Synthesis of Upper Rim Functionalized Calixarene‐Based Poly(norbornenes)

Abstract

A modified synthesis of 25‐allyl‐26,27,28‐trihydroxycalix[4]arene is reported. This calix[4]arene was utilized to prepare calix[4]arenes containing norbornene and calix[4]arene containing azo dyes and norbornene on their upper rims. The calixarene monomers were reacted with Grubbs' second generation catalyst to give poly(norbornenes) containing calixarenes. The poly(norbornenes) were determined to possess molecular weights between 45 100 and 116 200 with PDIs between 1.4 and 1.9. Thermal analysis showed that the azo dye containing polymers were less thermally stable than the non‐azo dye containing polymers with decompositions beginning at 140 °C and 395 °C, respectively. The azo dye containing polymers displayed λmax at 430 nm in THF solutions that underwent a bathochromic shift to 520 nm when acidified with HCl(g), due to the formation of the azonium ion.magnified image

Design of Thermochromic Polynorbornene Bearing Spiropyran Chromophore Moieties: Synthesis, Thermal Behavior and Dielectric Barrier Discharge Plasma Treatment

“…It is well known that polynorbornene is a rather flexible chain, arising from its low T g value [ 79 , 80 ]. This value can be manipulated via incorporation of different molecules into the side chain of the polymers [ 46 , 47 , 48 , 49 , 50 , 51 , 52 , 53 , 54 , 55 , 56 , 57 , 58 , 59 , 60 , 61 , 62 ]. Therefore, it is anticipated that the functionalization of norbornene monomers with the spiropyran moieties increases the T g values of their corresponding polymers.…”

“…Ring opening metathesis polymerization (ROMP) of norbornene monomers has been a very successful approach to control the polymer’s molecular structure, size, and bulk properties [ 46 , 47 , 48 , 49 , 50 , 51 , 52 , 53 ]. In the past, we have used Grubbs catalyst in the synthesis of various substituted polynorbornenes [ 54 , 55 , 56 , 57 , 58 , 59 , 60 , 61 ]. We also developed several series of polynorbornene containing aryl- and hetaryl-azo chromophores as candidates for long-term storage information, as well as in photonic devices [ 62 ].…”

Proton Sensing Color Changing Organoiron and Organic Macromolecules

“…Moreover, incorporation of azo dyes into these molecules enables their use as chromoionophores for metal ion recognition and for liquid-liquid extraction of metal ions [67]. The synthesis of highly colored polynorbornene bearing calixarene moieties was reported in 2010 [68]. The [4] arene.…”

“…The [4] arene. Ring opening metathesis polymerization of these monomers using Grubbs' catalyst resulted in the production of polynorbornene with azo moieties in the upper rim of the calixarene molecules [68]. The molecular weights of the colored polymers were in the range of 42,100 and 61,200 with PDI values of 1.4 and 1.9, respectively.…”

“…The molecular weights of the colored polymers were in the range of 42,100 and 61,200 with PDI values of 1.4 and 1.9, respectively. Due to the presence of the azo moieties, these polymers revealed k max at 430 nm which displayed a bathochromic shift to 520 nm upon their acidification via exposure to HCl (g) [68].…”