Transfer copolymerizing

The photo-induced charge-transfer copolymerization entity consists of a donor monomer and an acceptor monomer, without initiator. Reported combinations usually consist of an aryl vinyl monomer as the donor component and a 1,2-disubstituted vinyl monomer as the acceptor component. 

Generally, the photo-induced charge-transfer copolymerization follows a radical mechanism and produces alternating copolymers. Accompanying cyclobutane formation is usually observed, which provides information for understanding the mechanism. 

A charge-transfer complex (CT complex or CTQ is involved in all thermal charge-transfer polymerizations and in most of the photo-induced charge-transfer copolymerizations. Mixing of a donor (D), such as VCZ, with an acceptor, such as tetracyanoethylene (TCNE), immediately produces color [31] due to the formation of a CT complex ... 

The initiation mechanism of photo-induced charge-transfer copolymerization of donor-acceptor monomer pairs is clarified by integrating the results from organic chemistry and polymer chemistry. A reasonable suggestion for the initiating species in certain cases may be a tetramethylene 1,4-diradical. The excited complex of the donor/acceptor monomers undergoes multiple follow-up reactions to produce the... 

FOU Fourttier, D., Hoogenboom, R., Thijs, H.M.L., Paulus, R.M., and Schubert, U.S., Tunable pH- and temperature-sensitive copolymer libraries by reversible addition-fragmentation chain transfer copolymerizations of methacrylates. Macromolecules, 40, 915, 2007. 

In many cases of start reactions, a monomer is added on to the initiator to form an active center. The active center may be an anion, cation, or free radical in addition polymerization, or, for example, an electron-deficient compound or an unoccupied ligand position in polyinsertion (see Chapter 19). Spontaneous thermal addition polymerizations of monomers which proceed in the absence of added catalyst or initiator are relatively rare. The free radical thermal polymerization of styrene (Chapter 20) and the charge transfer copolymerization of monomers of opposed polarities (Chapter 22) are examples of genuine spontaneous polymerizations. These genuine spontaneous polymerizations can often only be distinguished with difficulty from nongenuine spontaneous polymerizations which are started by unsuspected impurities remaining in these systems. 

P. F. W. Simon and A. H. E. Muller, Synthesis of hyperbranched and highly branched methacrylates by self-condensing group transfer copolymerization . Macromolecules, 2001,34, 6206-13. 

Tacticity measurements can be correlated with reaction mechanisms and physical properties. For example, the incorporation of an electron donor into the polymerization catalyst formulation has been found to increase isotacticity in a propylene-1-butene copolymer [123], and the distribution of propylene and 1-butene contents as a function of molecular weight varied, depending on donor type. External donors, such as dimethox-ysilane, decrease the butene content more than internal electron donors (in this case, di-n-butyl phthalate). Mechanisms of new polymerization reactions, such as the group-transfer copolymerization of methyl methacrylate and lauryl methacrylate, can be elucidated by comparing NMR-derived structural details [124]. The presence of unanticipated peaks in the spectrum of poly(ethylene-co-norbomene) suggest the occurrence of epimerization... 

CATALYTIC SYSTEMS AND THEIR APPLICATIONS EM COORDINATIVE CHAIN TRANSFER COPOLYMERIZATION (CCTCOP)... 

Pierik, B., Masclee, D., and Van Herk, A. (2001). Catalytic chain transfer copolymerization of methyl methacrylate and methyl acrylate. Macromol. Symp., /65(Developments in Polymer Synthesis and Characterization) 19-27. 

Menard Raphael, Negrell-Guirao Claire, Ferry Laurent, Sonnier Rodolphe, and David Ghislain. Synthesis of new flame-retardants by radical chain transfer copolymerization of glycidyl methacrylate and dimethoxy-phosphorylmethyl methacrylate. Eur. Polym. J. 57 no. 7 (2014) 109-120. 

Ziegler-Natta Polymerizations Quinodimethane Polymers Charge-Transfer Copolymerizations Reactions on Polymers Polymeric Dyes... 

Charge Transfer Copolymerization Chemical Spectroscopy Relaxation Phenomena in Polymers Water-Borne Polymers... 

Some monomers having an acid hydrogen such as acrylic acid, a-keto acids,and ethylenesulfonamide undergo a hydrogen-transfer copolymerization (cf. eqn [42]). 

Iodine transfer copolymerization of MMA with styrene was performed in bulk at 60 °C in the presence of iodoacetonitrile or iodoform as ttansfer agents and Et2AlCl as Lewis add, which reduces the electron density of the double bond of MMA (Scheme 23a). However, this system was not investigated in detail and such studies would deserve more attention. ... 

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