Poly phase transfer catalysts

Cinchona-Derived Chiral Poly(Phase-Transfer Catalysts) for Asymmetric Synthesis... 

Halex rates can also be increased by phase-transfer catalysts (PTC) with widely varying stmctures quaternary ammonium salts (51—53) 18-crown-6-ether (54) pytidinium salts (55) quaternary phosphonium salts (56) and poly(ethylene glycol)s (57). Catalytic quantities of cesium duoride also enhance Halex reactions (58). 

Baneijee et al. reported a number of soluble poly-imido [134], polyazomethine [135], and polyazoxy phos-phonates [136] by the two phase polycondensation method with or without any phase transfer catalyst. Resulting polymers exhibit high thermal stability and fire retardancy. 

Phase-separated polymers, 215 Phase separation, 217-222 Phase transfer catalysts, 288, 563-564 Phase-transfer-catalyzed alkaline hydrolysis of nylon-4,6, 570 of nylon-6,6, 569-570 PHB. See Poly(3-hydroxybutanoic acid) (PHB)... 

Based on this hypothesis we reversed the order in which the reactants are brought into contact. Consequently, we added an aqueous solution of BPA, sodium hydroxide, and phase transfer catalyst into a well-stirred solution of cyanogen bromide in carbon tetrachloride. Under these conditions poly(iminocarbonates) of high molecular weight were readily obtained (Fig. 8.)... 

In general, if condensation polymers are prepared with methylated aryl repeat units, free radical halogenatlon can be used to introduce halomethyl active sites and the limitations of electrophilic aromatic substitution can be avoided. The halogenatlon technique recently described by Ford11, involving the use of a mixture of hypohalite and phase transfer catalyst to chlorinate poly(vinyl toluene) can be applied to suitably substituted condensation polymers. 

When TBAB is used as a phase-transfer catalyst, sodium hydroxide as a base, and DCE as a solvent, both the molecular weight and yield of the poly(carbonate) are relatively high. Bisphenol AF-derived poly(carbonate) (2) having reduced viscosity of 0.35 dl/g is obtained in a 84% yield at ambient temperature under the... 

Table 9.1. Effects of Phase-Transfer Catalyst and Organic Solvent on the Yield and Reduced Viscosity of Bisphenol-AF-Derived Poly(Carbonate)6...

Hay et al.w,n have prepared high-molecular-weight a Bisphenol-A-derived poly(formal) (6) using a phase-transfer catalyst in DCM. A Bisphenol-AF-derived poly(formal) (7) is also synthesized by solution polycondensation of Bisphenol AF (1) with DCM in highly polar cosolvents in the presence of potassium hydroyxide (Scheme 3).12 Aprotic polar solvents such as A/W-dimethylformamide... 

Phase-transfer techniques are widely used for the preparation of polymers. For example, potassium fluoride is used to produce poly(etherketone)s under phase-transfer conditions (Scheme 10.18). Use of this reagent allows the chloroaro-matics to be used as starting material as opposed to the more expensive flu-oroaromatics that are usually employed [23]. This method is suitable for the synthesis of high molecular weight semicrystalline poly(ether ketone)s, although the presence of excess potassium fluoride in the reaction mixture can lead to degradation reactions. The use of a phase transfer catalyst can allow the use of water-soluble radical initiators, such as potassium peroxomonosulfate used to promote the free-radical polymerization of acrylonitrile [24],... 

Cation-Binding Properties of Crown Ethers, Lariat Ethers, Bibracchial Lariat Ethers, and Poly(ethylene glycols) as Potential Phase-Transfer Catalysts... 

The utilization of polar polymers and novel N-alkyl-4-(N, N -dialklamino)pyridinium sedts as stable phase transfer catalysts for nucleophilic aromatic substitution are reported. Polar polymers such as poly (ethylene glycol) or polyvinylpyrrolidone are thermally stable, but provide only slow rates. The dialkylaminopyridininium salts are very active catalysts, and are up to 100 times more stable than tetrabutylammonium bromide, allowing recovery and reuse of catalyst. The utilization of b is-dialkylaminopypridinium salts for phase-transfer catalyzed nucleophilic substitution by bisphenoxides leads to enhanced rates, and the requirement of less catalyst. Experimental details are provided. 

This article reports on the synthesis of photosensitive polymers with pendant cinnamic ester moieties and suitable photosensitizer groups by cationic copolymerizations of 2-(cinnamoyloxy)ethyl vinyl ether (CEVE) (12) with other vinyl ethers containing photosensitizer groups, and by cationic polymerization of 2-chloroethyl vinyl ether (CVE) followed by substitution reactions of the resulting poly (2-chloroethyl vinyl ether) (PCVE) with salts of photosensitizer compounds and potassium cinnamate using a phase transfer catalyst in an aprotic polar solvent. The photochemical reactivity of the obtained polymers was also investigated. 

The most straightforward way to obtain polymeric phosphonium salts involves introducing the phosphonio groups on to a suitable polymeric structure, for example by reacting tertiary phosphines with a poly(chloromethylstyrene) (reaction 99). The polymeric phosphonium salts obtained in this way are mostly used as polymer-supported phase-transfer catalysts for nucleophilic substitutions reactions under triphase conditions. 

Further, methods using phase transfer catalysts are suitable for the production of transparent poly(siloxane)/PC copolymers (27). As phase transfer catalyst a methyltributyl ammonium salt is used. 

Poly(vinylbenzyl chloride) (VBC) is an ideal starting material onto which a variety of functional groups can be attached through relatively simple reactions and mild reaction conditions. Functionalized polymers are of interest in a variety of applications including but not limited to fire retardants, selective sorption resins, chromatography media, controlled release devices and phase transfer catalysts. An example of the wide applicability of functionalized polymers is provided by trimethyl ammonium functionalized poly(VBC). 

Neumann, R. and Sasson, Y., Poly(ethylene glycols) as phase-transfer catalysts in the alkoxylation of halobenzenes of alkyl aryl ethers, Tetrahedron, 1983, 39, 3437. 

Totten, G.E., Clinton, N.A. and Matlock, P.L., Poly(ethylene glycol) and derivatives as phase transfer catalysts, J. Macromol. Sci., Rev. Macromol. Chem. Phys., 1998, C38, 77. 

DHHYDROBROMINATION Phase-transfer catalysts. Poly(ethylene glycols). 

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