Large melting point depression of 2–3‐nm length‐scale nanocrystals formed by the self‐assembly of an associative polymer: Telechelic,pyrene‐labeled poly(dimethylsiloxane)

Large melting point depressions for organic nanocrystals, in comparison with those of the bulk, were observed in an associative polymer: telechelic, pyrene‐labeled poly(dimethylsiloxane) (Py‐PDMS‐Py). Nanocrystals formed within nanoaggregates of pyrenyl units that were immiscible in poly(dimethylsiloxane). For 5 and 7 kg/mol Py‐PDMS‐Py, physical gels resulted, with melting points exceeding 40 °C and with small‐angle X‐ray scattering peaks indicating that the crystals were nanoconfined, were 2–3 nm long, and contained roughly 18–30 pyrenyl dye end units. In contrast, 30 kg/mol Py‐PDMS‐PY was not a gel and exhibited no scattering peak at room temperature; however, after 12 h of annealing at ?5 °C, multiple melting peaks were present at 5–30 °C. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3470–3475, 2004     

Third‐generation amphiphilic conetworks. I. Synthesis and swelling behavior of poly(N,N‐dimethyl acrylamide)/polydimethylsiloxane conetworks

A strategy has been developed for the synthesis of novel amphiphilic conetworks (APCNs) of poly(N,N‐dimethyl acrylamide) (PDMAAm) and polydimethyl‐siloxane (PDMS) segments crosslinked with polyhydrosiloxanes. The synthesis proceeds in three steps in one pot (see Figure 2 for reactions and abbreviations): (1) the preparation of a charge containing three components (an asymmetric–telechelic macromonomer, MA‐PDMS‐V, plus two symmetric–telechelic crosslinkers, MA‐PDMS‐MA and V‐PDMS‐V), (2) the free‐radical terpolymerization of N,N‐dimethyl acrylamide, MA‐PDMS‐V, and MA‐PDMS‐MA into a slightly crosslinked and soluble graft of a PDMAAm backbone carrying‐PDMS‐V branches, and (3) the crosslinking of PDMS branches with polyhydrosiloxanes. The effects of key experimental parameters (e.g., composition, molecular weights, and initiator and crosslinker concentrations) on synthesis details and swelling behavior have been studied. The water uptake/permeability of APCNs is significantly increased by the addition of homo‐PDMAAm to graft charges, crosslinking of the graft, and, after the desirable morphology is stabilized, removing the homo‐PDMAAm by water extraction. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 295–307, 2007     

Synthesis of crosslinked poly(butyl methacrylate‐co‐pentaerythritol triacrylate) gel by single electron transfer‐living radical polymerization and its oil‐absorbing properties

A novel high oil‐absorbing crosslinked gel was synthesized by copolymerization of butyl methacrylate (BMA) with a small amount of pentaerythritol triacrylate (PETA) crosslinker using single electron transfer‐living radical polymerization (SET–LRP) initiated with carbon tetrachloride (CCl₄) and catalyzed by Cu(0)/hexamethylenetetramine (HMTA) in N, N‐dimethylformamide (DMF). The polymerization followed first‐order kinetics as indicated by linear increase of monomer concentration with reaction time. Effects of reaction temperature, crosslinker, initiator, and catalyst on the oil‐absorbing properties of the crosslinked gel were investigated in detail. The oil absorptions of the crosslinked gel to chloroform, toluene could reach 51.9, 34.5 g/g, respectively. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Poly(n‐alkylsilsesquioxane)s: Synthesis,characterization, and modification with poly(dimethylsiloxane)

Self‐supported translucent films constituted of poly(n‐octylsilsesquioxane) or poly(n‐dodecylsilsesquioxane) were obtained from the hydrolysis and condensation of n‐octyltriethoxysilane (OTES) or n‐dodecyltriethoxysilane (DTES), respectively. Dense films were obtained in the absence of organic solvents, with dibutyltin diacetate as catalyst. These films exhibited good optical transparency and thermal stability. The incorporation of oligomeric dimethylsiloxane units (D^Me,Me) in these materials, derived from silanol‐terminated poly(dimethylsiloxane) (PDMS) or 1,1,3,3‐tetramethyl‐1,3‐diethoxydisiloxane (TMDES), was carried out during the hydrolysis and condensation of OTES and DTES and was confirmed by solid‐state ²⁹Si NMR. Poly(n‐octylsilsesquioxane) showed a glass‐transition temperature at ?65 °C, due to the increase in the free volume, promoted by the bulky n‐octyl groups. The differential scanning calorimetric (DSC) curves of the polymer derived from DTES were characterized by first‐order transitions at temperatures ranging from ?15.8 to ?0.7 °C. Further studies of these networks by low‐temperature XRD evidenced narrowing of the diffraction halos suggesting a partial order–disorder transition for these materials at lower temperatures. Good thermal stability up to 350 °C and the solvent‐free production process make these polymers potential candidates for the development of self‐supported hydrophobic protective coatings. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1220–1229, 2010     

Amphiphilic membranes crosslinked and reinforced by POSS

This article concerns the synthesis and characterization of novel tricomponent amphiphilic membranes consisting of hydrophilic poly(ethylene glycol) (PEG) and hydrophobic polydimethylsiloxane (PDMS) segments cocrosslinked and reinforced by octasilane polyhedral oligomeric silsesquioxane (octasilane‐POSS) cages. Rapid and efficient network synthesis was effected by cocrosslinking diallyl‐telechelic PEG (A‐PEG‐A) and divinyl‐telechelic PDMS (V‐PDMS‐V) with pentamethylpentacyclosiloxane (D₅H), using Karstedt's catalyst in conjunction with Et₃N cocatalyst and water. Films were prepared by pouring charges in molds and crosslinking by heating at 60 °C for several hours. The films were characterized by sol fractions and equilibrium swelling both in hexane and water, extent of crosslinking, contact angle hysteresis, oxygen permeability, thermogravimetric analysis, and mechanical properties. The crosslinking of octasilane‐POSS achieved by the same catalyst system was studied in separate experiments. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4337–4352, 2004     

Preparation of high molecular weight polybenzoxazine prepolymers containing siloxane unites and properties of their thermosets

High‐molecular‐weight polybenzoxazine prepolymers containing polydimethylsiloane unit in the main‐chain have been synthesized from α,ω‐bis(aminopropyl)polydimethylsiloxane (PDMS) (molecular weight = 248, 850, and 1622) and bisphenol‐A with formaldehyde. Moreover, another type of prepolymers was prepared using methylenedianiline (MDA) as codiamine with PDMS. The weight average molecular weight of the obtained prepolymers was estimated from size exclusion chromatography to be in the range of 8000–11,000. The chemical structures of the prepolymers were investigated by ¹H NMR and IR analyses. The prepolymers gave transparent free standing films by casting their dioxane solution. The prepolymer films after thermally cured up to 240 °C gave brown colored transparent and flexible polybenzoxazine films. Tensile test of the films revealed that the elongation at break increased with increasing the molecular weight of PDMS unit. Dynamic mechanical analysis of the thermosets showed that the T_gs were as high as 238–270 °C. The thermosets also revealed high thermal stability as evidenced by the 5% weight loss temperatures in the range of 324–384 °C from thermogravimetic analysis. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Study on siloxane‐modified polyurethane dispersions from various polydimethylsiloxanes

In this work, various polydimethylsiloxanes (PDMS) are incorporated with isophorone diisocyanate (IPDI), 2,2‐bis(hydroxymethyl)propionic acid (DMPA), and poly(tetramethylene oxide) (PTMO) by the prepolymer process to synthesize a series of siloxane‐modified polyurethane dispersions (PUDs) with 35 wt % solid content, viscosities of 20–100 cps, and particle sizes of 40–130 nm. Hydrophobic PDMS was introduced into the PU chain either based on random distribution or through the block segment arrangement. We also establish the composition‐property relationship of PDMS‐PUD, which includes PDMS's type and molecular weight and PDMS‐PUD film's contact angle and mechanical property. The tensile strength of PDMS‐PUD film is decreased with increasing amount of PDMS. Scanning electron microscopy for chemical element analysis indicated that PDMS migrated to the surface much more easily in the block arrangement than in the random distribution. Also, some PDMS‐PUD films show a peau‐like surface, so their PUDs are considered promising to be used in processes for textiles. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3482–3490, 2005     

Ideal tetrafunctional amphiphilic PEG/PDMS conetworks by a dual‐purpose extender/crosslinker. I. Synthesis

The synthesis of a new type of amphiphilic conetwork (APCN) consisting of well‐defined hydrophilic poly(ethylene glycol) (PEG) and hydrophobic polydimethylsiloxane (PDMS) segments is described. The conetwork is ideal (the lengths of each PEG and PDMS chain segments, respectively, are identical) and tetrafunctional (exactly four chains emanate from each crosslink site). The synthesis of the conetworks was achieved by the use of a novel dual‐purpose extender/crosslinker Y (bis [(dimethylsilyl)oxy]‐[(etoxydimethylsilyl)oxy]phenylsilane, (SiPh(SiH)₂OEt)), in two steps: (1) Synthesis of a new linear random multiblock copolymer (MBC) (AY)_n(BY)_m, where A is the hydrophilic PEG and B is the hydrophobic segment, and (2) Crosslinking the multiblocks by catalytic condensation of the SiOEt groups in the Y units. The extender/crosslinker fulfills two totally different functions: First, it extends two incompatible hydrophilic and hydrophobic prepolymers (PEG and PDMS) to a random MBC, and, subsequently, it cross‐links the multiblocks to the target APCN. The synthesis and characterization of the extender/crosslinker is also presented. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4953–4964, 2005     

Synthesis and sulfonation of poly(arylene ether)s containing tetraphenyl methane moieties

Novel poly(arylene ether)s with sulfonic acid containing pendent groups were successfully synthesized by the nucleophilic displacement of aromatic dihalides with bisphenols in an aprotic solvent in the presence of excess potassium carbonate followed by sulfonation with chlorosulfonic acid. The sulfonation took place only at the controlled positions on the phenyl rings due to the novel bisphenol structures designed. The sulfonic acid group containing polymers were very soluble in common organic solvents, such as dimethyl sulfoxide, N,N′‐dimethylacetamide, and dimethylformamide, but swelled only slightly in water. These sulfonic acid group containing polymers were readily cast into tough and smooth films from organic solvents. The synthesized polymers had high glass‐transition temperatures of 171.0–240.7 °C and high molecular weights of 15,600–33,000 Da. These films could potentially be used as proton‐exchange membranes for fuel cells. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1779–1788, 2004     

Influence of interfaces on the rates of crosslinking in poly(dimethyl siloxane) coatings

We have determined with infrared spectroscopic ellipsometry how the nature of the interface between a thin poly(dimethyl siloxane) (PDMS) coating and its substrate affects the rate of PDMS crosslinking reactions. Reactions between vinyl (? CH?CH₂) end groups on PDMS and silyl (SiH) groups in a crosslinker (hydrosilylation) and between SiH groups and silanol (SiOH) groups, during the so‐called postcure crosslinking stage, have been probed in situ. The overall consumption of SiH follows first‐order reaction kinetics. The first‐order reaction coefficient (k₁) for the hydrosilylation crosslinking reaction is the same for coatings on three different substrates: native oxide on silicon (SiO₂/Si), polystyrene (PS), and poly(ethylene terephthalate). For the slower postcure reactions, however, the rate of SiH consumption depends on the substrate. In 2.5‐μm PDMS coatings on PS, k₁ is about seven times greater than k₁ in the same coating on SiO₂/Si. In PDMS coatings on a PDMS substrate, when the effect of the interface is thus minimal, k₁ is 16 times higher than on SiO₂/Si. The dependence of k₁ on the type of interface is probably the result of the interfacial segregation and complexation of the Pt catalyst for the postcure reactions. We propose that polar surfaces more strongly attract Pt and form complexes that inhibit the postcure reactions. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1421–1431, 2004     

Synthesis of polybutadiene‐graft‐poly(dimethylsiloxane) and polyethylene‐graft‐poly(dimethylsiloxane) copolymers with hydrosilylation reactions

We report preliminary results for the synthesis of polyethylene‐graft‐poly(dimethylsiloxane) copolymers obtained by catalytic hydrogenation of polybutadiene‐graft‐poly(dimethylsiloxane) copolymers (PB‐g‐PDMS). These last copolymers were synthesized by hydrosilylation reactions between commercial polybutadiene and ω‐silane poly(dimethylsiloxane). The reaction was carried in solution catalyzed by cis‐dichloro bis(diethylsufide) platinum(II) salt. The PB‐g‐PDMS copolymers were analyzed by ¹H and ¹³C NMR spectroscopies, and the relative weight percentages of the grafted poly(dimethylsiloxane) macromonomer were determined from the integrated peak areas of the spectra. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2920–2930, 2004     

Photocrosslinking system based on a poly(vinyl phenol)/thermally degradable diepoxy crosslinker blend

Photocrosslinkable systems with thermally cleavable properties based on blends of poly(vinyl phenol) (PVP) and diepoxides were investigated. Thermally cleavable diepoxides as crosslinkers were prepared and characterized. As a thermally cleavable linkage, a tertiary ester moiety was incorporated into the crosslinker molecule. PVP/crosslinker blended films containing photoacid generators (PAGs) became insoluble in solvents after UV irradiation and subsequent post‐exposure‐bake (PEB) treatment. With a rise in the PEB temperature, the insoluble fraction of the irradiated films increased, passed through a maximum value, decreased, and increased again at elevated baking temperatures. The insolubilization profiles of the irradiated films were complicated and strongly dependent on the type of PAG used, the structure of the crosslinkers, and the PVP/crosslinker ratio. A mechanism for the thermal degradation was studied with Fourier transform infrared spectroscopy. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3055–3062, 2002     

A new thermoplastic vulcanizate (TPV)/organoclay nanocomposite: Preparation,characterization, and properties

The preparation, characterization, and properties of the new thermoplastic vulcanizate (TPV)/organoclay nanocomposites are reported in this article. The nanocomposites were prepared by the melt intercalation method. The organoclay was first treated with glycidyl methacrylate, which acts as a swelling agent for organoclays, as well as a grafting agent for TPV (in the presence of dicumyl peroxide) during the melt mixing. The nanocomposite was intercalated, as evidenced by X‐ray diffraction. The tensile modulus of the 5% TPV/organoclay nanocomposite was higher than that of the 20% talc‐filled microcomposite. The storage modulus of the nanocomposite was higher than that of the pristine TPV. The most important observation is obtained from dynamic mechanical analysis, which reveals that the glass‐transition temperature of the polypropylene phase of the nanocomposite increases (as compared to virgin TPV), whereas the ethylene–propylene–diene monomer phase remains almost the same. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2900–2908, 2004     

Poly(2‐oxazoline) hydrogels crosslinked with aliphatic bis(2‐oxazoline)s: Properties,cytotoxicity, and cell cultivation

A series of hydrogels from 2‐ethyl‐2‐oxazoline and three bis(2‐oxazoline) crosslinkers—1,4‐butylene‐2,2′‐bis(2‐oxazoline), 1,6‐hexamethylene‐2,2′‐bis(2‐oxazoline), and 1,8‐octamethylene‐2,2′‐bis(2‐oxazoline)—are prepared. The hydrogels differ by the length of aliphatic chain of crosslinker and by the percentage of crosslinker (2–10%). The influence of the type and the percentage of the crosslinker on swelling properties, mechanical properties, and state of water is studied. The equilibrium swelling degree in water ranges from 2 to 20. With a proper selection of the crosslinker, Young's modulus can be varied from 10 kPa to almost 100 kPa. To evaluate the potential for medical applications, the cytotoxicity of extracts and the contact toxicity toward murine fibroblasts are measured. The hydrogels with the crosslinker containing a shorter aliphatic exhibit low toxicity toward fibroblast cells. Moreover, the viability and the proliferation of pancreatic β‐cells incubated inside hydrogels for 12 days are analyzed. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1548–1559     

A facile approach to fabricate hierarchically structured poly(3‐hexylthiophene‐2,5‐diyl) films

Microstructured surfaces have great potentials to improve the performances and efficiency of optoelectronic devices. In this work, a simple robust approach based on surface instabilities was presented to fabricate poly(3‐hexylthiophene‐2,5‐diyl) (P3HT) films with ridge‐like/wrinkled composite microstructures. Namely, the hierarchically patterned films were prepared by spin coating the P3HT/tetrahydrofuran (THF) solution on a polydimethylsiloxane (PDMS) substrate to form stable ridge‐like structures, followed by solvent vapor swelling to create surface wrinkles with the orientation guided by the ridge‐like structures. During spin coating of the P3HT/THF solution, the ridge‐like structures were generated by the in‐situ template of the THF swelling‐induced creasing structures on the PDMS substrate. To our knowledge, it is the first report that the creasing structures are used as a recoverable template for patterning films. The crease‐templated ridge‐like structures were well modulated by the THF swelling time, the modulus of the PDMS substrate, the P3HT/THF solution concentration and the selective/blanket exposure of the PDMS substrate to O₂ plasma. UV–vis and fluorescence spectrometry measurements indicated that the light absorption and fluorescent emission were improved on the hierarchically patterned P3HT films, which can be utilized to enhance the efficiencies of organic solar cells. Furthermore, this simple versatile method based on the solvent swelling‐induced crease as the in‐situ recoverable template has been extended to pattern other spin‐coated films with different compositions. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 928–939     

Hydrogen bonding interactions,crystallization, and surface hydrophobicity in nanostructured epoxy/block copolymer blends

Hydrogen bonding interactions, phase behavior, crystallization, and surface hydrophobicity in nanostructured blend of bisphenol A‐type epoxy resin (ER), for example, diglycidyl ether of bisphenol A (DGEBA) and poly(ε‐caprolactone)‐block‐poly(dimethyl siloxane)‐block‐poly(ε‐caprolactone) (PCL–PDMS–PCL) triblock copolymer were investigated by Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry, transmission electron microscopy, small‐angle X‐ray scattering, and contact angle measurements. The PCL–PDMS–PCL triblock copolymer consisted of two epoxy‐miscible PCL blocks and an epoxy‐immiscible PDMS block. The cured ER/PCL–PDMS–PCL blends showed composition‐dependent nanostructures from spherical and worm‐like microdomains to lamellar morphology. FTIR study revealed the existence of hydrogen bonding interactions between the PCL blocks and the cured epoxy, which was responsible for their miscibility. The overall crystallization rate of the PCL blocks in the blend decreased remarkably with increasing ER content, whereas the melting point was slightly depressed in the blends. The surface hydrophobicity of the cured ER increased upon addition of the block copolymer, whereas the surface free energy (γ_s) values decreased with increasing block copolymer concentration. The hydrophilicity of the epoxy could be reduced through blending with the PCL–PDMS–PCL block copolymer that contained a hydrophobic PDMS block. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 790–800, 2010     

Preparation of novel,high‐modulus,swollen‐ or jungle‐gym‐type polyimide gels end‐crosslinked with 1,3,5‐tris(4‐aminophenyl)benzene

A novel preparation approach for high‐performance polyimide gels that are swollen or have a jungle‐gym‐type structure is proposed. A new rigid and symmetric trifunctional amine, 1,3,5‐tris(4‐aminophenyl)benzene (TAPB), was synthesized as a crosslinker. Three different kinds of amic acid oligomers derived from pyromellitic dianhydride (PMDA), 4,4′‐oxydiphthalic anhydride (ODPA), p‐phenylenediamine (PDA), and 4,4′‐oxydianiline (ODA) were end‐crosslinked with TAPB at a high temperature to make polyimide networks with different structures. Transparent polyimide gels were obtained from the ODPA–ODA/TAPB series with high compression moduli of about 1 MPa at their equilibrium swollen states in N‐methylpyrrolidone. Microscopic phase separation occurred during the gelation–imidization process when polyimide networks were generated from PMDA–PDA/TAPB and PMDA–ODA/TAPB. After these opaque polyimide networks were dried, a jungle‐gym‐like structure was obtained for the PMDA–PDA/TAPB and PMDA–ODA/TAPB series; that is, there was a high void content inside the networks (up to 70%) and little volume shrinkage. These polyimide networks did not expand but absorbed the solvent and showed moduli as high as those of solids. Therefore, using the highly rigid crosslinker TAPB combined with the flexible monomers ODPA and ODA and the rigid monomers PMDA and PDA, we prepared swollen, high‐performance polyimide gels and jungle‐gym‐type polyimide networks, respectively. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2501–2512, 2002     

Novel synthesis of polyethylene–poly(dimethylsiloxane) copolymers with a metallocene catalyst

Polyethylene–poly(dimethylsiloxane) copolymers were synthesized in solution from an ethylene monomer and an ω‐vinyl poly(dimethylsiloxane) (PDMS) macromonomer at 363 and 383 K with EtInd₂ZrCl₂/methylaluminoxane as a catalyst. The copolymers obtained were characterized with Fourier transform infrared spectroscopy, ¹H and ¹³C NMR, size exclusion chromatography, and differential scanning calorimetry. The rheological properties of the molten polymers were determined under dynamic shear flow tests at small‐amplitude oscillations, whereas the physical arrangement of the phase domains was analyzed with scanning electron microscopy (SEM)/energy dispersive X‐ray (EDX). The analysis of the catalyst activity and the resulting polymers supported the idea of PDMS blocks or chains grafted to polyethylene. The changes in the rheological behavior and the changes in the Fourier transform infrared and NMR spectra were in agreement with this proposal. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2462–2473, 2004     

Partially pyrolyzed poly(dimethylsiloxane)‐based networks: Thermal characterization and evaluation of the gas permeability

In this investigation, the preparation and characterization of partially pyrolyzed membranes based on poly(dimethylsiloxane) (PDMS) are described. These membranes were obtained by the crosslinking of silanol‐terminated PDMS with multifunctional nanoclusters derived from the reaction of pentaerythritoltriacrylate with 2‐aminoethyl‐3‐aminopropyltrimethoxysilane and the in situ polycondensation of tetraethylortosilicate, followed by the thermal treatment of the resulting membranes at different temperatures. The partially pyrolyzed membranes were characterized with infrared spectroscopy, thermogravimetry, elemental analyses, dynamic mechanical analysis, small‐angle X‐ray scattering, and scanning electron microscopy. The membranes exhibited improvements in the thermal stability and mechanical strength. Even with distinct compositions with respect to the Si/O and Si/C ratios, the flexibility of these materials was maintained. The flux rates of the gases through the membranes were measured for N₂, H₂, O₂, CH₄, and CO₂, at 25 °C. The permeability of the membranes changed with increases in the pyrolysis and oxidation temperatures. These membranes could be described as PDMS chains separated by inorganic clusters. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 299–309, 2007.     

Defect‐Controlled Preparation of UiO‐66 Metal–Organic Framework Thin Films with Molecular Sieving Capability

Metal–organic framework (MOF) UiO‐66 thin films are solvothermally grown on conducting substrates. The as‐synthesized MOF thin films are subsequently dried by a supercritical process or treated with polydimethylsiloxane (PDMS). The obtained UiO‐66 thin films show excellent molecular sieving capability as confirmed by the electrochemical studies for redox‐active species with different sizes.