Copolymers Telomerization

Depending on the choice of transfer agent, mono- or di-cnd-functional polymers may be produced. Addition-fragmentation transfer agents such as functional allyl sulfides (Scheme 7.16), benzyl ethers and macromonomers have application in this context (Section 6.2.3).212 216 The synthesis of PEG-block copolymers by making use of PEO functional allyl peroxides (and other transfer agents has been described by Businelli et al. Boutevin et al. have described the telomerization of unsaturated alcohols with mercaptoethanol or dithiols to produce telechelic diols in high yield. 

Amiduri, B Boutevin, B. and Gramain, P Synthesis of Block Copolymers by Radical Polymerization and Telomerization. VoL 127, pp. 87-142. 

Fluorinated radicals play a significant role in synthetic organo-fluorine chemistry, for example, in electrophilic radical addition to alkenes, single-electron transfer reactions (SET), telomerization of fluoroalkenes with perfluoroalkyl iodides, polymerization to fluoropolymers and copolymers, and thermal, photochemical and radiation destruction of fluorocarbons. Furthermore, such free radicals are of interest for studying structures, reaction kinetics and ESR spectroscopic parameters.38... 

Photolysis of this polymer gives radicals on which side chains can be formed, giving graft polymerization 122, 123, 153). Similarly the polymerization of styrene (152) or vinyl acetate (157) in the presence of bromotrichloromethane gives telomers carrying terminal bromine atoms and trichloromethyl groups. By ultraviolet irradiation (3500 A) in the presence of methyl methacrylate the carbon-bromine links are broken and block copolymers are formed. The telomerization of acrylonitrile and acrylic acid with bromoform is based on the same technique the end groups of both polyacrylonitrile and polyacrylic acid were photolyzed in the presence of acrylamide and afforded polyacrylamide blocks linked to polyacrylonitrile or polyacrylic acid blocks (164, 165). 

Synthesis of Block Copolymers by Radical Polymerization and Telomerization... 

Bamford is considered as the pioneer of this research. His investigations led to a series of various publications dealing with the synthesis of block and graft copolymers [99]. The following example [100] using the co-tribromomethy 1 polymer produced from the radical telomerization of a conventional monomer with the tetrabromomethane illustrates this kind of polymerization ... 

A similar strategy was reported by Asahi Glass which prepared fluoroacrylic (FA) diblock copolymem used as surface active agents [117]. Acrylates containing perfluorinated groups were telomerized with mercapto acetic acid followed by the condensation of the telomer produced with polypropylene oxide (PPO) to yield PPO-t-PFA diblock copolymers. 

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