Functionalization of parylene during its chemical vapor deposition

Two possible mechanisms for the reaction of four halogenated (metha)acrylate‐based molecules with Parylene [poly (paraxylylene)] during its chemical vapor deposition were proposed. The chemical reactivity of acrylate double bond with the paraxylylene biradical was calculated for all four (metha)acrylate‐based molecules. These calculations allowed the evaluation of the energetically favorable mechanism and indeed a direct correlation was found between both predicted and experimental reactivities. Next, the reactivity of the (metha)acrylate‐modified Parylene films was evaluated through their reaction with different amines. The obtained amidated Parylene films were characterized with X‐ray photoelectron spectroscopy, Kaiser test for primary amines, and fluorescence microscopy. The strong reactivity of (metha)acrylate‐modified Parylene films toward nucleophilic substitution emphasizes a general method for the functionalization of self‐supported Parylene films grown on the reacting solutions using the novel solid on liquid deposition process. This paves the way to the development of multifunctional materials in a one‐step process resulting from the deposition Parylene over liquid patterns. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

A unique stepped multifunctionality of perfluorinated aryl compound and its versatile use in synthesizing grafted polymers with controlled structures and topologies

A unique stepped multifunctionality of perfluorinated aryl compound for the first time was studied by using model reactions between 2,5‐dipentafluorophenyl‐1,3,4‐oxadiazole (FPOx) and mono functional p‐cresol at different reaction conditions. Four distinctively different levels of reactivity were discovered for the para and ortho C? F of FPOx, which could be easily triggered by the reaction temperature in the range of r.t. to 160 °C. C? F of all levels of reactivity could react quantitatively with nucleophiles (such as phenoxide); and by controlling the reaction conditions, the low‐level‐reactivity C? F would not interfere with the reaction of C? F of higher reactivity. Application of this multistepped reactivity of FPOx in quantitative postpolymerization functionalization of polymer was successfully demonstrated. Stoichiometric amount of p‐cresol, with the molar feed ratio of p‐cresol in relative to the repeat unit of the polymer of FPOx and 6F‐BPA in the range of 1–4, could be readily grafted onto the polymer by simply controlling the reaction temperature. FPOx‐based, versatile one‐pot synthesis of high molecular‐weight grafted polymers with well‐controlled structures and topologies were also demonstrated. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis of polymeric 1‐iminopyridinium ylides as photoreactive polymers

Two synthetic routes to polymeric 1‐imino pyridinium ylides as new photoreactive polymeric architectures were investigated. In the first approach, polymerization of newly synthesized 1‐imino pyridinium ylide containing monomers yielding their polymeric analogues was achieved by free radical polymerization. Alternatively, reactive precursor polymers were synthesized and converted into the respective 1‐imino pyridinium ylide polymers by polymer analogous reactions on reactive precursor polymers. Quantitative conversion of the reactive groups was achieved with pentafluorophenyl ester containing polymers and newly synthesized photoreactive amines as well as by the reaction of poly(4‐vinylbenzoyl azide) with a photoreactive alcohol. The polymers obtained by both routes were examined regarding their photoreaction products and kinetics in solution as well as in thin polymer films. Contact angle measurements of water on the polymer films before and after irradiation showed dramatic changes in the hydrophilicity of the polymers. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 832–844, 2010     

Characterization of parylene‐N and parylene‐C photooxidation

Parylene‐N and parylene‐C are polymers of interest for microelectronic and medical coating applications. Modifications for improved surface properties could make them even more useful in such applications. Parylene‐N and parylene‐C films were exposed to ultraviolet light in the presence of oxygen and analyzed with Rutherford backscattering spectrometry, secondary‐ion mass spectroscopy, X‐ray photoelectron spectroscopy, and infrared spectroscopy. This study shows that such exposure results in the formation of aldehyde and carboxylic acid groups near the surface of the films. At the maximum exposure dose, the concentration of oxygen in both parylene‐N and parylene‐C is about 13% at the film surface, and it decreases exponentially with increasing depth. Further modeling and optimization of this process would allow it to be used to tailor the surface concentration of oxygenated species in parylene for the optimization of adhesion and wettability or for the chemical binding of other moieties. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1486–1496, 2003     

Photoreactive main‐chain liquid‐crystalline polyesters: Synthesis,characterization, and photochemistry

Three series of semiflexible and rigid main‐chain polyesters containing photoreactive mesogenic units derived from p‐phenylenediacrylic acid (PDA) and cinnamic acid have been synthesized by high‐temperature polycondensation. The thermal and mesomorphic properties of the polymers have been determined. The photochemical behavior of polymer P‐[1]‐T, which contains a PDA unit, has been studied both in solution and in films. In solution, [2+2] photocycloaddition, E/Z photoisomerization, and photo‐Fries rearrangement can take place. In contrast, the dominant process in spin‐coated films is the [2+2] photocycloaddition reaction, which causes crosslinking of the polymer. In films, the photochemistry and induction of anisotropy are strongly influenced by the aggregation of the PDA phenylester unit. A dichroism of about 0.2 has been induced in films by irradiation with linearly polarized UV light, and thus the capability of these films to induce optical anisotropy and align liquid crystals has been demonstrated. Liquid‐crystalline cells have been made with polarized irradiated films of P‐[1]‐T as aligning layers. A commercial liquid‐crystalline mixture has been used for this study, and a similar liquid‐crystalline order determined by polarized Fourier transform infrared to a commercial cell with rubbed polyimide as an aligning layer has been detected. Because of crosslinking of the irradiated P‐[1]‐T photoaligning layer, the photoinduced anisotropy is stable at high temperatures, and the liquid‐crystalline molecules are insoluble in the irradiated polymer. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4907–4921, 2005     

Synthesis of photoreactive calixarene derivatives containing pendant cyclic ether groups

New photoreactive calixarene derivatives containing cationically polymerizable pendant oxetane groups (calixarenes 1a , b , 2a , b , and 3a , b ) were synthesized in good yields by the substitution reaction of C‐methylcalix[4]resorcinarene (CRA), p‐methylcalix[6]arene (MCA), and p‐tert‐butylcalix[8]arene (BCA) with (3‐methyloxetan‐3‐yl)methyl 4‐toluenesulfonate and (3‐ethyloxetan‐3‐yl)methyl 4‐toluenesulfonate with potassium hydroxide as a base and tetrabutylammonium bromide as a phase‐transfer catalyst in N‐methyl‐2‐pyrrolidone, respectively. Calixarene derivatives containing cationically polymerizable pendant oxirane groups (calixarenes 4 , 5 , and 6 ) were also prepared in good yields by the substitution reaction of CRA, MCA, and BCA with epibromohydrin, respectively, with cesium carbonate as a base in N‐methyl‐2‐pyrrolidone. The thermal stability of the obtained calixarene derivatives containing pendant oxetane groups or oxirane groups was examined with thermogravimetric analysis, and it was found that these calixarene derivatives had thermal stability beyond 340 °C. The photochemical reaction of calixarenes 1 , 2 , and 3 containing pendant oxetane groups was examined with certain photoacid generators in the film state. In this reaction system, calixarene 1a , composed of a CRA structure and pendant (3‐methyloxetan‐3‐yl)methyl groups, showed the highest photochemical reactivity when bis‐[4‐(diphenylsulfonio)phenyl]sulfide bis(hexafluorophosphate) was used as the catalyst. The photochemical reaction of calixarenes 4 , 5 , and 6 containing pendant oxirane groups was also examined, and it was found that the photoinitiated cationic polymerization of calixarenes 4 , 5 , and 6 proceeded smoothly under the same conditions; however, the reaction rates were lower than those of the corresponding calixarenes 1 , 2 , and 3 containing pendant oxetane groups. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1169–1179, 2001     

Preparation and properties of ionic‐liquid‐containing poly(ethylene glycol)‐based networked polymer films having lithium salt structures

Ionic‐liquid‐containing polymer films were prepared by swelling poly(ethylene glycol)‐based networked polymers having lithium salt structures with an ionic liquid, 1‐ethyl‐3‐methylimidazolium bis(fluorosulfonyl)imide (EMImFSI), or with an EMImFSI solution of lithium bis(trifluoromethanesulfonyl) imide (LiTFSI). Their fundamental physical properties were investigated. The networked polymer films having lithium salt structures were prepared by curing a mixture of poly(ethylene glycol) diglycidyl ether and lithium 3‐glycidyloxypropanesulfonate or lithium 3‐(glycidyloxypropanesulfonyl)(trifluoromethanesulfonyl)imide with poly(ethylene glycol) bis(3‐aminopropyl) terminated. The obtained ionic‐liquid‐containing films were flexible and self‐standing. They showed high ionic conductivity at room temperature, 1.16–2.09 S/m for samples without LiTFSI and 0.29–0.43 S/m for those with 10 wt % LiTFSI. Their thermal decomposition temperature was above 220 °C, and melting temperature of the ionic liquid incorporated in the film was around ?16 °C. They exhibited high safety due to good nonflammability of the ionic liquid. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Dendronized polymers via Diels–Alder “click” reaction

A modular approach toward the synthesis of polymers containing dendron groups as side chains is developed using the Diels–Alder “click” reaction. For this purpose, a styrene‐based polymer appended with anthracene groups as reactive side chains was synthesized. First through third‐generation polyester dendrons containing furan‐protected maleimide groups at their focal point were synthesized. Facile, reagent‐free, thermal Diels–Alder cycloaddition between the anthracene‐containing polymer and latent‐reactive dendrons leads to quantitative functionalization of the polymer chains to afford dendronized polymers. The efficiency of this functionalization step was monitored using ¹H and ¹³C NMR spectroscopy and FTIR and UV–vis spectrometry. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 410–416, 2010     

Polymerizable anthracene derivatives for labeling emulsion copolymers

We describe the synthesis of three anthracene–methacrylate monomers [9‐methacryloxymethyl‐10‐methyl anthracene ( 4 ), 9‐methacryloxyethyloxymethyl‐10‐methyl anthracene ( 5 ), and 9‐methacryloxy‐10‐methyl anthracene ( 6 )] as well as their emulsion copolymers containing butylacrylate. When films prepared from latex dispersions containing 4 or 5 were heated, the anthracene (An) group was cleaved from the polymer at temperatures above 120 °C. Lower temperatures induced this reaction when strong acids were present. In 4 and 5 , the polymerizable group is connected to the An ring via a 9‐CH₂O? linkage. The cleavage reaction requires more stringent conditions when the connection involves a benzylic ether ( 5 ) instead of a benzylic ester. Polymers prepared from 6 , with an An? O? bond, were stable for 1 h at 150 °C in the presence of 0.5 wt % p‐toluene sulfonic acid. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1495–1504, 2001     

Synthesis and photochemical reaction of cyclic oligomers: Synthesis and photopolymerization of novel C‐methylcalix[4]resorcinarene and p‐alkylcalix[n]arene derivatives containing spiro ortho ether groups

New photoreactive calixarene derivatives containing spiro ortho ester groups (calixarenes 3a–3c ) were synthesized by the reaction of 2‐bromomethyl‐1,4,6‐trioxaspiro[4.4]nonane with 2,8,14,20‐tetramethyl‐4,6,10,12,16,18,22,24‐octakis(carboxymethoxy)calix[4]resorcinarene, 5,11,17,23,29,35‐hexamethyl‐37,38,39,40,41,42‐hexakis(carboxymethoxy)calix[6]arene, and 5,11,17,23,29,35,41,47‐octa‐tert‐butyl‐49,50,51,52, 53,54,55,56‐octakis‐(carboxymethoxy)calix[8]arene, which were prepared by the reaction of C‐methylcalix[4]resorcinarene, p‐methylcalix[6]arene, and p‐tert‐butylcalix[8]arene, respectively. The thermal stability of the obtained calixarene derivatives containing spiro ortho ester groups was examined with thermogravimetric analysis, and it was found that these calixarene derivatives had good thermal stability. The photoinitiated cationic polymerization of spiro ortho ester groups in calixarene derivatives 3a–3c was examined with certain photoacid generators in the film state. Interestingly enough, the reaction of calixarene derivatives did not proceed with only photoirradiation; however, the reaction proceeded smoothly when the photoirradiation was followed by heating. Furthermore, calixarene 3a , composed of a C‐methylcalix[4]resorcinarene structure, showed the highest photochemical reactivity in this reaction system. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1293–1302, 2002     

Photochemical functionalization of hydrogen-terminated diamond surfaces: a structural and mechanistic study

Hydrogen-terminated diamond surfaces can be covalently modified with molecules bearing a terminal vinyl (C=C) group via a photochemical process using sub-band-gap light at 254 nm. We have investigated the photochemical modification of hydrogen-terminated surfaces of nanocrystalline and single-crystal diamond (111) to help understand the structure of the films and the underlying mechanism of photochemical functionalization. A comparison of the rates of photochemical modification of single-crystal diamond and nanocrystalline diamond films shows no significant difference in reactivity, demonstrating that the modification process is not controlled by grain boundaries or other structures unique to polycrystalline films. We find that both single-crystal and polycrystalline hydrogen-terminated diamond samples exhibit negative electron affinity and are functionalized at comparable rates, while oxidized surfaces with positive electron affinity undergo no detectable reaction. Gas chromatography-mass spectrometry (GC-MS) analysis shows the formation of new chemical products in the liquid phase that are formed only when the alkenes are illuminated in direct contact with H-terminated diamond, while control experiments with other surfaces and in the dark show no reaction. Our results show that the functionalization is a surface-mediated photochemical reaction and suggest that modification is initiated by the photoejection of electrons from the diamond surfaces into the liquid phase.     

Synthesis and functionalization of dendron‐polymer conjugate based hydrogels via sequential thiol‐ene “click” reactions

Fabrication and functionalization of hydrogels from well‐defined dendron‐polymer‐dendron conjugates is accomplished using sequential radical thiol‐ene “click” reactions. The dendron‐polymer conjugates were synthesized using an azide‐alkyne “click” reaction of alkene‐containing polyester dendrons bearing an alkyne group at their focal point with linear poly(ethylene glycol)‐bisazides. Thiol‐ene “click” reaction was used for crosslinking these alkene functionalized dendron‐polymer conjugates using a tetrathiol‐based crosslinker to provide clear and transparent hydrogels. Hydrogels with residual alkene groups at crosslinking sites were obtained by tuning the alkene‐thiol stoichiometry. The residual alkene groups allow efficient postfunctionalization of these hydrogel matrices with thiol‐containing molecules via a subsequent radical thiol‐ene reaction. The photochemical nature of radical thiol‐ene reaction was exploited to fabricate micropatterned hydrogels. Tunability of functionalization of these hydrogels, by varying dendron generation and polymer chain length was demonstrated by conjugation of a thiol‐containing fluorescent dye. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 926–934     

Synthesis and properties of fluorine‐containing poly(aryl ether oxadiazole)s

Fluorine‐containing poly(aryl ether 1,3,4‐ozadiazole)s were synthesized by the nucleophilic aromatic substitution reaction of 2,5‐bis(2,3,4,5,6‐pentafluorophenyl)‐1,3,4‐oxadiazole and various bisphenols in the presence of potassium carbonate. The polymerizations were carried out at 30 °C in 1‐methyl‐2‐pyrrolidinone to avoid the gelation caused by a crosslinking reaction at para and ortho carbons to the 1,3,4‐oxidiazole ring. The obtained polymers were all para‐connected linear structures. The obtained fluorine‐containing poly(aryl ether 1,3,4‐ozadiazole)s showed excellent solubility and afforded tough, transparent films by the solution‐casting method. They also exhibited a high glass transition temperature depending on the molecular structure, and the glass transition temperature could be controlled by the bisphenols in the range of 157–257 °C. They showed good thermal stability and excellent hydrophobicity due to the incorporation of the 2,3,5,6‐tetrafluoro‐1,4‐phenylene moiety. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2855–2866, 2007     

Functional benzoxazines containing ammonium salt of carboxylic acid: Synthesis and highly activated thermally induced ring‐opening polymerization

1,3‐Benzoxazine monomers having ammonium salt of carboxylic acid have been developed. These 1,3‐benzoxazines 1a and 1b were easily synthesized from the corresponding tetrabutylammonium salts of glycine and β‐alanine, respectively. The glycine‐derived benzoxazine 1a exhibited remarkably high reactivity, which allowed its thermally induced ring‐opening polymerization in bulk at 100 °C, at which N‐methyl‐1,3‐benzoxazine 1d did not undergo the polymerization at all. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis and properties of butyl rubber–poly(ethylene oxide) graft copolymers with high PEO content

Butyl rubber‐poly(ethylene oxide) (PEO) graft copolymers with high PEO content (40–83 wt %) were synthesized by the functionalization and activation of the double bond moiety of butyl rubber containing high (7 mol %) isoprene content and subsequent reaction with PEO of different molecular weights from 750 to 5000 g/mol. The properties of these copolymers, along with other butyl rubber‐PEO graft copolymers were studied in films and in aqueous solution. Despite the high PEO content, films of the copolymers were quite stable in water with respect to mass loss and were capable of releasing an encapsulated probe molecule in a manner that was dependent on the PEO content. At high PEO content they were resistant to the adhesion and growth of C2C12 cells. Despite the resistance of films to dissolution, it was possible to prepare nanosized aqueous assemblies via a THF‐water exchange process and the sizes of the assemblies were tuned by their method of preparation. The assemblies were also able to encapsulate a probe molecule and were found to be nontoxic in vitro. Combined, this set of properties makes these new amphiphilic copolymers promising for a wide range of potential applications. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 3383–3394     

Synthesis and photochemical properties of novel pentamethylated norbornadiene containing polyimides

A novel pentamethylated norbornadiene (NBD) based dianhydride, α,α′‐bis‐(3,4,5,6,7‐pentamethylcyclopenta‐2,4‐dienyl)meta‐xylene‐1,2‐dianhydride (3), was prepared from α,α′‐bis‐(pentamethylcyclopentadienyl)meta‐xylene (1) and acetylene dicarboxylic acid. The bis‐adduct formed via Diels–Alder reaction afforded tetra‐acid (2), which was chemically cyclodehydrated to lead the targeted dianhydride (3). New polyimides containing NBD moieties in the main chain were prepared from the dianhydride monomer (3) and various aromatic diamines. The chemical structure of the polymers was confirmed by both ¹H and ¹³C NMR analysis. Their Molecular weights were also measured by SEC. All of these polyimides are soluble at room temperature in common organic solvents, such as chloroform, dichloromethane, THF, DMSO, DMF, and NMP, and show good thermal stabilities. The photochemical isomerization of the NBD into quadricyclane (QC) was investigated by UV/vis spectrophotometry from polymer films using visible sunlight as irradiation source. It was found that the kinetic rate of the conversion NBD‐QC which proceeded smoothly is a first kinetic order. The stored energies released by the transformation of QC groups into NBD ones of the irradiated polymer films were also evaluated by DSC measurement and were found to be around 90 kJ mol^?1. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Durable bonding of silica nanoparticles to polymers by photoradiation for control of surface properties

Improvement of superhydrophobic surfaces durability is a critical key for potential commercial applications such as self‐cleaning and ice repellency. In this study, functionalization of silica nanoparticles by photoreactive benzophenone groups was made in order to covalently bond nanoparticles to polymer substrates to obtain durable coatings. Upon ultraviolet irradiation reactive excited triplet benzophenone species are formed enabling them to react with the polymer matrix through hydrogen abstraction. Two matrices were studied: radiation‐curable urethane acrylate and epoxy. The bonding of the particles to the surfaces was evaluated using atomic force microscope nanomanipulation and cross‐section analysis. The results have shown a greater stability of the photoreactive silica nanoparticles. Copyright © 2014 John Wiley & Sons, Ltd.     

Synthesis and characterization of novel biodegradable unsaturated poly(ester amide)s

A series of novel biodegradable unsaturated poly(ester amide)s (UPEAs) were synthesized through the solution polycondensation of two unsaturated monomers, di‐p‐nitrophenyl fumarate and L ‐phenylalanine 2‐butene‐1,4‐diol diester p‐toluene sulfonate, and four other saturated monomers in different combinations. The UPEAs were obtained in fairly good yields with N,N‐dimethylacetamide (DMA) as the solvent. The number‐average and weight‐average molecular weights of the UPEAs, measured by gel permeation chromatography, ranged from 10 to 30 kg/mol, they had a rather narrow molecular weight distribution of 1.40. The chemical structures of the novel biodegradable UPEAs were confirmed by both IR and NMR spectra. The UPEAs had higher glass‐transition temperatures than saturated PEAs of similar structures, and their glass‐transition temperatures were affected more by the CC double bond located in the diamide part than by those in the diester part. The solubility of the polymers was poor in water but better in DMA and dimethyl sulfoxide. With the availability of these inherent CC double bonds in the UPEA backbones, these UPEAs have the functionality of CC bonds, such as photochemical reactivity or the ability to react with or be modified by other bioactive or other environmentally sensitive compounds, and this can easily extend their applications to biomedical and pharmaceutical areas. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1463–1477, 2005     

New anion conducting membranes based on functionalized styrene–butadiene–styrene triblock copolymer for fuel cells applications

In this work, the functionalization of polystyrene‐b‐poly(butadiene)‐b‐polystyrene triblock copolymer (SBS) with vinylbenzyl chloride and benzoyl peroxide (BPO) or α,α′‐azo‐bis‐isobutyronitrile (AIBN) as free radical initiators was reported. The functionalization degree (FD), calculated by ¹H NMR spectroscopy and confirmed by elemental analysis, was highly tunable (from 4 to 10 mol %) and positively correlated to the starting percentage of radical initiator. More specifically, at the same initiator molar percentage grafting efficiency is higher using BPO rather than AIBN. Quaternization reaction of the grafted benzyl chloride groups with the bifunctional tertiary amine 1,4‐diazabicyclo[2.2.2]octane (Dabco) led to a chemically and thermally stable homogeneous anion‐exchange membrane. Electrochemical parameters were evaluated for Dabco‐quaternized grafted copolymers having different FDs, and compared with a commercial Tokuyama benchmark membrane. Experimental data showed a positive correlation between FD and both water swelling and ionic conductivity. Best trade‐off between ionic conductivity and water swelling was found for membrane having FD 9.1 mol %, which conductivity is comparable with the Tokuyama benchmark one and water uptake is only slightly higher. The results are discussed based on the molecular parameters with particular reference to ionic content and distribution. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis and photochemical reaction of novel p-alkylcalix[n]arene derivatives containing cationically polymerizable groups

New photoreactive p-methylcalix[6]arene (MCA) derivatives containing cationically polymerizable groups such as propargyl ether (calixarene 1), allyl ether (calixarene 2), and ethoxy vinyl ether (calixarene 3) groups were synthesized with 80, 74, and 84% yields by the substitution reaction of MCA with propargyl bromide, allyl bromide, and 2-chloroethyl vinyl ether (CEVE), respectively, in the presence of either potassium hydroxide or sodium hydride by using tetrabutylammonium bromide (TBAB) as a phase transfer catalyst (PTC). The p-tert-butylcalix[8]arene (BCA) derivative containing ethoxy vinyl ether groups (calixarene 4) was also synthesized in 83% yield by the substitution reaction of BCA with CEVE by using sodium hydride as a base and TBAB as a PTC. The MCA derivative containing 1-propenyl ether groups (calixarene 5) was synthesized in 80% yield by the isomerization of calixarene 2, which contained allyl ether groups, by using potassium tert-buthoxide as a catalyst. The photochemical reactions of carixarene 1, 3, 4, 5, and 6 were examined with certain photoacid generators in the film state. In this reaction system, calixarene 3 containing ethoxy vinyl ether groups showed the highest photochemical reactivity when bis-[4-(diphenylsulfonio)phenyl]sulfide bis(hexafluorophosphate) (DPSP) was used as the catalyst. On the other hand, calixarene 1 containing propargyl ether groups had the highest photochemical reactivity when 4-morpholino-2,5-dibuthoxybenzenediazonium hexafluorophosphate (MDBZ) was used as the catalyst. It was also found that the prepared carixarene derivatives containing cationically polymerizable groups such as propargyl, allyl, vinyl, and also 1-propenyl ethers have good thermal stability. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1805–1814, 1999