Polystyrene soluble, linear

The preparation of polymer bound Ni-chelates (54) of the acac type started from chloromethylated polystyrene and pentane-2,4-dione leading with catalytic amounts of sodium ethoxide to the polymer diketone (53) (Eq. 21) Seven % of pendent diketone groups of soluble linear (55) were converted with 1,2-diamtnoethane and Ni(II) to the polymer Sdiifr base chelate (54). In the reaction of (55) to (54) two pendent diketon must react. But surprisingly no network formation was reported. 

Continuous homogeneous catalysis is achieved by membrane filtration, which separates the polymeric catalyst from low molecular weight solvent and products. Hydrogenation of 1-pentene with the soluble pofymer-attached Wilkinson catalyst affords n-pentane in quantitative yield A variety of other catalysts have been attached to functionalized polystyrenes Besides linear polystyrenes, poly(ethylene glycol)s, polyvinylpyrrolidinones and poly(vinyl chloride)s have been used for the liquid-phase catalysis. Instead of membrane filtration for separating the polymer-bound catalyst, selective precipitation has been found to be very effective. In all... 

The soluble polymer-supported catalysts have also been used for asymmetrically catalyzed reactions Following a procedure for the preparation of insoluble polymeric chiral catalysts a soluble linear polystyrene-supported chiral rhodium catalyst has been prepared. This catalyst displays high enantiomeric selectivity compared to the low molecular weight catalyst. Thus, hydroformylation of styrene using this catalyst produces aldehydes in high yields. The branched chiral hy drotropaldehy de is formed in 95% selectivity. 

Fig. 15.4.59. Scheme for solid phase synthesis of oligoethers on a soluble linear polystyrene support. 

Soluble linear polystyrene can also be used to prepare recyclable sulfoxide reagents for Swern oxidations [104]. While the styrene copolymer sulfoxides 68 are not strictly catalysts, they are easily recycled by precipitation with cold methanol. Reoxidation of the sulfide with f-BuOOH reformed the starting polymeric sulfoxide 68. While some decrease in yield was seen from cycle to cycle through four cycles, the products were not contaminated with polymer - an advantage in high throughput chemistry where separations need to be as simple as possible. 

The organic and aqueous phases are prepared in separate tanks before transferring to the reaction ketde. In the manufacture of a styrenic copolymer, predeterrnined amounts of styrene (1) and divinylbenzene (2) are mixed together in the organic phase tank. Styrene is the principal constituent, and is usually about 90—95 wt % of the formulation. The other 5—10% is DVB. It is required to link chains of linear polystyrene together as polymerization proceeds. DVB is referred to as a cross-linker. Without it, functionalized polystyrene would be much too soluble to perform as an ion-exchange resin. Ethylene—methacrylate [97-90-5] and to a lesser degree trivinylbenzene [1322-23-2] are occasionally used as substitutes for DVB. 

Linear non-cross-linked polystyrene has been used for organic synthesis since it is readily soluble in common organic solvents (i.e., dichloromethane, chloroform, tetrahydrofuran, toluene, ethyl acetate, and pyridine) but precipitates upon addition of water or methanol [123-126]. However, no examples of the use of this polymer in conjunction with microwave chemistry have been reported. 

In the early 1970 s, Bayer et al. reported the first use of soluble polymers as supports for the homogeneous catalysts. [52] They used non-crosslinked linear polystyrene (Mw ca. 100 000), which was chloromethylated and converted by treatment with potassium diphenylphosphide into soluble polydiphenyl(styrylmethyl)phosphines. Soluble macromolecular metal complexes were prepared by addition of various metal precursors e.g. [Rh(PPh3)Cl] and [RhH(CO)(PPh3)3]. The first complex was used in the hydrogenation reaction of 1-pentene at 22°C and 1 atm. H2. After 24 h (50% conversion in 3 h) the reaction solution was filtered through a polyamide membrane [53] and the catalysts could be retained quantitatively in the membrane filtration cell. [54] The catalyst was recycled 5 times. Using the second complex, a hydroformylation reaction of 1-pentene was carried out. After 72 h the reaction mixture was filtered through a polyamide membrane and recycled twice. 

Straight chain alkanes from Applied Science, aromatics from Fisher Scientific Company and polystyrene standards from Waters Associates were used without purification for the linear molecular size calibration of the GPC. Since the solubility of the larger alkanes in THF is very low, appproximately 0.2 -1 mg of each standard was dissolved in 50 microliters of the THF for the molecular size calibrations. 

In a related application, polyelectrolyte microgels based on crosslinked cationic poly(allyl amine) and anionic polyfmethacrylic acid-co-epoxypropyl methacrylate) were studied by potentiometry, conductometry and turbidimetry [349]. In their neutralized (salt) form, the microgels fully complexed with linear polyelectrolytes (poly(acrylic acid), poly(acrylic acid-co-acrylamide), and polystyrene sulfonate)) as if the gels were themselves linear. However, if an acid/base reaction occurs between the linear polymers and the gels, it appears that only the surfaces of the gels form complexes. Previous work has addressed the fundamental characteristics of these complexes [350, 351] and has shown preferential complexation of cationic polyelectrolytes with crosslinked car-boxymethyl cellulose versus linear CMC [350], The departure from the 1 1 stoichiometry with the non-neutralized microgels may be due to the collapsed nature of these networks which prevents penetration of water soluble polyelectrolyte. 

Where do soluble lignins fit with respect to conformation They seem to be rather compact molecules in solution—the opposite of the highly expanded cellulose molecule. They are not as compact as a simple solid sphere. Yet, the chains of the lignin macromolecules in solution are more densely packed than those of a linear flexible polymer such as polystyrene... 

In this section the use of polystyrene and copolymers of styrene with various cross-linking agents as supports for solid-phase organic synthesis is discussed. Copolymers of styrene with divinylbenzene are the most common supports for solid-phase synthesis. Depending on the kind of additives used during the polymerization and on the styrene/divinylbenzene ratio, various different types of polystyrene can be prepared. However, non-cross-linked polystyrene has also been used as a support for organic synthesis [10,16-22], Linear, non-cross-linked polystyrene is soluble in organic solvents such as toluene, pyridine, ethyl acetate, THF, chloroform, or DCM, even at low temperatures, but can be selectively precipitated by the addition of methanol or water. 

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