Synthesis of photoreactive isopropyl-substituted poly(phenylene ether ether ketone)

Isopropyl substituted poly(phenylene ether ether ketone) with a high molecular weight was prepared by nucleophilic substitution reaction of isopropyl-substituted difluoro diaryl ether with hydroquinone. This polymer was amorphous and soluble in common organic solvents, such as THF, chloroform, and cyclohexanone. Thermogravimetry of the polymer showed good thermal stability, indicating that a 10% weight loss of the polymer was observed at 470°C in nitrogen. The glass transition temperature of the polymer was 145°C. The polymer had a broad UV absorption band over 250–380 nm. The polymer acted as a photosensitive resist of negative type for UV radiation. The resist had a sensitivity of 40 mJ/cm² and a contrast of 2.8, when it was developed with DMF at room temperature. © 1997 John Wiley & Sons, Inc.     

Synthesis and micropatterning properties of a novel base‐soluble,positive‐working,photosensitive polyimide having an o‐nitrobenzyl ether group

A novel positive‐working, photosensitive polyimide, poly[1,4‐phenyleneoxy‐1,4‐phenylene‐2,2′‐di(2‐nitrobenzyloxy)benzophenone‐3,3′,4,4′‐tetracarboxdiimide] (OPI‐Nb), developable with an aqueous base was prepared by the o‐nitrobenzylation of a polyimide, poly(1,4‐phenyleneoxy‐1,4‐phenylene‐2,2′‐dihydroxybenzophenone‐3,3′,4,4′‐tetracarboxdiimide) (OPI), derived from 2,2′‐dihydroxy‐3,3′,4,4′‐benzophenonetetracarboxylic dianhydride (DHBA) and 4,4′‐oxydianiline, and it micropatterning properties were investigated. The o‐nitrobenzylation of OPI to OPI‐Nb was conducted with o‐nitrobenzyl bromide in N‐methyl‐2‐pyrrolidinone containing Et₃N. The DHBA monomer was synthesized by exhaustive KMnO₄ oxidation of bis(2‐dimethoxy‐3,4‐dimethylphenyl)methane obtained by etherification of bis(2‐hydroxy‐3,4‐dimethylphenyl)methane with iodomethane, followed by deprotection of the methoxy groups and cyclodehydration of the obtained 2,2′‐dihydroxy‐3,3′4,4′‐benzophenonetetracarboxylic acid. The intermediate bis(2‐hydroxy‐3,4‐dimethylphenyl)methane was prepared by the condensation of 2,3‐dimethylphenol with paraformaldehyde. The degree of o‐nitrobenzylation was determined to be over 94 mol % from ¹H NMR absorption of benzylic CH₂ protons. The aromatic OPI was perfectly soluble in a dilute aqueous NaOH solution and tetramethylammonium hydroxide (TMAH), whereas OPI‐Nb was not even swellable in them. In the micropatterning process, OPI‐Nb showed a line‐width resolution of 0.4‐μm and a sensitivity of 5.4 J/cm² when its thin films were irradiated with 365‐nm light and developed with a 2.38% aqueous TMAH solution at room temperature for 90 s. The thickness loss of OPI‐Nb films measured after postbaking at 350 °C was in the 8–9% range. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 776–788, 2007     

Lamellar cluster structure formation resulting from interchain interaction in a novel aromatic polyimide based on PMDA monomer

The aggregation structure of a novel polyimide ( PIM ‐ 6 ) with six methylene flexible spacing groups in biphenyl side chain synthesized by the traditional two‐step imidisation process was investigated by polarized light microscope (PLM), small angle X‐ray scattering (SAXS), wide angle X‐ray scattering (WAXS), and molecular simulation approach. The agreement between the experimental data and simulation result reveals that due to the predominant interchain interaction, each three backbones stack together to form a distinct lamellar cluster with side chains packed inside dispersedly. The thickness of the lamellar cluster is about 16.0 A°, corresponding to a strong peak at 5.5° in SAXS pattern. As the backbone is not perfectly parallel to each other in each lamellar cluster, the distance between each backbone ranges from 5.8 to 8.8 A° possibly relating to the weak peak at 9.8° in WAXS pattern. Meanwhile, no birefringence or apparent phase texture has been observed by PLM indicating an amorphous nature in this film. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

Synthesis of photoreactive poly(ether ether ketone)s containing alkyl groups

Poly(ether ether ketone)s containing alkyl groups were prepared by nucleophilic substitution reaction of alkyl-substituted difluoro diaryl ethers with hydroquinone or by electrophilic substitution reaction of alkyl-substituted diaryl ether with 4,4′-oxydibenzoic acid in PPMA. Polycondensations proceeded smoothly and produced polymers having inherent viscosities up to 0.5-–1.6 dL/g. The polymers were quite soluble in strong acid, dipolar aprotic solvents, and chloroform at room temperature. Thermogravimetry of the polymers showed excellent thermal stability, indicating that 10% weight loses of the polymers were observed in the range above 450°C in nitrogen atmosphere. The glass transition temperatures of the polymers ranged from 128 to 146°C. Furthermore, Polymer 3b functioned as a photosensitive resist of negative type for UV radiation. The resist had a sensitivity of 42 mJ/cm² and a contrast of 2.5, when it was postbaked at 100°C for 10 min, followed by development with THF/acetone at room temperature. © 1996 John Wiley & Sons, Inc.     

Synthesis of diallyl‐containing polyimide and the effect of allyl groups on properties

A diallyl‐containing bisphenol, 1,1‐bis(3‐allyl‐4‐hydroxyphenyl)‐1‐(6‐oxido‐6H ‐dibenzo [c,e][1,2] oxaphosphorin‐6‐yl) ethane ( 1 ), was prepared by a two‐step procedure. Then, a diallyl‐containing diamine, 1,1‐bis(3‐allyl‐4‐(4‐aminophenoxy)‐phenyl)‐1‐(6‐oxido‐6H‐dibenzo [c,e][1,2] oxaphosphorin‐6‐yl)ethane ( 3 ), was prepared from the nucleophilic substitution of ( 1 ) with 4‐fluoronitrobenzene, followed by the reduction by Fe/HCl. A flexible polyimide ( 4 ) with curable diallyl linkages was prepared from the condensation of ( 3 ) and 4,4′‐oxydiphthalic anhydride in m‐cresol in the presence of isoquinoline. Curing polyimide ( 4 ) at 300 °C leads to thermosetting polyimide ( 5 ). We discussed the amounts of allyl group on T_g, coefficient of thermal expansion, and thermal stability of thermosetting polyimides, and found that thermal properties and dimensional stability of thermosetting polyimides increase with the amounts of cured allyl moieties. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 513–520     

Low‐CTE photosensitive polyimide based on semialicyclic poly(amic acid) and photobase generator

A negative‐type photosensitive polyimide (PSPI) based on semialicyclic poly(amic acid) (PAA), poly(trans‐1,4‐cyclohexylenediphenylene amic acid), and {[(4,5‐dimethoxy‐2‐nitrobenzyl)oxy]carbonyl} 2,6‐dimethylpiperidine (DNCDP) as a photobase generator has been developed as a next‐generation buffer coat material. The semialicyclic PAA was synthesized from 3,3′,4,4′‐biphenyltetracarboxylic dianhydride and trans‐1,4‐cyclohexyldiamine in the presence of acetic acid, and the PAA polymerization solution was directly used for PSPI formulation. This PSPI, consisting of PAA (80 wt %) and DNCDP (20 wt %), showed high sensitivity of 70 mJ/cm² and high contrast of 10.3, when it was exposed to a 365‐nm line (i‐line), postexposure baked at 190 °C for 5 min, and developed with 2.38 wt % tetramethylammonium hydroxide aqueous solution containing 20 wt % isopropanol at 25 °C. A clear negative image of 6‐μm line and space pattern was printed on a film, which was exposed to 500 mJ/cm² of i‐line by a contact printing mode and fully converted to poly(trans‐1,4‐cyclohexylenebiphenylene imide) pattern upon heating at 250 °C for 1 h. The PSPI film had a low coefficient of thermal expansion of 16 ppm/K compared to typical PIs, such as prepared from 3,3′,4,4′‐biphenyltetracarboxylic dianhydride and 4,4′‐oxydianiline. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1317–1323, 2010     

Synthesis and properties of ultralow dielectric porous polyimide films containing adamantane

A series of novel ultralow dielectric porous polyimide (PI) films containing adamantane groups was prepared via the thermolysis of polyethylene glycol (PEG) oligomers mixed into PI matrix. Scanning electron microscopy results indicated that the porous PI films showed closed pores with an average diameter of 120 ± 10 nm. Good thermal properties with 5% weight loss temperature of 499 °C in air atmosphere and glass transition temperature in excess of 310 °C were shown for porous PI films. Notably, the ultralow dielectric constant of porous PI films with 1.85 at 1 MHz was obtained and revealed via broadband dielectric spectroscopy. The effects of the chemical structure of the PI matrix and PEG content on the decomposition behavior of PEG and the performance of porous films were investigated. Wide‐angle X‐ray diffraction results indicated that the PI matrix with large d‐spacing generated weaker interactions between the PEG and PI backbone than those of PI matrix with small d‐spacing. As a result, the PEG for the PI matrix with large d‐spacing was completely decomposed. As indicated by the broadband dielectric spectroscopy results, lower dielectric porous PI films were prepared when the PEG contents in the PI matrix increased from 0 to 20 wt %. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 549–559     

Synthesis of optically active alicyclic polyimides from a chiral,nonracemic dianhydride

Optically active alicyclic polyimides were prepared for the first time from (?)‐[1S*,5R*,6S*]‐3‐oxabicyclo[3.2.1]octane‐2,4‐dione‐6‐spiro‐3′‐(tetrahydrofuran‐ 2′,5′‐dione) [(?)‐DAn] via polycondensation with diamines and subsequent chemical or thermal imidization. The dianhydride (?)‐DAn was synthesized by an asymmetric Diels–Alder reaction of a chiral itaconic acid derivative as a key step. Colorless or slightly yellow flexible films were obtained for the (?)‐DAn‐derived polyimides {PI[(?)‐DAn]s}. PI[(?)‐DAn]s showed good solubility toward dipolar aprotic solvents and pyridine. For 1,4‐dioxane and chloroform, the optically active polyimides showed slightly better solubility than the corresponding polyimides prepared from rac‐DAn [PI(rac‐DAn)s]. PI[(?)‐DAn]s showed glass‐transition temperatures of 267–268 °C and 10% weight‐loss temperatures of 416–424 °C in nitrogen. These values were almost identical to those of PI(rac‐DAn)s. The circular dichroism spectra of PI[(?)‐DAn]s showed exciton coupling patterns indicating that to some extent these polyimides had a higher order structure in solution. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4038–4044, 2002     

Synthesis and properties of highly refractive polyimides derived from fluorene‐bridged sulfur‐containing dianhydrides and diamines

Highly refractive and transparent polyimides (PIs) based on fluorene‐bridged and sulfur‐containing monomers have been developed. An aromatic dianhydride, 4,4′‐[p‐thiobis(phenylenesulfanyl)]diphthalic anhydride (3SDEA), was polymerized with several fluorene‐containing diamines, including commercially available 9,9′‐bis(p‐aminophenyl)fluorene (APF), 9,9′‐bis[4‐(p‐aminophenoxy)phenyl]fluorene (OAPF), and newly synthesized 9,9′‐bis[4‐(p‐aminophenyl)sulfanylphenyl]fluorene (ASPF) to afford series A PIs. Meanwhile, series B PIs were obtained from a new dianhydride, 4,4′‐[(9H‐fluorene‐9‐ylidene)bis(p‐phenylsulfanyl)]diphthalic anhydride (FPSP) and two aromatic diamines, ASPF and 4,4′‐thiobis[(p‐phenylenesulfanyl)aniline] (3SDA) via a two‐step polycondensation procedure. The PIs exhibit good thermal stabilities, such as relatively high glass transition temperatures in the range of 220–270 °C and high initial thermal decomposition temperatures (T_10%) exceeding 490 °C. The 9,9′‐disubstituted fluorene moieties endow the PI films with good optical transparency. The optical transmittances of the PI films at 450 nm are all higher than 80% for the thickness of about 10 μm. Furthermore, the highly aromatic fluorene moiety and flexible thioether linkages in the molecular chains of the PIs provide them with high refractive indices of 1.6951–1.7258 and small birefringence of 0.0056–0.0070. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1510–1520, 2008     

Effect of thermal history on the deformation and failure of polyimides

Thermal‐processing structure‐property relationships for polyetherimide (PEI), poly(4,4′‐oxydiphenylene pyromellitimide) (POPPI), and phenylethynyl‐terminated imide (PETI‐5) composite matrices are reported from a fundamental perspective. For thermoplastic PEI, deformation and failure depend primarily on free volume as evidenced by moisture‐absorption, mechanical‐property, and mass‐density changes as a function of annealing. The deformation of POPPI can be divided into the following three regimes as a function of annealing temperature: (1) physical aging‐induced glassy state free‐volume decreases, (2) thermally activated microvoid collapse, and (3) chemical degradation. In the case of PETI‐5, macroscopic defects, free volume, and polymer morphology control deformation. The effects of residual crystallinity on deformation are reported, and it is shown that mechanical toughness can be significantly decreased upon annealing below the glass‐transition temperature. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2947–2959, 2001     

Phosphinated phenols from acid‐fragmentation of bisphenols and their unsymmetrical diamine derivatives for copolyimides

Four novel diamines (9–12) were prepared by a two‐step procedure from phosphinated phenols (1–4) that were prepared from acid‐fragmentation of four bisphenols, including bisphenol A, 4,4′‐isopropylidenebis(2,6‐dimethylphenol), cis(4‐hydroxyphenyl)cyclohexane, and 9,9′‐bis(4‐hydroxyphenyl)fluorene, followed by nucleophilic addition of 9,10‐dihydro‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO). Copolyimides based on (9–12) /4,4′‐diaminodiphenyl ether (ODA)/dianhydride were prepared. The structure‐property relationship on the copolyimides was discussed. Due to the structural similarity, (9) /ODA‐based copolyimides were compared with (10) /ODA‐based copolyimides, while (11) /ODA‐based copolyimides were compared with (12) /ODA‐based copolyimides. The dimethyl substitutents cause (10) /ODA‐based copolyimides to display higher T_g, modulus, dimensional stability, contact angle, and better solubility than (9) /ODA‐based copolyimides. (12) /ODA‐based copolyimides that exhibit fluorene moieties display higher T_g and thermal stability, but a lower contact angle and poorer solubility than (11) /ODA‐based copolyimides that exhibit cyclohexane moieties. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 390–400     

Structure and properties of polyimide films during a far‐infrared‐induced imidization process

The conversion of poly(amic acid) into polyimide (PI) was achieved with far‐infrared radiation (FIR) and conventional thermal treatments. The structure and properties of PI films during different stages of imidization were studied with Fourier transform infrared spectroscopy, weight‐loss analysis during imidization, tensile property measurements, and dynamic mechanical thermal analysis. The effects of the imidization degree, postimidization, and solvent on the thermal and mechanical properties of PI films were quantitatively investigated. The corresponding structural changes were also examined. The experimental results showed that the imidization process proceeded more quickly and more completely in an FIR oven than in a conventional oven. A prolonged FIR treatment at a lower temperature (25–100 °C) accelerated the imidization process. The tensile stress–strain curves had a fanlike distribution with the development of the FIR imidization process and a fishtail distribution with conventional thermal imidization. During FIR imidization, the best tensile properties were obtained at 340 °C, and thermooxidative degradation occurred at about 420 °C. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2490–2501, 2004     

Thermomechanical properties and phase structure of epoxy/silica nano‐hybrid materials constructed from a linear silicone oligomer

Epoxy‐grafted silicone oligomer (ESO), which has a linear silicone chain in the backbone moiety, was synthesized from a trifunctional alkoxysilane via a sol–gel reaction. Characterization of ESO was performed with ¹H and ²⁹Si NMR, Fourier transform infrared, and gel permeation chromatography. The number‐average molecular weight of ESO was 3300. By adding the silicone oligomer as the inorganic source in the curing process of the epoxy resin, novel epoxy/silica hybrid materials were prepared. It was observed by transmission electron microscope that fine silica‐rich domains of about 5‐nm diameter were uniformly dispersed in the cured epoxy matrix. Thermomechanical properties of the hybrid materials were also investigated. The storage modulus in the rubbery region and the peak area of the tan δ curve at the glass‐transition region increased and decreased, respectively, with the hybridization of the silica network. The mobility of the epoxy network chains should be considerably suppressed by the hybridization with the silica network. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1631–1639, 2005     

Structural characterization and gas‐transport properties of brominated matrimid polyimide

The commercial polyimide Matrimid was modified by bromination for the purpose of improving its membrane‐transport properties as a gas‐separation material and providing functional group reactivity for further modifications. The unmodified and brominated polymers were characterized by elemental analysis and one‐dimensional and two‐dimensional NMR, which revealed that one bromine atom per repeat unit was incorporated regioselectively onto the indane aromatic ring. The thermal and physical properties of the polymers before and after bromination were also investigated. The gas‐transport properties of the unmodified and brominated polymers were compared. © 2002 Government of Canada. Exclusive worldwide publication rights in the article have been transferred to Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4193–4204, 2002     

The molecular structure of poly(biphenyl dianhydride-p-phenylenediamine) polyimide thin films by infrared spectroscopy: Thickness dependence of structure in the nano- to micrometer range

The molecular structure of poly[biphenyl dianhydride-p-phenylenediamine] (BPDA–PDA) polyimide in ultrathin (3–300 nm) films on silicon has been characterized by polarized infrared spectroscopy in conjunction with ellipsometry and X-ray reflectivity measurements. In spite of the high degree of crystalline packing of the polymer chains, the results show that an unexpected and significant content of imide rings exhibit local structural perturbations, including out-of-plane twisting. Further, the fraction of perturbed rings increases with increasing film thickness while, in contrast, the high degree of in-plane uniaxial film symmetry and planar stacking of the chains remain constant with thickness. These results reveal a new structural aspect of localized ring disorder that arises within the otherwise well-ordered, chain-stacked structure of BPDA–PDA polyimide films. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1247–1260, 1998     

Synthesis and properties of sulfonated polyimides derived from bis(sulfophenoxy) benzidines

A series of aromatic sulfonated polyimides (SPIs) bearing sulfophenoxy side groups have been successfully synthesized and evaluated as polymer electrolyte membranes for fuel cell applications. The SPIs had high viscosity and gave tough and flexible membranes. The SPI membranes showed anisotropic membrane swelling in water with much larger dimensional change in thickness direction than in plane one. They showed the better proton‐conducting performance even in the lower relative humidity (RH) range than the other SPI membranes, for example, a high proton conductivity of 0.05 S/cm at 50 % RH and 120 °C. They maintained high mechanical strength and conductivity after aging in water at 130 °C for 500 h, showing much better water stability compared with the main‐chain‐type SPI and side‐chain‐type SPI membranes reported so far. In polymer electrolyte fuel cells (PEFCs) operated at 90 °C and 84–30%RH, they showed fairly high cell performances and have high potential for PEFC applications. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1463–1477, 2009     

Synthesis,structure, and properties of polyimide and polyurethane‐urea‐imide copolymers

Several, novel polyimide–polyurethane‐urea‐imide (PI‐PUI) copolymers with different polyimide (PI) contents were prepared by an in situ interpenetrating reaction between polyurethane‐urea‐imide (PUI) precursor and poly(amide acid). Changing the ratio of the PUI precursor and poly(amide acid) resulted in a change of the properties of the PI‐PUI copolymers from plastic to elastomer. Fourier transform infrared spectra revealed the characteristic absorption bands of PI‐PUI copolymers; differential scanning calorimetry (DSC) analyses revealed that the glass‐transition temperature of the soft‐segment‐rich phase decreased as the PI content increased in PI‐PUIs, meaning that the soft segments (i.e., PEG) were more incompatible and had better crystallizability with a high‐PI‐segment content in PI‐PUI. Wide‐angle X‐ray diffraction curves exhibited more ordered structure within the disordered PI‐PUI copolymer's state with an increasing PI content, which further agreed with the DSC results. Scanning electron micrographs clearly showed that the molecular chains in PI‐PUI with a high‐PI‐content packed, ordered lamellar structure. Thermogravimetric curves indicated that the heat resistance of PI‐PUI was better than pure PUI. The introduction of the PI component into PUI by an in situ interpenetrating reaction method is an effective way to improve the thermal stability and solvent resistance of PUI. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 216–225, 2004     

Non‐surfactant template‐directed synthesis of SiO2‐polyimide hybrid self‐standing films with ordered mesoporous structure

The silica‐PI hybrid self‐standing films with ordered mesoporous structure have been prepared by using dibenzoyl‐L ‐tartaric acid (L ‐DBTA) as non‐surfactant template under mild sol–gel route. Polyimide matrix was obtained from polyamic acid (PAA) via thermal imidization process and the template was removed in this process. The PI‐based hybrid film with 20 wt% SiO₂ obtained from DBTA presented the ordered mesoporous channels with average pore size of about 2.0 nm and BET surface area of 1167 m²/g. FTIR and SEM studies indicated that the hydrogen bond interaction between the carboxylic groups of DBTA and benzamide bonds of PAA made the PAA possibly participate in the assembly process of the aggregates of the non‐surfactant template molecules. The mechanical, thermal and some physical properties of these hybrid films materials were also characterized. Copyright © 2010 John Wiley & Sons, Ltd.     

Modulating structural stability and acid sensitivity of photosensitive polymer micelles simply via one‐batch UV irradiation

This article describes the photosensitive polymer micelles whose structural stability and acid sensitivity can be widely tuned simply via one‐batch UV irradiation. To this end, the well‐defined poly(5‐ethyl‐5‐methacryloyloxy‐methyl‐2‐styryl‐[1,3]dioxane)‐block‐poly[poly(ethylene glycol) methacrylate] (PEMSD‐b‐PPEGMA) copolymers were synthesized via RAFT polymerization under mild visible light radiation at 30 °C. The results demonstrated that the irradiation of the homogeneous acetone solution with UV light only induced Z‐isomerization of their cinnamyl groups, while irradiating PEMSD chains in the bulky micellar cores only induced dimerization. Moreover, the micelles of previously Z‐isomerized copolymer could be effectively stabilized without changing their acid sensitivity on irradiating for shortly 3 min, while UV irradiation for 30 min could remarkably improve the acid stability of these micelles. These novel properties are of potential applications in controlled drug delivery. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Preparation of novel photoreactive polycarbazole‐based microparticles: Reactivity features

Four types of innovative benzophenone (BPh)‐ or aryl azide (ArAz)‐containing photoreactive polycarbazole (polyCbz)‐based microparticles (MPs) were prepared using an oxidative liquid phase polymerization system. Their photochemical reactivity was evaluated by their reaction with highly inert poly(2‐chloro‐paraxylelene) (Parylene C) films. Possible mechanisms for the photochemical reaction of those MPs with Parylene C were discussed. The highly photoreactive BPh was found to react more inside the particle causing internal cross‐linking of MP polyCbz chains, fusion between adjoining particles and deformation of their spherical structure. In contrast, the less reactive but more selective ArAz‐containing MPs were found to react much more with Parylene C. The strong reactivity of such photoreactive MPs toward Parylene C films emphasizes a general method for the functionalization of stable nonfunctional polymeric coatings. This paves the way to simple and solvent‐free functionalization of nonfunctional coatings and materials by light. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011