Conventional molecular weight control

Free-radical polymerization can also be conducted in microflow systems. A fairly good level of molecular-weight control and molecular-weight distribution control can be attained, although the level is not as high as those of conventional living-radical polymerizations. 

Since radicals arc neither formed nor destroyed during reversible chain transfer, RAFT polymerization must, like conventional radical polymerization, be initiated by a source of free radicals as shown in Scheme 9.38. RAFT polymerization is usually carried out with conventional radical initiators. Most often thermal initiators (e.g. AIBN, ACP, BPO, K2SnOs) are used. S polymerization may be initiated thermally between 100-130°C. Polymerizations initiated with UV irradiation, a gamma source " or a plasma tleld have been reported. In these polymerizations, radicals generated directly from the RAFT agent may be responsible for initiation. It was initially suggested by Pan and coworkers that the mechanism for molecular weight control in and y-... 

Cationic polymerization without stabilization of a carbocationic intermediate can be carried out in a microflow system. Good molecular weight control and molecular weight distribution control are attained by virtue of characteristic features of microflow systems (microflow-systempolymerization technology, MCPT). Conventional controlled/living cationic polymerization based on cation stabilization can be also carried out in a microflow system. 

The catalytic systems used still require improvement with respect to stability, activity, and molecular weight control. New modifying ligands have already been proposed " and less conventional aqueous media have been applied in conjunction with water-soluble ligands.f f Most important, however, appears the search for less expensive nickel... 

Scale of Operation Coulometric methods of analysis can be used to analyze small absolute amounts of analyte. In controlled-current coulometry, for example, the moles of analyte consumed during an exhaustive electrolysis is given by equation 11.32. An electrolysis carried out with a constant current of 100 pA for 100 s, therefore, consumes only 1 X 10 mol of analyte if = 1. For an analyte with a molecular weight of 100 g/mol, 1 X 10 mol corresponds to only 10 pg. The concentration of analyte in the electrochemical cell, however, must be sufficient to allow an accurate determination of the end point. When using visual end points, coulometric titrations require solution concentrations greater than 10 M and, as with conventional titrations, are limited to major and minor analytes. A coulometric titration to a preset potentiometric end point is feasible even with solution concentrations of 10 M, making possible the analysis of trace analytes. 

Most of the resin systems used in commodity composites are slight modifications of the standard commercial mol ding grade material. Usually certain selected properties, such as purity or molecular weight range or distribution, are enhanced or carehiUy selected. In addition, special additives, such as flow controllers, thermal stabilizers, or antioxidants, are often added by the resin manufacturer prior to shipment. Many of the conventional or commodity-type resins used in thermoplastic composites are Hsted in Table 1 and the preparation of each of these is described. AH resins and blends described in the hterature are not Hsted, and the synthesis described is not the only procedure available, but is usually the most common commercial process. 

The higher molecular-weight soHd epoxy resins are used in formulations that usually consist of a resin, hardener, reinforcing filler, pigments, flow control agents, and other modifiers. In addition to using conventional hardeners in these formulations, epoxy resins can also be hardened with other resins, ie, acryhcs or polyesters. 

Radical polymerization is often the preferred mechanism for forming polymers and most commercial polymer materials involve radical chemistry at some stage of their production cycle. From both economic and practical viewpoints, the advantages of radical over other forms of polymerization arc many (Chapter 1). However, one of the often-cited "problems" with radical polymerization is a perceived lack of control over the process the inability to precisely control molecular weight and distribution, limited capacity to make complex architectures and the range of undefined defect structures and other forms of "structure irregularity" that may be present in polymers prepared by this mechanism. Much research has been directed at providing answers for problems of this nature. In this, and in the subsequent chapter, we detail the current status of the efforts to redress these issues. In this chapter, wc focus on how to achieve control by appropriate selection of the reaction conditions in conventional radical polymerization. 

Dithiocarbamatc 16 has been used to prepare low dispersity PMAA ( Mw 1 Mn-1.2).52 Photopolymerization of S in the presence of dithiocarbamate 16 also displays some living characteristics (molecular weights that increase with conversion, ability to make block copolymer). However, 17 appears to behave as a conventional initiator in S polymerization.53 The difference in behavior was attributed to the relatively poor leaving group ability of the 2-carboxyprop-2-yI radical. This hypothesis is supported by MO calculations. Dithiocarbamatc 17 was used to control polymerizations of MMA,54 HEMA54 and NIPAM.5... 

First, in composites with high fiber concentrations, there is little matrix in the system that is not near a fiber surface. Inasmuch as polymerization processes are influenced by the diffusion of free radicals from initiators and from reactive sites, and because free radicals can be deactivated when they are intercepted at solid boundaries, the high interfacial area of a prepolymerized composite represents a radically different environment from a conventional bulk polymerization reactor, where solid boundaries are few and very distant from the regions in which most of the polymerization takes place. The polymer molecular weight distribution and cross-link density produced under such diffusion-controlled conditions will differ appreciably from those in bulk polymerizations. 

---