Transfer polymerisation

H.G.M. Edwards, K.S. Johal and A.F. Johnson, FT-Raman spectroscopic monitoring of the gronp-transfer polymerisation of methyl methacrylate, Vib. Spectrosc., 41, 160-169 (2006). 

It is well known that AB diblock copolymers form micelles in solvents that are selective for one of the blocks. By varying the nature of the solvent, it is also possible to form micelles with the A block in the core or with the B block in the core. However, we have recently demonstrated that certain hydrophilic AB diblock copolymers can form either A-core micelles or B-core micelles in aqueous media. In the original example, both blocks were based on tertiary amine methacrylates and the diblock copolymer was prepared by group transfer polymerisation, a special type of anionic polymerisation which is particularly... 

The cleavage of C-I bond can be achieved from various methods [373-375]. However, according to well chosen monomers, two main ways have been developed in order to control telomerisation from alkyl iodides iodine transfer polymerisation (ITP) and degenerative transfer. ITP can be easily applied to fluorinated monomers whereas degenerative transfer concerns the controlled polymerisation of methyl methacrylate, butyl acrylate [376] or styrene [377] and will not be discussed in this chapter. 

Several investigations have shown that iodine transfer polymerisation can occur by emulsion or radical initiation. When emulsion initiation is chosen, a per-fluoroalkyl iodide is involved and limits the molecular weights [378,379]. This is not described here but several articles and patents from Tatemoto are sug-... 

Coordination Group-transfer Polymerisation of Alkyl (Meth)acrylates... 

Figure 3 Dual channel DRI and UVl Visible detection SEC traces for PMMA from catalytic chain transfer polymerisation...

Mertoglu M, Gamier S, Laschewsky A, Skrabania K, Storsberg J. Stimuli responsive amphiphilic block copolymers for aqueous media synthesised via reversible addition fragmentation chain transfer polymerisation (RAFT). Polymer 2005 46(18) 7726-40. 

Functionalised antimicrobial polymers can be developed by chain transfer (reversible addition-fragmentation transfer) polymerisation involving amino derivatives of methacrylate containing polydimethylsiloxane, which are further quarternised to yield new cationic polymers and are useful as antimicrobial coatings. 

Nurmi L, Lindqvist J, Randev R, Syrett J, Haddleton DM (2009) Glycopolymers via catalytic chain transfer polymerisation (CCTP), Huisgens cycloaddition and thiol-ene double click reactions. Chem Commun 2727... 

Bergius, W.N.A., Hutchings, L.R., Sarih, N.M., Thompson, R.L., Jeschke, M., Fisher, R. Synthesis and characterisation of end-functionalised poly(N-vinylpyrrolidone) additives by reversible addition-lragmentation transfer polymerisation. Polym. Chem. 4, 2815-2827 (2013)... 

Stopped-flow FTIR spectroscopy was used to follow group transfer polymerisation (GTP) and cyclic oligomeric carbonate formation. The effect of catalyst structure, propagating end stereochemistry and degree of polymerisation on the rate of monomer addition in GTP was investigated (329). 

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... 

Atom radical transfer polymerisation (ATRP) has its roots in atom transfer radical addition (ATRA), which involves the formation of 1 1 adducts of alkyl halides and alkenes, and is also catalysed by transition metal complexes. ATRP is a modification of the Kharasch addition reaction (Kharasch et al. 1945) although there may be some differences (Minisci 1975). A general mechanism for ATRP is shown in Scheme 10.5. In ATRP the radicals or the active species are generated through a reversible redox process catalysed by a transition metal complex (Mtn-L/... 

Similar results were obtained with a blend of chain-end labelled PMMA (prepared by group transfer polymerisation) and an immiscible partner, poly(2-ethylhexyl methacrylate), of low T, (263 K) [36],... 

Haddleton DM, Edmonds R, Heming AM, Kelly EJ, Kukulj D (1999) Atom transfer polymerisation with glucose and cholesterol derived initiators. New J Chem 23(5) 477-479... 

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