A Hard Templating Approach to Functional Mesoporous Poly(norborn‐2‐ene)‐Based Monolithic Supports

Abstract

A hard‐templating method is presented for the synthesis of functional ring‐opening metathesis polymerization (ROMP) derived, poly(norborn‐2‐ene)‐based monolithic supports prepared under solvent‐induced phase separation conditions using the first‐generation Grubbs initiator RuCl2(PCy3)2(CHPh) (1, Cy = cyclohexyl). Norborn‐2‐ene (NBE), 1,4,4a,5,8,8a‐hexahydro‐1,4,5,8‐exo,endo‐dimethanonaphthalene (DMN‐H6) and trimethylolpropane‐tris‐(5‐norbornene‐2‐yl‐carboxylate (TMPTNC) are used as monomers and crosslinkers, respectively. 2‐Propanol and toluene are used as macro‐ and microporogen. Silica (SiO2) nanowires (SNWs) surface‐modified with NBE are used as hard templates. exo,endo‐Norborn‐5‐ene‐2‐ylmethanol (NBE‐CH2OH) is used as functional comonomer. The tailored porogenic system together with the surface‐functionalized SNWs allows for a full dispersion of the SNWs in the polymerization mixture and their incorporation into the monolithic structure during the phase separation process. This way, ROMP‐derived monoliths with pore dimensions of 10–15 nm, specific surface areas up to 3.7 m2 g−1, and pore porosities up to 33% are obtained after removal of the SNWs by chemical etching at room temperature.

Ru- and Ir-complex decorated periodic mesoporous organosilicas as sensitizers for artificial photosynthesis

“…21 Among the reported norbornene derivatives, those containing alkoxysilane groups have attracted great interest in the polymer industry as promising silyl agents to produce a variety of polymeric composite materials. [22][23][24][25][26] Although siloxane norbornenes have been prepared by olefin hydrosilylation of 2,5-norbornadienes, 27 currently the most promising strategy to obtain them is through the Diels-Alder reaction between a vinyltrialkoxysilane and dicyclopentadiene. 28 As previously mentioned, iEDDA reactions between norbornene and tetrazine derivatives lead to interesting N-chelating ligands for the coordination of a wide variety of transition metals.…”

Hydrosilylation of Alkynes Under Continuous Flow Using Polyurethane‐Based Monolithic Supports with Tailored Mesoporosity

“…The drop from 920 to 100–120 µL g −1 is in line with a decreased microporosity and an increased mesoporosity in monoliths P3 – P5 . Notably, complementary to a recently reported template‐based approach, [ 40 ] this is the first successful report on a tuning of the pore diameters of monolithic materials in the low mesopore region via SIPS.…”

“…Notably, complementary to a recently reported template-based approach, [40] this is the first successful report on a tuning of the pore diameters of monolithic materials in the low mesopore region via SIPS.…”