Nitrogen, functionalized resins

Relatively little research has been done on nitrogen functionalized resins. Figure 6 depicts the commercial resins 10, 11 and 12, their maximum recommended operating temperature and the resin type. 

Nitrogen and phosphor functionalized adsorbents for the adsorption of Co(II). Hereby, Amberlyst A2I was selected for its nitrogen functionality. It is a macroreticular polystyrene - crosslinked by divinylbenzene - anion exchange resin functionalized with an alkylamine group. As a phosphorous functionalized adsorbent, polymerbounded PPhj has been selected. It is a gel-type polystyrene - crosslinked by 2 [%] divinylbenzene - resin functionalized with a PPh2 group. 

A simple way to produce polymers with specific nitrogen functions in controlled concentration is to prepare phenol-formaldehyde resins in which part of the phenol is substituted by aniline (for amine-type nitrogen) or... 

A limitation of this approach was the fact that the cyclization could not be accomplished on the resin. This would preclude further functionalization of the core. Therefore an alternate approach was to link the resin to the core via an aminoalcohol spacer as in 93. Furthermore, since linkage was conducted through the P-ketoester component rather than through the nitrogen atom, dihydropyridines 94 could now be formed on the solid support. When the 4-aryl substituent of 94 was nitro, on-resin reduction to the corresponding amine was possible. This allowed for further addition of diversity elements to the core scaffold before cleavage from the resin. 

Positive photoresists, by contrast, are based on water-soluble novolak resins with naphthalene diazoquinone sulfonate (NDS) as the photosensi-tiser. On photolysis the NDS causes a rearrangement in the polymer to yield nitrogen gas plus an indene carboxylic acid. This latter functional group considerably increases the solubility of the polymer, hence solubilising those areas of the polymer that had been exposed to light. 

Grafting on the resin was achieved via a nucleophilic substitution of the benzylic chlorine by the deprotonated OH-linker of 52 (Scheme 29) by using a mixture of KO Bu, 18-crown-6 and CsBr. Determining the nitrogen content of solid phase samples by elemental analyses was accomplished, to verify the functionalization of the polymer. This enables calculation of the degree of functionalization. Usually, an occupancy of more than 20 percent of the theoretical sites was achieved. Saponification of the functionalized Merrifield resin P-52 leads to the monoanionic NJ, 0 functionalized solid phase. Subsequent reaction with [ReBrtCOlsJ afforded the polymer mounted tricarbonyl rhenium complex P-52-Re (Scheme 29). 

Adhesives based on hydrolysis resistant chemistry (i.e., adhesives D and E) show a high retention of initial properties after exposure to an aggressive corrosion environment and the failure occurs cohesively within the adhesive. The cure reactions of these adhesives involve the formation of hydrolysis resistant carbon-nitrogen bonds in reactions involving the free N-H functionality of the Versamid or Genamid hardener with the oxirane functionality of the epoxy resin that is present in the adhesive formulation ... 

The resins studied (Rohm and Haas and Ionac) were all functionalized, cross-linked, styrene polymers with the exception of poly (4-vinyl-pyridine). Porous, macroreticular resins included the polymeric analogs of N,2V-dimethylbenzylamine (A21 polyDMBA, Rohm and Haas), N,N-dimethylaniline, and l-phenyl-2- (N,2V-dimethylamino) ethane (poly-Alipham), The last two materials were prepared in this laboratory. Nitrogen content of the porous resins was 4.1, 2.5, and 2.6 mequiv/gram, respectively. Poly(4-vinylpyridine) (6.9 mequiv/gram) had a gel-type structure. 

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