Tailored Hydrocarbon and Functionalised

Catalyst and monomer development in acyclic diene metathesis remains a subject of interest, the goal being to obtain macromolecules with well-defined backbone structures and architectures by easily accessible and less expensive means. By the application of an appropriate design of monomers and a careful choice of catalysts, a variety of non-functionalised and functionalised dienes have been polymerised via metathesis condensation to high molecular weight polymers. 

a series of well-defined polyolefins, including perfectly branched polyethylene and ethylene/a-olefin copolymers, have been synthesised via acyclic diene metathesis polycondensation [scheme (28)] [47] these well-defined polyolefins have been designed to model the crystallisation of polyethylene and olefin copolymers. 

The technique illustrated by scheme (28) gives control of the number of methylene groups between branch points as well as the length and identity of the branch itself [1]. 

If this complex is sufficiently stable, then no further reaction occurs, and the polycondensation is obviated. However, as mentioned above, by using controlled monomer design, a variety of functionalised polymers (typical by with Mn = 10 000—30 000 and Mw/Mn = 2.0) can be synthesised polyethers [15,48 50], poly(thioether)s [48], polyesters [51,52], polycarbonates [53], polyketones [54], polysiloxanes [55-58], poly(carbosiloxane)s [59], poly(carbosilane)s [60], poly(carbodichlorosilane)s [61] and polymers with a conjugated % system [62]. 

It has also been possible to design a series of segmented functionalised copolymers (with polyether or polysiloxane segments) using a, co-dienyl tele-chelic oligomers for metathesis polycondensation [63]. 

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