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RhCl(P 3)3

IPor more on history, see [419, 420. 610]. 2"L'expression (1/2) + o:]n) represente une fonction de x et de 0: telle que, si on la -'/I" multiplie par un fonction quelconque F(o:) et si. apres avoirecrit do:, on integre entre les Iimites 0: et 0: = '/1", on aura change la fonction proposee F(o:) en une pareille fonction de x, multipliee par la demi-circonference '/1"." 3If f(x) is not continuous, the situation is more ccmplex (see Section F.3).

CH2P 2RhCl(P 3)2

2:::=1 Cos (x -

9-65



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The chloromethylated polystyrene is usually obtained by chloromethylation of polystyrene (Eq. 9-38), although polymerization of p-vinyl benzyl chloride has also been used [Arshady et al., 1976]. A less desirable variation of this approach is the physical entrapment of a catalyst, substrate, or reagent within a polymer. There are a number of considerations in the choice of the polymer to be used as a support availability and cost, mechanical, thermal, and chemical stability, porosity, and compatibility with reagents and solvents. The use of a commercially available, inexpensive polymer is clearly preferable to a more expensive polymer or one that must be speci cally synthesized for the purpose. The support polymer must be chemically and thermally inert under the conditions necessary for its functionalization and subsequent use. Heterogeneous polymer catalysts, reagents, and substrates require the support to possess a reasonable degree of mechanical strength. Some degree of crosslinking is usually employed for this purpose. The physical form of the functionalized polymer is also a consideration in terms of its application. The polymer support as well as the functionalized polymer should be porous to allow access of the reagent(s) and solvent(s), if any, to achieve a homogeneously active polymer. A polymer reagent, catalyst, or substrate with only surface activity would result if the polymer were nonporous. Compatibility of the functionalized polymer (more speci cally, the regions in the vicinity of the functional groups) with reagents and solvents is also needed to achieve high reaction rates and high yields. Polystyrene is presently the overwhelming choice as the polymer support [Frechet and Farrall, 1977; Frechet et al., 1988; Messing, 1974]. The polystyrene used is a crosslinked polymer prepared by copolymerization of styrene with divinylbenzene (DVB). (The divinylbenzene is usually the commercially available mixture containing the meta and para isomers





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the delta function appearing in physics. At the end of the section we describe briefly a general method of identifying and constructing representations of delta functions [8].

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Fig. 3-9 Inhibition and retardation in the thermal, self-initiated polymerization of styrene at 100 C. Plot 1, no inhibitor; plot 2, 0.1% benzoquinone; plot 3, 0.5% nitrobenzene; plot 4, 0.2% nitrosobenzene. After Schulz [1947] (by permission of Verlag Chemie GmbH and Wiley-VCH, Weinheim).

F.1.1

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but at a slower rate and lower polymer molecular weight. The difference between inhibitors and retarders is simply one of degree and not kind. Figure 3-9 shows these effects in the thermal polymerization of styrene [Schulz, 1947]. Polymerization is completely stopped by benzoquinone, a typical inhibitor, during an induction or inhibition period (plot 2). At the end of this period, when the benzoquinone has been consumed, polymerization proceeds at the same rate as in the absence of inhibitor (plot 1). Nitrobenzene, a retarder, lowers the polymerization rate without an inhibition period (plot 3). The behavior of nitrosobenzene, fNO, is more complex (plot 4). It is initially an inhibitor but is apparently converted to a product that acts as a retarder after the inhibition period. This latter behavior is not at all uncommon. Inhibition and retardation are usually the cause of the irreproducible polymerization rates observed with insuf ciently puri ed monomers. Impurities present in the monomer may act as inhibitors or retarders. On the other hand, inhibitors are invariably added to commercial monomers to prevent premature thermal polymerization during storage and shipment. These inhibitors are usually removed prior to polymerization or, alternatively, an appropriate excess of initiator may be used to compensate for their presence. 3-7a Kinetics of Inhibition or Retardation

The rectangular barrier Ye (x) is perhaps the simplest function one can think of whose fixed-area vanishing-width limit yields a delta function. It is defined (see Figure EI) by

The kinetics of retarded or inhibited polymerization can be analyzed using a scheme consisting of the usual initiation (Eq. 3-14), propagation (Eq. 3-15), and termination (Eq. 3-16) reactions in addition to the inhibition reaction

Ye( ) -

3-134

{O, l/e,

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