Methylmethacrylate , atom-transfer

Star poly(methylmethacrylates) were synthesized via atom transfer polymerization using a small carbosilane dendrimer functionalized with a tertiary bromide moiety as an initiator core (Figure 12)100,101. a convergent approach to star polymers with a carbosilane dendrimer core was described in a report by Allgaier and coworkers102, in which living poly(butadienyl-lithium) arms were coupled with various SiCl-terminated carbosilane den-drimers. Utilizing smaller dendrimers with lower functionality was found to yield nearly ideal results in terms of substitution and polydispersity. 

Alipour, M., et al. (2001). Living radical polymerization of methylmethacrylate, methylacrylate and their block copol5mers with acrylonitrile by atom transfer radical polymerization. Iran Polym. J., 10(2) 99-106. 

As mentioned above, the cleavage of Si-Si-bonds in polysilanes upon irradiation with UV-light is very efficient and results in the formation of silicon radicals. These radicals react with olefins to initiate radical polymerizations. Especially the polymerization of methylmethacrylate and styrene with a variety of polysilanes as photoinitiators has been studied in detail [104]. The advantage of this kind of initiation is the possibility to prepare polysilane-polyolefin hybrids [105]. All modifications of radical polymerizations, such as the atom transfer radical polymerization (ATRP), are possible with polysilanes as photoinitiators [106]. 

The iron species [Fe(X)2 CN(PP)CH(Me) = CH(Me)N(Pr ) ] (X = Cl, Br), containing highly donating imidazolyidene ligands, have been found to be extremely active and efficient catalysts for the atom transfer radical polymerisation of styrene and methylmethacrylate. A variety of indenyl ruthenium complexes containing either phenylacetylide (C = CPh) or vinyl (CH = CHPh) ligands have been found to catalyse the dimerisation of phenylacetylene to ( )-and (Z)-l,4-diphenyl-l-en-3-yne with the activity of the catalyst dependent upon the nature of the phosphine co-ligand bound to ruthenium. The vinylidene-ruthenium(II) complexes [Ru(Cl)(L)2(C = CHR)] (R = Bu, ferrocenyl L =... 

The graft copolymer products, poly(met)acrylates branched to polyester-suUbnes, can be produced next way [200]. Firstly, the polyestersulfone is being chlormethylenized by monochlordimethyl ester. The product is used as macrostarter for the graft radical polymerization of methylmethacrylate (I), methylacrylate (II) and butylacrylate (III) in dimethylformamide according to the mechanism of transferring of atoms under die influence of the catalytical system FeCyisophthalic acid. The branched copolymer with I has only one glassing temperature while copolymer with II and III has three. 

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