Synthesis and Photochemical Reaction of Poly(ester)s Containing Donor–Acceptor Type Norbornadiene Residues in the Both Main and Side Chains

Abstract

ABSTRACT:The synthesis and photochemical valence isomerization of polymers containing donor-acceptor type norbornadiene (D-A NBD) residues in both main and side chains, by the polyaddition of 5-(4-methoxyphenyl)-1,4,6,7,7-pentamethyl-2,5-norbornadiene-2,3-dicarboxylic acid diglycidyl ester (D-A NDGE) with terephthaloyl chloride follows by substitution reactions of the resulting polymer with potassium 5-(4-methoxyphenyl)-1,4,6,7,7-pentamethyl-3-methylester-2,5-NBD-2-carboxylate, potassium 5-(4-methoxyphenyl)-1,4,6,7,7-pentamethyl-3-(N,N-dipropylcarbamoyl)-2,5-NBD-2-carboxylate, and potassium 5-(4-methoxyphenyl)-1,4,6,7,7-pentamethyl-3-(N-methyl-Nphenylcarbamoyl)-2,5-NBD-2-carboxylate, respectively. The photochemical valence isomerization of the synthesized poly(ester)s (P-1-P-4, and P-5a-c) was examined in tetrahydrofuran solution or in the film state upon irradiation with a 500-W xenon lamp, and it was found that each photochemical reaction proceeded very smoothly. It was also observed that the rate of the photochemical reaction of the NBD polymers increased efficiently by the addition of 4,4 0 -bis-(diethylamino)benzophenone (BEBP) as a photo-sensitizer in the film state. The stored thermal energies of the irradiated polymers were evaluated by DSC analysis to be 75-153 J/g. [DOI 10.1295/polymj.37.246] KEY WORDS Donor-Acceptor Type Norbornadiene / Polyaddition / Photochemical Valence Isomerization / Photo-sensitizer / Stored Thermal Energy / The photochemical valence isomerization between norbornadiene (NBD) and quadricyclane (QC) is of great interest as a solar energy conversion and storage system, 1-4 because NBD can convert solar energy into 96 kJ/mol of thermal energy through the strain in QC.Nishikubo et al. [5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20] reported the synthesis of photoreactive polymers containing NBD residues in the main chain or the side chain, and it was observed that the NBD residues in the polymers converted smoothly to form QC ones. These NBD-containing polymers had high stored thermal energies. However, these synthesized polymers were not suitable to applications as a material for solar energy conversion and storage systems, because they did not have strong absorption band into visible region and did not have good durabilities in the reversible photochemical reaction.On the other hand, it is known that donor-acceptor type norbornadiene (D-A NBD) derivatives had absorption band into visible region and converted to the corresponding QC derivatives in high quantum yield. 21,22 Furthermore, Nishikubo et al. [23][24][25][26] synthesized the polymers containing D-A NBD moieties in the main chain or side chain and examined their photo-chemical valence isomerization. It was found that their synthesized polymers had high photochemical reactivities and good fatigues of resistance. [23][24][25][26] Furthermore, it is expected that the thermal storage energies of the polymers increase with increasing the ratio of the NBD moieties.From these backgrounds, in this article, we examined...

Features of heterogeneous catalytic transformations of strained carbocyclic compounds of the norbornene series

“…В [125] изучено влияние пористой структуры цеолитов и условий проведения реакции на селективность димеризации НБН. Показано, что в среде хлоралканов в аргоне конверсия НБН достигает 100%, а селективность по димерам составляет 90% в присутствии цеолитов HZSM-12 17 19 ASM-40 -мезопористый алюмосиликаты с атомарным соотношением Si/Al = 40. 20 ZSM-12 -богатый кремнеземом цеолит с одномерной 12-членной системой кольцевых каналов и раскрытием пор 5.7 × 6.1 Å, что несколько больше, чем у ZSM-5.…”

“…2022;17(4):275-297 ВВЕДЕНИЕ Норборнадиен (НБД), норборнен (НБН) и их производные занимают важное место в органическом и нефтехимическом синтезе [1]. За 70-летнюю историю эти соединения нашли применение в парфюмерной промышленности [2][3][4][5], медицине [6][7][8][9], сельском хозяйстве [10][11][12] в производстве полимерных материалов с уникальными свойствами [13][14][15][16][17][18][19][20][21][22], микроэлектронике и фотонике [23][24][25][26][27], в качестве конвертеров солнечной энергии [28][29][30][31][32][33][34], топлив с различными свойствами [35][36][37][38][39][40][41][42][43][44][45][46][47] и так далее. Количество публикаций и патентов, связанных с получением и использованием производных НБН и НБД, в 2022 г. превысило 35 тыс.…”

Photochemical and Photophysical Studies of and in Bulk Polymers

“…50 This " nonclassical " excimer emission arises from conformations in which As mentioned in the section on " Chromophores or Other Reactive Groups in a Polymer, " residual amounts of sensitizers in a polymer can absorb light in competition with guest molecules, causing changes in guest reactions and reactivity. 57 Sensitizers can also absorb light and transfer potential energy to the polymer backbone, affecting the quantum yield and polarization of emitted light. 58 Functional groups intrinsic to a polymer can also sensitize reactions of guest molecules.…”