Co-styrene

IUPAC recommendations suggest that a copolymer structure, in this case poly(methyl methacrylate-co-styrene) or copoly(methyl methacrylate/slyrene), should be represented as 1. The most substituted carbon of the configurational repeat unit should appear first. This same rule would apply to the copolymer segments shown in Section 7.1. However, as was mentioned in Chapter I, in this book, because of the focus on mechanism, we have adopted the more traditional depiction 2 which follows more readily from the polymerization mechanism. 

Very recent relevant observations reveal that the TCS approach albeit certainly significant as conceptual and operational tool in the issue of metal nanoclusters size control, requires a substantial further perfection. Resin sulfonated Bayer K1221 is a co styrene-divinylbenzene commercially available gel-type resin, in beaded form. Its cross-linking degree is ca. 4% mol and therefore K1221 is expectedly quite similar to DOMA-VP and MTEMA-DMAA 4-4 for example. In fact ISEC analysis reveals a nanoporosity featured by 4.0 and 2.0 nm nanopores only. The expectation is that a Pd°/K1221 nanocomposite obtained with a classic procedure [5,9,10] will exhibit diameters strictly ranging from 2 to 4 nm. 

Figure 13 Typical swelling and deswelling rates of cross-linked poly(acryloyl pyrroli-dine-co-styrene) between 27°C and 37°C. AS15 ( ) AS20 (A). The numbers indicate the content of styrene in the feed composition in moles during polymerization. Membrane thickness is 0.5 mm in the dried state. (From Ref. 34.)...

The cobalt(II)15 and zinc(II)16 complexes of phthalocyanine(Pc), octcyano-Pc, and tetrasulfon-ato-Pc incorporated in poly(4-vinylpyridine-co-styrene) or Nafion films coated on graphite have also been examined as catalytic devices for dihydrogen electrogeneration in phosphate buffer. These catalytic systems were strongly suggested to be dominated by the electron transfer within the polymer matrix. The best catalytic film is that constituted of the nonsubstituted Con-Pc complex in poly(4-vinylpyridine-co-styrene), giving a turnover number of 2 x 10s h-1 at an applied potential of —0.90 V vs. Ag Ag Cl. 

Figure 2. G-value for radical production for poly(methacrylic acid-co-styrene) as a function of copolymer composition.

Several types of bidentate ligands, different from diphosphines, for example bipyridines and phenantrolines, have been proven to give active catalysts, particularly in the CO-styrene copolymerisation [25], but, particularly with ethene, diphosphines give higher performances. 

A mechanistic study by Haynes et al. demonstrated that the same basic reaction cycle operates for rhodium-catalysed methanol carbonylation in both homogeneous and supported systems [59]. The catalytically active complex [Rh(CO)2l2] was supported on an ion exchange resin based on poly(4-vinylpyridine-co-styrene-co-divinylbenzene) in which the pendant pyridyl groups had been quaternised by reaction with Mel. Heterogenisation of the Rh(I) complex was achieved by reaction of the quaternised polymer with the dimer, [Rh(CO)2l]2 (Scheme 11). Infrared spectroscopy revealed i (CO) bands for the supported [Rh(CO)2l2] anions at frequencies very similar to those observed in solution spectra. The structure of the supported complex was confirmed by EXAFS measurements, which revealed a square planar geometry comparable to that found in solution and the solid state. The first X-ray crystal structures of salts of [Rh(CO)2l2]" were also reported in this study. 

The deliberate introduction of multifunctional branching into anionically prepared polydiene and poly (diene-co-styrene) polymers produces materials with unique morphological and viscoelastic properties (1-3). Work has included synthesis of symmetric star polymers produced by reaction of living polyanionic "arms" with multi-functional chlorosilane (4-9),... 

Macchioni and coivorkers [147] have investigated the effect of the counterion on CO/Styrene copolymerization catalyzed by [Pd(ti -Ti -C8Hi20Me)bipy]X, (92, Figure 1.21) where X is the counterion. The bipyridine ligand shows dynamic behavior and a series of NMR spectra recorded between 204 and 302 K (Figure 1.21) pro-... 

Since the late 1960 s a few papers have demonstrated compositional analysis of various polymer systans by Raman spectroscopy. For example, Boerio and Yuann (U) developed a method of analysis for copolymers of glycidyl methacrylate with methyl methacrylate and styrene. Sloane and Bramston-Cook (5) analyzed the terpolymer system poly(methyl methacrylate-co-butadiene-co-styrene). The composition of copolymers of styrene-ethylene dimethacrylate and styrene-divinylbenzene was determined by Stokr et (6). Finally, Water (7) demonstrated that Raman spectroscopy could determine the amount of residual monomer in poly(methyl methacrylate) to the % level. This was subsequently lowered to less than 0.1% (8). In spite of its many advantages, the potential of Raman spectroscopy for the analysis of polymer systems has never been fully exploited. 

Scheme 8.4 Various zinc(ii)salphens have been coordinated to mPy-BIAN (PdMe), forming active catalysts for CO/styrene polymerization reactions.

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