Sulfonium salts polymeric resins

Two-phase systems, usually consisting of a strongly alkaline aqueous rfiase and methylene chloride, are also effective and convenient. Trialkylsulfonium salts with methylsulfate counterions can be used alone under these conditions, whereas those with halide counterions generally benefit from added phase transfer catalysts (equation 2). Dodecyldimethylsulfonium chloride was found to be an effective phase transfer reagent. A sulfonium salt covalently attached to a polymeric resin was found most effective when a phase transfer agent was also employed. ... 

Recycling occurs in the following way. Ph2S is tethered to a polymeric resin so that the sulfonium salt and subsequent ylide are made in the usual way, but they are also tethered to the resin. Once the ylide has been made, the metal complex is introduced and the alkylidene forms. The Ph2S by-product that also appears, however, is tethered to the resin and may be reused in the next cycle. This method also allows for facile separation and purification of the desired alkylidene because by-product is not in the same phase as product. The... 

Compositions having, upon polymerization, good adhesion and sealing properties were described by Nippon Soda [137] in 1986. The composition comprised an epoxidized polybutadiene, epoxy resin, onium salt, and sensitizer. Grace Japan [138] patented the simultaneous photopolymeriza-tion of epoxy compounds and compounds containing unsaturated groups by the use of free radical photoinitiators and sulfonium salts in 1986. 

The structures of these ylide polymers were determined and confirmed by IR and NMR spectra. These were the first stable sulfonium ylide polymers reported in the literature. They are very important for such industrial uses as ion-exchange resins, polymer supports, peptide synthesis, polymeric reagent, and polyelectrolytes. Also in 1977, Hass and Moreau [60] found that when poly(4-vinylpyridine) was quaternized with bromomalonamide, two polymeric quaternary salts resulted. These polyelectrolyte products were subjected to thermal decyana-tion at 7200°C to give isocyanic acid or its isomer, cyanic acid. The addition of base to the solution of polyelectro-lyte in water gave a yellow polymeric ylide. 

For some applications, for example curing of epoxy resins, the in situ generation of cationic initiators is required. This may be achieved by photochemical decomposition of suitable promotors to radicals, which in the presence of diazonium, sulfonium, or halonium salts (not able to initiate the polymerization by itself) are converted into corresponding cationic initiators [45-48]. 

Quantum yields of acid, and iodobenzene or phenyl sulfide were measured by irradiating. 03 molar acetonitrile solutions of diphenyl iodonium hexafluoroarsenate and triphenyl sulfonium hexa-fluoroarsenate. Photosensitizers were included at identical optical density (1.0) at the wavelength of irradiation (366 nm). Relative polymerization rates were calculated as a function of the gelation time of a solution of 50% acetone, and 50% cycloaliphatic diepoxide resin ARALDITE CY-179 (v/v) containing the photosensitizer and onium salt as above. Experimental details were published previously.(8,15) IRGACURE and ARALDITE are registered trademarks of the Ciba-Geigy Corporation. 

Sulfonium Polymers. Polysulfonium salts have been extensively studied because of the versatile possibilities of their application. They can be used as ion-exchange resins, polymer supports in peptide synthesis, polymeric reagents, and... 

Commercially-available diaryliodonium (CD-1012, Sartomer) and triaryl-sulfonium (CD-1010, Sartomer) salts were found to initiate polymerization of multifunctional epoxide and vinyl ether monomers [24]. Figure 17a shows a line structure achieved by polymerization of a mixture of poly(bisphenol A-co-epichlorohydrin) glycidyl end-capped and 3,4-epoxycyclohexylmethyl 3,4-epoxylcyclohexanecarboxylate (K126, Sartomer) initiated by CD-1012. To check the potential spatial resolution, we focused the laser using high-NA optics to polymerize commercial resin SCR701 (JSR) and a lateral spatial resolution of 100 nm was obtained (Fig. 17b). 

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