Radical copolymerization of methyl 2-norbornene-2-carboxylate and 2-phenyl-2-norbornene with styrene, alkyl acrylate, and methyl methacrylate: Facile incorporation of norbornane framework into polymer main chain and its effect on glass transition temperature

Radical copolymerization of alkyl cyclobutenecarboxylates fused with cycloaliphatic framework with alkyl (meth)acrylates

“…As was reported in our previous publication, incorporation of norbornane framework in polymer backbone is effective to raise T g of copolymers obtained by the copolymerization with n BA . A similar effect can be expected for the fused cyclobutane units incorporated by the polymerization of alkyl cyclobutenecarboxylates in this study.…”

“…As clearly observed in these plots, all the points for 4‐6a are on a same linear relationship with a slope value of 1.76. The slope value can be directly related to an efficiency of raising T g of poly( n BA)‐based copolymers, and we have reported that the values for styrene and methyl 2‐norbornene‐2‐carboxylate repeating units are 1.43 and 2.91, respectively . Thus, the value 1.76 for 4‐6a demonstrates that these repeating units are more effective in the T g ‐raising ability than styrene, though the effects do not reach the level of methyl 2‐norbornene‐2‐carboxylate.…”

“…As described in the literature, when norbornene was used as a cycloolefin, products were obtained as a mixture of three isomers, where the 1 H NMR‐calculated composition of the desired [2 + 2] adduct 7 is highest in the case of methyl ( 7‐9 a , [ 7 a ]/[ 8 a ]/[ 9 a ] = 63:27:10–77:17:6 in our experiments, while 69:19:12 in the literature) and 2‐hydroxyethyl ( 7‐9 b , [ 7 b ]/[ 8 b ]/[ 9 b ] = 51:41:8) esters, but alkyl norbornenecarboxylate 8 predominates in the case of γ‐BL ester ( 7‐9 c , [ 7 c ]/[ 8 c ]/[ 9 c ] = 26:53:21–27:55:18). As for the two undesired products 8 and 9 , alkyl 2‐norbornene‐2‐carboxylates 8 can copolymerize with alkyl acrylates but not with alkyl methacrylates according to our previous study, while the reactivity of 1,2‐substituted crotonate‐derivative 9 in radical copolymerizarion is assumed to be much lower on the basis of reported low radical polymerizability of methyl and ethyl 1‐crotonates . Unfortunately, it is not possible to isolate each isomer from the mixture because of their similar properties and an identical molecular weight.…”

“…Meanwhile, we have recently reported that alkyl 2‐norbornenecarboxylate can be radically copolymerized with alkyl acrylate, affording polymers having norbornane framework in the polymer backbone . We have also demonstrated that the thus obtained norbornane‐containing copolymers are promising candidates for 193 nm photoresist applications by revealing dissolution rate vs. exposure dose relationship of some copolymers of alkyl 2‐norbornenecarboxylate with alkyl (meth)acrylates .…”

Norbornene/n-Butyl methacrylate copolymerization over α-Diimine nickel and palladium catalysts supported on multiwalled carbon nanotubes

“…However, these polymers suffer the biggest weakness in brittleness. To overcoming the weakness, a series of copolymers of NB and polar monomers have been studied . However, due to the catalyst poisoning in the direct copolymerization of NB and polar monomers, the simple and efficient synthesis of well‐defined catalysts, which show an increased stability to polar monomers remains a scientific challenge.…”