Binary initiating system

Organic peroxide-aromatic tertiary amine system is a well-known organic redox system 1]. The typical examples are benzoyl peroxide(BPO)-N,N-dimethylani-line(DMA) and BPO-DMT(N,N-dimethyl-p-toluidine) systems. The binary initiation system has been used in vinyl polymerization in dental acrylic resins and composite resins [2] and in bone cement [3]. Many papers have reported the initiation reaction of these systems for several decades, but the initiation mechanism is still not unified and in controversy [4,5]. Another kind of organic redox system consists of organic hydroperoxide and an aromatic tertiary amine system such as cumene hydroperoxide(CHP)-DMT is used in anaerobic adhesives [6]. Much less attention has been paid to this redox system and its initiation mechanism. A water-soluble peroxide such as persulfate and amine systems have been used in industrial aqueous solution and emulsion polymerization [7-10], yet the initiation mechanism has not been proposed in detail until recently [5]. In order to clarify the structural effect of peroxides and amines including functional monomers containing an amino group, a polymerizable amine, on the redox-initiated polymerization of vinyl monomers and its initiation mechanism, a series of studies have been carried out in our laboratory. 

Organolanthanide(III)-based binary initiator systems were used by Yu et al. 

Summarised briefly, the reason for their agnosticism appears to be that the authors were unable to see any pattern in the multitude of qualitative and semi-quantitative results which they obtained with a large number of binary initiator systems (ZK). However, it appears to us that there is nothing in these results which could not be explained in terms of ionisation equilibria of the type suggested by these authors earlier (reaction (14) and its analogues). In fact no evidence for or against our (and their earlier) views is derivable from the experiments with ZK until the electrochemical aspects of these two-component systems have been explored. 

In 1986, Kennedy and Faust published a similar controlled/living polymerization of isobutene by the cumyl acetate/boron trichloride [C6H5C(CH3)20C(0)CH3/BC13] and related binary initiating systems [35,62],... 

Styrene polymerization was performed by using binary initiator systems such as Nd(acac)3/AlR3 or Nd(P507)3/AlR3 Syndio-rich polystyrene was obtained at a ratio of Al/Nd=10-12 [57]. More recently, it was shown that the... 

Organolanthanide(III) based binary initiator systems were used by Yu et al. [65] for stereospecific polymerization of butadiene and isoprene. Typically, the po-... 

Binary initiator systems of AlCl3/(-)-menthoxytriethyltin, AlCls-germanium, or AlCls-silicone for 265 polymerization are also known. N-Phenylmaleimide (66), a monomer with a C2 axis of symmetry, also gave an optically active homopolymer (267). Compound 267 can be optically active only if the main chain has in excess one of two enantiomeric trans structures, 268a and 268b. Helical structure has also been proposed for N-substituted maleimide polymers. 

Several binary initiator systems have also been developed. Ozaki et and Ishizone et demonstrated... 

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