Free radical chain polymerisation transfers

Free radical chain polymerisation is the method used to prepare the most common polymers. A free radical is generated and reacts with one molecule of monomer (initiation). Then monomer molecules react with this first species, leading to formation of a long chain by successive additions of monomer (propagation). Finally, chains are terminated by reaction of two chains bearing radicals (termination). As radicals are very reactive species, side reactions are likely to occur and modify the simple process (transfer). 

Functional oligomers with a terminal alpha-substituted acrylate group can be synthesised by catalytic free-radical chain transfer polymerisation based on cobalt II or II chelates. The apphcations of such oligomers in the design of low molec.wt., graft and block copolymer emulsions and dispersions for waterborne, two-component PU paints are reviewed. The emulsions and dispersions are shown to have composition and molec.wt. control and to exhibit... 

The photoinduced addition of a thiol (RSH) to an olefinic double bond has been used to produce polymer networks by taking multi-functional monomers [37-44]. The thiol-ene polymerisation proceeds by a step growth addition mechanism which is propagated by a free radical, chain transfer reaction involving the thiyl radical (RS ). The initial thiyl radicals can be readily generated by UV-irradiation of a thiol in the presence of a radical-type photoinitiator. The overall reaction process can be schematically represented as follows ... 

Mention may finally be made of graft polymers derived from natural rubber which have been the subject of intensive investigation but which have not achieved commercial significance. It has been found that natural rubber is an efficient chain transfer agent for free-radical polymerisation and that grafting appears to occur by the mechanism shown in Figure 30.8. 

Chain polymerisation necessarily involves the three steps of initiation, propagation, and termination, but the reactivity of the free radicals is such that other processes can also occur during polymerisation. The major one is known as chain transfer and occurs when the reactivity of the free radical is transferred to another species which in principle is capable of continuing the chain reaction. This chain transfer reaction thus stops the polymer molecule from growing further without at the same time quenching the radical centre. 

Figure 1 Reaction scheme for the free-radical polymerisation (I is the initiator, R the fragment of initiator, M the monomer and AH the chain transfer agent).

In solution polymerisation, the reaction is carried out in presence of a solvent. The monomer is dissolved in a suitable inert solvent along with the chain transfer agent. A large number of initiators can be used in this process. The free radical initiator is also dissolved in the solvent. The ionic and coordination catalysts can either be dissolved or suspended in the medium. The solvent facilitates the contact of monomer and initiator and helps the process of dissipation of exothermic heat of reaction. It also helps to control viscosity increase. 

If free-radical polymerisation is carried out in an ideal back-mixed flow reactor, the concentrations of the reactant species become constant and the molecular weight distributions can be obtained from eqns. (83) and (84). Figure 8 shows how changes in P /Pn with conversion compare for the two reactor types. These plots represent idealised behaviour, in practice, Pw/Pn will be influenced by changes in at high conversion and by the occurrence of chain transfer reactions. 

In the hrst step, a redox reaction occurs between Ce(IV) and the -CH2OH end group of PEO, generating a free radical in a-position of the -OH group of PEO. In a consequent step, the radical is transferred from the PEO chain to the vinyl monomer. The radicals formed initiate the actual polymerisation reaction (propagation) ... 

Conversely, when the rate of propagation is faster than chain transfer, products arising from telomerisation and polymerisation are formed in greater concentration. In this section, free-radical addition to fluoroalkenes will be dealt with first, in order to establish... 

The chain length in free radical polymerisations is usually lower than would be expected from the mechanism of termination. The reason for this discrepancy is that the growing polymer chain can transfer the radical to other species, leading to termination of one chain, and thus generating a new radical that will react further. The following transfer mechanisms may occur ... 

The first element of this definition requires that the substance consist of a minimum of three repeat units of monomer(s) in reacted form bonded to another monomer or other reactant [9]. Other reactants, in this case, may not necessarily be monomers, but are incorporated into the polymer to provide a particular function. Other reactants may include a free-radical initiator used to initiate a vinyl-free radical polymerisation (e.g., peroxide used to make polyethylene or polyacrylic acid), a chain transfer agent used to control molecular weight, e.g., mercaptan used in free-radical polymerisations, or crosslinkers used to build molecular weight, e.g., divinyl benzene. 

Many publications dealing with the free-radical homo/copolymerisation of saturated fatty acid acrylates and methacrylates appeared between 2001 and 2011, particularly using living systems such as atom transfer radical polymerisation (ATRP) [91-112]. Monomers were prepared, for example, by the reaction of acrylic and methacrylic acid chlorides with fatty alcohols of different chain length, as shown in Scheme 4.23 in the case of methacrylates (which also includes their ATRP conditions). A very... 

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