Synthesis and photochemical reaction of novel p‐alkylcalix[6]arene derivatives containing acryloyl or methacryloyl groups

Iyo, Masami; Tsutsui, Kosuke; Kameyama, Atsushi; Nishikubo, Tadatoimi

doi:10.1002/(sici)1099-0518(19990815)37:16<3071::aid-pola4>3.3.co;2-4

Cited by 8 publications

(9 citation statements)

References 3 publications

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“…Their inclusion properties can be modified by lower‐rim (hydroxyl groups) modification by esterification, etherification, conversion to amines or thiols, and so forth 7–12. They have acquired unique applications in analysis probes,13 membranes,14 decontaminating agents for wastewater,15 dendrimers,16 high‐performance polymers,17 curing agents,18, 19 and so forth 20. Lower‐rim bridging (linkage between hydroxy groups) has enabled the introduction of another macrocyclophane into the parent calixarenes 21–23.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of fully lower‐rim, carbonate‐bridged calix[8]arenes and their curing behavior

Sugioka

Hay

2001

J. Polym. Sci. A Polym. Chem.

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Novel fully lower-rim, carbonate-bridged calix [8]arene derivatives were successfully synthesized in high yield by the condensation of p-alkyl substituted calix[8]arenes with triphosgene. Different bases and catalysts were used for the preparation depending on the p-alkyl substituted groups of the calix[8]arenes. The conformational features of the derivatives were examined by 1 H NMR analysis. Thermosetting formulations were prepared from a mixture of bisphenol A polycarbonate with calix[8]arene carbonate derivatives using sodium benzoate as a catalyst. Their crosslinking behaviors were studied using differential thermal/thermogravimetric analysis. No glass-transition temperatures were observed after annealing at 280 -300°C . EXPERIMENTAL Materials and InstrumentsReagent-grade solvents and chemicals were used as received unless otherwise indicated. 4-t-Butyl phenol and p-cresol were purchased from Aldrich.

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Section: Introductionmentioning

confidence: 99%

Synthesis of fully lower‐rim, carbonate‐bridged calix[8]arenes and their curing behavior

Sugioka

Hay

2001

J. Polym. Sci. A Polym. Chem.

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“…4,5 Nishikubo et al reported the synthesis, properties, and photoreactivity of photo-functional materials based on calixarenes containing polymerizable groups, such as vinyl ether, 3 methacrylate, 6 propargyl ether, 3 oxetane, 7 oxirane, 7 and spiro ortho-ester groups.…”

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confidence: 99%

“…3 Certain calixarenes and their derivatives are amorphous in the solid state and have good film-forming properties. 4,5 Nishikubo et al reported the synthesis, properties, and photoreactivity of photo-functional materials based on calixarenes containing polymerizable groups, such as vinyl ether, 3 methacrylate, 6 propargyl ether, 3 oxetane, 7 oxirane, 7 and spiro ortho-ester groups. 8 It was shown that these calixarene derivatives have excellent thermal stability and high photochemical reactivity.…”

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confidence: 99%

“…8 It was shown that these calixarene derivatives have excellent thermal stability and high photochemical reactivity. Figure 1 illustrates the results of photocationic polymerization of calixarene derivatives containing oxirane groups derived from t-butylcalix [8]arene (BCA), p-methylcalix [6]arene (MCA), and calixresorcin [4]arene (CRA). 7 It was observed that the order of photochemical reactivity is as follows: CRA derivative > BCA derivative > MCA derivative.…”

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confidence: 99%

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Development of Novel Photo-Functional Materials Based on Cyclic Oligomers

Kudo

Nishikubo

2009

Polym. J.

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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...

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“…Recently, it was also suggested that calixarenes have unique characteristics such as small molecular size, good film-forming properties, 8,9 high glass transition temperature 10 (T g ), excellent thermal stability, 10,11 many reactive groups such as hydroxyl groups in small molecule, and so on. For example, Fujita et al found 8 that hexa-acetate of p-methylcalix [6]arene could be used as a negative type resist with ultrahigh resolution in electron beam lithography.…”

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confidence: 99%

Novel High Performance Materials. Calixarene Derivatives Containing Protective Groups and Polymerizable Groups for Photolithography, and Calixarene Derivatives Containing Active Ester Groups for Thermal Curing of Epoxy Resins

Nishikubo

Kameyama

Kudo

2003

Polym J

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ABSTRACT:This paper reviews our recent studies on the syntheses and functions of novel calixarene derivatives with excellent thermal stability as high performance materials. Calixarene derivatives containing protective groups such as tert-butoxycarbonyl (t-Boc), trimethylsilyl (TMS), and cyclohexenyl (CHE) groups were successfully prepared by the reaction of certain calixarenes, p-methylcalix [6]arene (1a), p-tert-butylcalix [8]arene (1c), and Cmethylcalix [4]resorcinarene (1d) with the corresponding protecting reagents. Calixarene containing radically polymerizable groups such as methacryloyl groups and cationic polymerizable groups such as propargyl, vinyl ether groups were prepared in good yields. Calixarene derivatives containing cyclic ethers such as oxirane, oxetane, and spiro orthoesters were also prepared. Calixarene derivatives thus obtained had good film forming property and thermal stability. It was proved that the photoinduced deprotection of the calixarene derivatives containing protective groups in the presence of a photo-acid generator proceeded easily to give the corresponding calixarenes with phenol groups. Photoinitiated polymerization of the calixarenes with various polymerizable groups using suitable photoinitiators in the film state proceeded efficiently to produce crosslinked films. Furthermore, thermal curing of epoxy resins with calixarenes (1a, 1c, 1d), and calixarenes containing active ester groups using certain catalysts were studied to found that the calixarenes were useful curing agents for epoxy resins.KEY WORDS Calixarene / Thermal Stability / Protective Group / Polymerizable Group / Photoinduced Deprotection / Radical Polymerization / Cationic Polymerization / Thermal Curing / Epoxy Resin / Calixarenes are cyclic oligomers prepared 1 ordinarily from the reaction of phenols with aldehydes, and have attracted much interest in the field of host-guest chemistry. 2 Therefore, over the last 20 years, synthesis 3 of various calixarene derivatives and chemical modification 4, 5 of calixarenes have been studied in attempting to induce the targeted character. We can consider that calixarene derivatives have further advantage in synthetic organic chemistry as starting materials due to polyfunctional hydroxyl groups, which are readily modified to various functional groups. That is, in polymer synthesis, calixarene derivatives can also be used as multifunctional initiators for the synthesis of starshaped polymers. Kennedy and his co-workers 6 reported the synthesis of a star-shaped polymer with eight arms of poly(iso-butylene) using calix [8]arene derivative as an initiator. Sawamoto and his co-workers 7 succeeded in producing certain star-shaped polymer with 4-8 arms of poly(methyl methacrylate) using cal- † To whom correspondence should be addressed. ixarene derivative as initiator.Recently, it was also suggested that calixarenes have unique characteristics such as small molecular size, good film-forming properties, 8, 9 high glass transition temperature 10 (T g ), excellent thermal stabilit...

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Synthesis and photochemical reaction of novel p‐alkylcalix[6]arene derivatives containing acryloyl or methacryloyl groups

Cited by 8 publications

References 3 publications

Synthesis of fully lower‐rim, carbonate‐bridged calix[8]arenes and their curing behavior

Synthesis of fully lower‐rim, carbonate‐bridged calix[8]arenes and their curing behavior

Development of Novel Photo-Functional Materials Based on Cyclic Oligomers

Novel High Performance Materials. Calixarene Derivatives Containing Protective Groups and Polymerizable Groups for Photolithography, and Calixarene Derivatives Containing Active Ester Groups for Thermal Curing of Epoxy Resins

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