New Large Refractive-Index Change Materials: Synthesis and Photochemical Valence Isomerization of the Calixarene Derivatives Containing Norbornadiene Moieties

Kudo, Hiroto; Ueda, Wataru; Sejimo, Kiyomitsu; Mitani, Kohji; Nishikubo, Tadatomi; Anada, Tetsuo

doi:10.1246/bcsj.77.1415

Cited by 16 publications

(12 citation statements)

References 29 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…1,1¢,1¢¢-Tris(4-glycidyloxyphenyl)methane (TGOPM) was prepared according to an established method. 13 Unless otherwise stated, reagents were purchased from commercial suppliers and used without any further purification.…”

Section: Experimental Procedures Materialsmentioning

confidence: 99%

“…The Dn D 's are dependent on the change of molar refraction (R) and density (r) before and after photoirradiation. 13 The difference of Dn D of HBP c -EPOX and HBP c -OX could be explained by the size of cyclic ether and the efficiency of photo-curing. The high reactivity and compact structure of glycidyl lead to higher crosslinking density, and as a consequence, HBP c -EPOX shows larger Dn D than HBP c -OX.…”

Section: Synthesis Of Hyperbranched Fluorinated Polymers M Miyasaka Ementioning

confidence: 99%

See 1 more Smart Citation

Synthesis of hyperbranched fluorinated polymers with controllable refractive indices

Miyasaka

Koike

Fujiwara

et al. 2011

Polym J

Self Cite

View full text Add to dashboard Cite

INTRODUCTIONPolymers containing fluorine atoms (fluorinated polymers) exhibit increased thermal stability, hydrophobicity, improved chemical resistance and decreased intermolecular attractive forces in comparison with their hydrocarbon analogs. These properties are derived from the fundamental atomic properties of fluorine, such as high ionization potential, low polarizability and high electronegativity. 1 The high ionization potential, combined with the low polarizability, leads to weak intermolecular interactions, which in turn leads to low-surface energy and low refractive indices of fluorinated polymers. Recently, fluoropolymers have received considerable attention as high-performance materials for applications in optoelectronic fields. Specifically, the refractive index is a very important property of polymers for photonic applications, for which highly fluorinated polymers such as Teflon (DuPont, Wilmington, DE, USA) and CYTOP (ASAHI GLASS CO., LTD., Tokyo, Japan) are well known and widely used in optical communication networks. Current optical communication networks are based on silica optical fiber and devices. To integrate with these devices and materials, and to reduce the optical loss, polymer materials with refractive index values close to that of the silica materials (1.46) are desired. 2 Therefore, materials with a controllable refractive index are required for the successful design and fabrication of photonic devices. For example, the widely used fluorinated polyimides usually have relatively low refractive indices 3 and this value can be easily manipulated by introducing polar groups and copolymerizing with comonomers containing heavier atoms, such as bromine to give high refractive indices. However, it appears difficult to lower the refractive index. We have modified fluoropolymers with the simple polyaddition of bis(epoxide)s with dicarboxylic acids and diols in the presence of quaternary onium salts and they exhibited a linear relationship between refractive indices and fluorine contents of the polymer. 4,5 Similar investigations have been conducted with fluorinated aromatic-aliphatic copolyethers, 6 fluorinated poly (phthalazinone ether)s 7 and hyperbranched fluorinated polyimides. 8 The relationship between the refractive index (n D ), density (r g cm À3 ), molecular weight (M g mol À1 ) and molecular refraction (R cm 3 mol À1 ) of a polymer is described by the Lorentz-Lorenz equation (Equation 1). 9According to the Lorentz-Lorenz equation, the polymers with low r give low n D . That is, hyperbranched polymers (HBPs) are good candidates for the production of low-density polymers because of their three dimensional globular architecture with higher branched structure. 10 Recent study has indicated that hyperbranched structures have an increasingly important role in reducing crystallinity, to avoid significant optical loss. For example, we have observed and reported that the HBPs show no birefringence due to their highly branched globular structure, preventing their polymer orientation. 11 On t...

show abstract

Section: Experimental Procedures Materialsmentioning

confidence: 99%

Section: Synthesis Of Hyperbranched Fluorinated Polymers M Miyasaka Ementioning

confidence: 99%

Synthesis of hyperbranched fluorinated polymers with controllable refractive indices

Miyasaka

Koike

Fujiwara

et al. 2011

Polym J

Self Cite

View full text Add to dashboard Cite

show abstract

“…From this viewpoint, we designed calixarene derivatives with pendant epoxy groups, and examined the reaction of the resulting calixarene derivatives and 3-phenyl-2,5-norbornadiene-2-carboxylic acid to obtain the corresponding calixarene derivatives with NBD moieties containing pendant hydroxyl groups (Scheme 4). 37 The synthesized calixarene derivatives BCA-NBD, MCA-NBD, CRA-NBD, CRA 10 -NBD, CRA(OH)-NBD were soluble in common organic solvents and had good film-forming properties. The photochemical valence isomerization of these calixarene derivatives with pendant NBD was examined in thin films.…”

Section: Calixarene Derivatives As Refractive-index-changing Materialsmentioning

confidence: 99%

Development of Novel Photo-Functional Materials Based on Cyclic Oligomers

Kudo

Nishikubo

2009

Polym. J.

Self Cite

View full text Add to dashboard Cite

Novel photo-functional materials, such as refractive-index-changing materials, argon fluoride (ArF) resist materials, and electron beam (EB) resist materials, were designed based on the structures of calixarenes, cyclodextrin, and noria. The synthesis and refractive-index properties of calixarene derivatives containing photo-reactive groups, including azobenzene, norbornadiene, anthracene, cinnamate, and chalcone, were examined, and refractive-index changes (Án D 's) of between 0.007 and 0.061 were observed. The synthesis and patterning properties of a single-layer ArF photoresist system of -CD derivative containing t-butyl ester and fluorine were examined, and a well-resolved 100 nm line and space pattern was obtained on a silicon wafer. A new ladder-like macrocycle, noria (water wheel in Latin), was also synthesized and its application as an EB resist material was examined. The noria derivatives noria-COO t Bu containing t-butyl ester groups, noria-BOC containing t-butyloxycarbonyl group, and noria-acetal containing acetal groups had good physical properties and photo-reactivity. EBresist based on noria-COO t Bu and noria-BOC provided clear line and space patterns at a resolution of 70 and 50 nm, respectively.The development of novel photo-functional materials has contributed substantially to progress in the electronic and optoelectronic industries. Photo-reactive groups, such as radical-or cation-polymerizable groups, photo-isomerizable groups, and photo-removable groups, are useful for obtaining ultraviolet (UV)-cured resins, refractive-index-changing materials, and photo-resist materials, respectively. The physical properties of photo-functional materials, such as film-forming characteristics, thermal stability, mechanical properties, and photo-reactivity, depend primarily on the polymer or oligomer structure. Generally, the photochemical reactivity increases with decreasing glass transition temperature (T g ), due to increase of the molecular motion of polymer chains and functional groups.The photo-chemical reactivity of oligomers is usually greater than that of polymers, due to the lower T g of oligomers compared with polymers. However, the mechanical properties, thermal stability and film-forming properties of oligomer derivatives are inferior to those of polymer derivatives. However, if a linear oligomer is changed to a cyclic oligomer by coupling reaction of the two ends, the physical properties of the resulting cyclic oligomer are expected to be superior to those of the linear oligomer. Therefore, we considered that photofunctional cyclic oligomers might combine the advantages of photo-functional polymers and photo-functional oligomers. That is, photo-functional cyclic oligomers might have both high photo-chemical reactivity and good physical properties.Calixarenes are typical cyclic oligomers containing many hydroxyl groups, and are prepared easily by the reaction of phenols with aldehydes (Scheme 1). 1Although it is well known that calixarenes are attractive materials for use as host molecules in th...

show abstract

“…[1][2][3] Recently, much attention has been devoted to the photochemical control of refractive indices for polymer films, owing to their potential in optical network technology. 3 Although there are extensive studies directed toward a photoinduced decrease in refractive indices for polymer films, [4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19] only a few attempts have been made to enhance the refractive index through photochemical transformations. 12,[20][21][22][23][24][25] For example, Langer et al 21 reported that irradiation of a polymerbearing thiocyanate pendants enhanced the refractive index (n) of the polymer by 0.031.…”

Section: Introductionmentioning

confidence: 99%

Effects of aryl substituents in N-acetyl-α-dehydroarylalanine naphthyl ester additive on the photoinduced refractive index change of poly(methyl methacrylate) film

Nakajima

Komatsu

Iikura

et al. 2010

Polym J

View full text Add to dashboard Cite

Aryl substituent effects on photoinduced refractive index changes were investigated with the use of poly(methyl methacrylate) (PMMA) films doped with (Z)-N-acetyl-a-dehydroarylalanine naphthyl esters ((Z)-1). Upon irradiation with Pyrex-filtered or unfiltered light from a high-pressure mercury lamp, (Z)-1 underwent heterolytic cleavage of the ester C(¼O)-O bond preferentially in both solution and PMMA film to afford arylmethylene-substituted (Z) oxazolone and naphthol derivatives as major products, irrespective of the aryl substituents introduced. Irradiation of (Z)-1 in the film with the unfiltered light enabled much more rapid photochemical transformation into the oxazolones and the intense ultraviolet absorption shifted to longer wavelength relative to that of the starting naphthyl esters. Analysis of the aryl substituent effects confirmed that the PMMA/(Z)-1 system, in which 1-naphthylmethylene-substituted oxazolone was formed along with 1-naphthol, enhanced the refractive index of this polymer film by as much as 0.020.

show abstract

New Large Refractive-Index Change Materials: Synthesis and Photochemical Valence Isomerization of the Calixarene Derivatives Containing Norbornadiene Moieties

Cited by 16 publications

References 29 publications

Synthesis of hyperbranched fluorinated polymers with controllable refractive indices

Synthesis of hyperbranched fluorinated polymers with controllable refractive indices

Development of Novel Photo-Functional Materials Based on Cyclic Oligomers

Effects of aryl substituents in N-acetyl-α-dehydroarylalanine naphthyl ester additive on the photoinduced refractive index change of poly(methyl methacrylate) film

Contact Info

Product

Resources

About