Protective encapsulation of acid‐sensitive catalysts using polyethylene ligands

The stability of polyethylene oligomer (PE_Olig)‐entrapped salen‐metal complexes toward acidolysis is described. These complexes dissolve in hot toluene and precipitate as hydrophobic powders. The salen species in these precipitates or in precipitates of admixtures of oligomeric complexes and unfunctionalized polyethylene are stable to acid when suspended in acidic methanol for 24 h at 25°C. The lack of metal leaching due to acid‐promoted demetalation was determined using both colorimetric and ICP‐MS analyses. The ICP‐MS results showed the amount of metal loss for PE_Olig‐salen‐metal complexes was 0.27%, 0.45%, and 0.79% for half‐salen Cr(III), salen Cr(III), and salen Mn(III) complexes, respectively. These results were in contrast to the reported behavior of low molecular weight salen metal complexes and to results seen with a salen complex bound to divinylbenzene (DVB) crosslinked polystyrene which demetalates under acidic conditions at room temperature. Salen complexes formed with PE_Olig complexes also demetalate when the PE_Olig‐bound species are in solution at elevated temperature and exposed to acid. These results show that as solids oligomeric polyethylene ligands even without added PE can serve as a protective encapsulating matrix for the solid forms of polymer‐supported catalysts. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Polyolefin soluble polyisobutylene oligomer‐bound metallophthalocyanine and azo dye additives

Metallophthalocyanines prepared with polyisobutyl (PIB) substituents have very high solubility in organic solvents including saturated hydrocarbons, toluene, and other low polarity organic solvents. In heptane, PIB‐bound metallophthalocyanines have solubility of about 0.1 g/mL at 25 °C, solubility values that are significantly higher than other substituted metallophthalocyanines. PIB terminally functionalized with metallophthalocyanines as well as PIB containing terminal azo dye groups also dissolve in molten hydrocarbon polymers like polyethylene or polypropylene. Thus, these highly chromogenic PIB‐bound dyes can be incorporated uniformly into the polyolefins to form colored polymer solids on cooling. Because only a low concentration of a highly hydrocarbon compatible dye is used, the crystallinity and thermal properties of the colored polyolefin products are not significantly affected. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 545–551     

Polyethylene as a nonvolatile solid cosolvent phase for catalyst separation and recovery

The studies described here show that a relatively low molecular weight, narrow polydispersity polyethylene (PE) wax (Polywax) can serve as a nontoxic and nonvolatile alternative to alkane solvents in monophasic catalytic organic reactions where catalysts and products are separated under biphasic conditions. In this application, a polymer that is a solid at room temperature substitutes for a conventional alkane solvent at ca. 80 °C. In addition to the advantages of being a nonvolatile, nontoxic, reusable solvent, this hydrocarbon polymer solvent, like heptane, can sequester nonpolar soluble polymer-bound catalysts after a reaction and separate them from products. The extent of this separation and its generality were studied using polyisobutylene (PIB)- and poly(4-dodecylstyrene)-bound dyes and PE-bound Pd allylic substitution catalysts, PIB-bound Pd cross-coupling catalysts, and PE- and PIB-bound metathesis catalysts. Catalytic reactions were effected using single-phase reaction mixtures containing Polywax with toluene, THF, or THF/DMF at ca. 80 °C. These solutions either separate into two liquid phases on addition of a perturbing agent or separate as a solid/liquid mixture on cooling. The hydrocarbon polymer-bound dyes or catalysts either separate into the hot liquid Polywax phase or coprecipitate with Polywax and are subsequently isolated as a nonvolatile Polywax solid phase that contains the dye or the recyclable catalyst.     

Micelle‐Enabled One‐Pot Guanidine Synthesis in Water Directly from Isothiocyanate using Hypervalent Iodine(III) Reagents under Mild Conditions

In this work, we developed a one‐pot synthesis of guanidine directly from isothiocyanate using DIB (diacetoxyiodobenzene) as a desulfurizing agent under micellar conditions in water. Our optimization study revealed that the use of 1 % TPGS‐750‐M as a surfactant with NaOH as an additive base at room temperature can convert a variety of isothiocyanates and amines into corresponding guanidines in excellent yields (69 – 95 %). This synthetic process in water can be applied to prepare guanidine at gram‐scale quantity. Our aqueous micellar medium also demonstrated high reusability as the reaction can be performed for several cycles without losing its efficiency. The reaction is metal‐free, utilizes water as solvent and practical (room temperature and open flask).