Ring-opening polymerisations

J. Lehmaim and co- Ring-Opening), Warsaw-Jablorma, Poland, June 23-25, 1975, p. 141. 

One variation of rearrangement polymerisation is ring-opening polymerisation. Important examples include the polymerisation of trioxane, ethylene oxide and e-caprolactam Figure 2.8 (a) to (c) respectively). It is to be noted that... 

The use of supported transition metal oxide and Ziegler-Natta-type catalysts for polymerising aliphatic olefins (alkenes) was extended in the 1960s and 1970s to the ring-opening polymerisation of cyclo-olefins. 

The monomer, norbomene (or bicyclo[2.2.l]hept-2-ene), is produced by the Diels-Alder addition of ethylene to cyclopentadiene. The monomer is polymerised by a ring-opening mechanism to give a linear polymer with a repeat unit containing both an in-chain five-membered ring and a double bond. Both cis-and trans- structures are obtainable according to the choice of catalyst used ... 

One variation in polyester intermediates that has roused some interest are those prepared by a ring-opening polymerisation of e-caprolactone and methyl-e-caprolactones with titanium catalysts and diol and triol initiators Figure 27.6). 

In recent years there has been some interest in the ring-opening polymerisation of cyclic trimers using a weak base such as lithium silanolate which gives high molecular weight products of narrow molecular weight distribution free of cyclic materials other than the unreacted trimer. 

Ring-opening reactions may also be used in order to make polymers by the step polymerisation mechanism. One commercially important example of this is the manufacture of nylon 6, which uses caprolactam as the starting material and proceeds via the ring-opening reaction shown in Reaction 2.15. 

Report 85 Ring Opening Polymerisation, N. Spassky, Universite Pierre et Marie Curie. Report 112 Polystyrene - Synthesis, Production and Applications, J.R. Wunsch, BASF AG. 

Controlling the exact architectnre of polymers has always attracted attention in macromolecular chemistry. Snccessfnl synthesis of alternating copolymers nsing ring opening metathesis polymerisation is of great interest also from a mechanistic perspective. NHC ligands were fonnd to be ideal to tune the selectivity of the metathesis initiators. 

ROMP Ring Opening Insertion Metathesis Polymerisation... 

This section deals with the most important control experiments to be considered when molecular complexes or NPs want to be proved as true catalysts. But in some cases both types of catalysts can be present in the same reaction. For example, in the ring opening polymerisation of l,l,3,3-tetramethyl-l,3-disilacyclobutane catalysed photo-chemically by Pt(acac)2, the co-existence of both homogeneous and colloidal catalytic species has been proved, giving each of them different type of polymers [10]. 

When this strained ring opens, this can give rise to polymerisation that can be very dangerous due to exothermicity. Note that it will be very difficult to explain an accident by decomposition leading to the destruction of the molecular structure or polymerisation. 

Polymers are formed via two general mechanisms, namely chain or step polymerisation, originally called addition and condensation, respectively, although some polymerisations can yield polymers by both routes (see Chapter 2). For example, ring opening of cyclic compounds (e.g., cyclic lactides and lactams, cyclic siloxanes) yield polymers either with added catalyst (chain) or by hydrolysis followed by condensation (step). Many polymers are made via vinyl polymerisation, e.g., PE, PP, PVC, poly(methyl methacrylate) (PMMA). It could be argued that the ethylenic double bond is a strained cyclic system. 

Since one of the substrates is a cyclic alkene there is now the possibility of ring-opening metathesis polymerisation (ROMP) occurring which would result in the formation of polymeric products 34 (n >1). Since polymer synthesis is outside the scope of this review, only alkene cross-metathesis reactions resulting in the formation of monomeric cross-coupled products (for example 30) will be discussed here. 

Report 85 Ring Opening Polymerisation, N. Spassky, Universite Pierre et Marie Curie. 

Cyclobutane has not been polymerised cationically (or by any other mechanism). Thermochemistry tells us that the reason is not thermodynamic it is attributable to the fact that the compound does not possess a point of attack for the initiating species, the ring being too big for the formation of a non-classical carbonium ion analogous to the cyclopropyl ion, so that there is no reaction path for initiation. The oxetans in which the oxygen atom provides a basic site for protonation, are readily polymerizable. Methylenecyclobutane polymerises without opening of the cyclobutane ring [72, 73]. 

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