (3,7-DMO) and 5,7-dimethylocta-l,6-diene (5,7-DMO), issued from terpene feedstock, as termonomers for the synthesis of ethylene-propylene-diene terpolymers (EPDM). Their reactivity is first compared to 7-methylocta-l,6-diene (MOCD), an industrial linear diene, in homopolymerization and cross-copolymerization. 'Itvo catalytic systems are used: TiCl,, 1 /3A1Cl3, 14MgC1, associated with Al(C,H,),, and VOCl, or VCl, associated with Al(C,H5),Cl. The influence of the diene structure on the observed order of reactivity is discussed. In a second part, the copolymerization and the terpolymerization of the different dienes with ethylene and propene are implemented. A drastic influence of the diene structure and concentration on the productivity (and activity) is observed. Potentiometric titrations of the vanadium, performed both in the absence and in the presence of dienes (and of other substituted olefins), indicate that the productivity loss mainly results from a reduction process of the vanadium, involving the di-or trisubstituted olefins

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.…”

“…In previous works we have investigated the copolymerization of 5,7‐DMO with ethylene15,16 and its terpolymerisation with ethylene and propylene,17–19 in the presence of various metallocene catalytic systems. High amounts of 5,7‐DMO could be incorporated in the chains with selected metallocenes.…”

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

“…Catalyst (1) yields copolymers with a single melting point around 125 8C and with a melting enthalpy (DH m ) of 81 J N g -1 for 3.4 mol-% of 5,7-DMO. This fact and the absence of the aa carbon of 5,7-DMO sequences (d = 40 ppm [6] ) on the 13 C NMR spectrum of the copolymer (Figure 3) are indicative of a relatively homogeneous distribution of diene units along the polyethylene chains with important loss in crystallinity as indicated by the low DH m of 59 J N g -1 . Homo-and copolymerisations of 5,7-DMO with ethylene using (Me 4 Cp)SiMe 2 (N-tert-Bu)TiCl 2 /MAO.…”

“…[6] Special attention is paid to a linear asymmetrically substituted diene, 5,7dimethylocta-1,6-diene (5,7-DMO), Scheme 2, available from the hydrogenation and cracking of a-pinene, obtained from the craft paper industry waste.…”

[(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

“…While 3,7-DMO has found some application as an intermediary in perfumery, 5,7-DMO is mainly used as fuel. [12] These dienes are very attractive comonomers Full Paper: [(g 5 -C 5 Me 4 )SiMe 2 (NtertBu)]TiCl 2 was used as catalyst in the presence of methylaluminoxane (MAO) for the copolymerisation of ethylene with 5,7-dimethylocta-1,6-diene (5, and with 3,7-dimethylocta-1,6-diene (3,, two linear non-conjugated dienes readily available from terpene feedstock. The effects of reaction temperature, Al/Ti mole ratio and diene concentration in feed on the polymerisation activity and on the incorporation rates of the diene were investigated.…”