Synthesis and light‐emitting properties of new poly(p‐phenylenevinylene) derivatives containing oxadiazole moiety

Two new poly(p‐phenylenevinylene) (PPV) derivatives containing the oxadiazole moiety (OXA–PPV1 and OXA–PPV2) were synthesized by the Wittig condensation polymerization reaction and their thermal and light‐emitting properties were investigated. The single‐layer and triple‐layer electroluminescent (EL) devices with configurations of ITO/OXA–PPV1/Al and ITO/OXA–PPV1/OXD/Alq₃/Al were fabricated. They both exhibited blue emission at 460 nm. For comparison, the PPV derivative containing the oxadiazole moiety only in the side chains (OXA–PPV2) was also synthesized. Both single‐layer and triple‐layer EL devices with OXA–PPV2 as the emissive layer emitted green‐light at 560 nm. The turn‐on voltages of the triple‐layer device was 11 V for OXA–PPV1 and 8 V for OXA–PPV2. The triple‐layer EL devices showed much better performance than that of the single‐layer devices. The spectra indicated that energy or electron transfer occurred from the side‐chain oxadiazole to the main‐chain styrene unit. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2424–2428, 2002     

Branched poly(p‐phenylenevinylene): Synthesis,optical and electrochemical properties

A series of poly(p‐phenylene vinylene) (PPV) derivatives with phenylene vinylene side chains (branched PPVs), PPV0, PPV1, PPV2, and PPV3, were synthesized by the Heck coupling reaction and characterized by TGA, absorption spectra, photoluminescence (PL) spectra, and electrochemical cyclic voltammetry. The branched PPVs showed two absorption peaks in the UV–vis region, corresponding to the conjugated side chains (UV absorption) and the main chains (the visible absorption). Especially the absorption spectrum of PPV3 covers a broad wavelength range from 300 to 500 nm. Introducing the electron‐donating alkoxy substituents on the PPV main chains and increasing the content of the alkoxy groups lead to bathochromic shift of both absorption and PL spectra from PPV1 to PPV2 to PPV3. The onset oxidation potential of the branched PPVs is lower by 0.1–0.2 V than that of PPV, indicating that the electron‐donating ability of the branched PPVs enhanced in comparison with that of PPV. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and light‐emitting properties of new poly(p‐phenylenevinylene) derivatives containing oxadiazole moiety

Two new poly(p‐phenylenevinylene) (PPV) derivatives containing oxadiazole moiety (OXA‐PPV1 and OXA‐PPV2) were synthesized by the Wittig condensation polymerization reaction. Their thermal and light‐emitting properties were investigated. The single‐ and triple‐layer electroluminescent (EL) devices with configurations of ITO/polymer/Al and ITO/polymer/OXD‐7/Alq₃/Al were fabricated. They exhibited blue emission at 470 nm for OXA‐PPV1 and green emission at 560 nm for OXA‐PPV2. The turn‐on voltages of triple‐layer device were 11 V for OXA‐PPV1 and 8 V for OXA‐PPV2. The triple‐layer EL devices showed much better performance than did the single‐layer devices. The spectra indicated energy transfer occurred from segments of side chain to polymer backbone. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 422–428, 2002     

Novel poly(3,4‐dialkoxythiophene)s carrying 1,3,4‐oxadiazolyl‐biphenyl moieties: synthesis and nonlinear optical studies

Two new donor–acceptor types of polymer, poly{2‐(biphenyl‐4‐yl)‐5‐[3,4‐dialkoxy‐5‐(1,3,4‐oxadiazol‐2‐yl)thiophen‐2‐yl]‐1,3,4‐oxadiazole}s, were synthesized starting from 2,2′‐sulfanediyldiacetic acid and diethyl ethanedioate through multi‐step reactions. The polymerization was carried out via the polyhydrazide precursor route. The optical and charge‐transporting properties of the polymers were investigated using UV‐visible and fluorescence emission spectroscopic and cyclic voltammetric studies. The polymers showed bluish‐green fluorescence in solutions. The electrochemical band gaps of the polymers were determined to be 2.16 and 2.22 eV. The nonlinear optical properties of the polymers were investigated at 532 nm using the single‐beam Z‐scan technique with nanosecond laser pulses. The polymers showed strong optical limiting behaviour due to effective three‐photon absorption. The values of the three‐photon absorption coefficients for the polymers were found to be 9 × 10^?24 and 17 × 10^?24 m³ W^?2, which are comparable to those of good optical limiting materials. Copyright © 2010 Society of Chemical Industry     

Synthesis and properties of novel deep red‐emitting copolymers based on a poly(p‐phenylenevinylene) derivative

A series of novel copolymers based on a poly(p‐phenylenevinylene) (PPV) derivative with different content of narrow band‐gap unit 2,1,3‐benzoselenadiazolevinylene (BSeV) was prepared via Stille coupling reaction. The copolymers emit light from deep red to near‐infrared (NIR) depending on BSeV content in the copolymers. The electroluminescence (EL) emission peaked at 752 nm for the copolymer with the content of 30 mol % BSeV is among the longest reported so far for the PPV polymers. The best device performance is observed for the copolymer with 1 mol % BSeV content with external quantum efficiency (QE_ext) of 0.26% and CIE coordinate 0.65, 0.34 (x,y). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4321–4327, 2006     

Influence of sulfuric acid bath on morphological structure and mechanical properties of poly(p‐phenylene‐1,3,4‐oxadiazole) fibers

Poly(p‐phenylene‐1,3,4‐oxadiazoles) (p‐PODs) spinning solution was prepared by one‐step polycondensation, and p‐POD fibers were obtained by wet spinning method using dilute sulfuric acid as coagulation bath. The morphology and mechanical properties of p‐POD fibers under different coagulating conditions, such as bath concentration and temperature, were qualitatively and quantitatively studied by microscopes, ultrasonic orientation measurement, WAXD, and other traditional methods. The microscopic observation indicated that the p‐POD fibers were of three‐layer structure which consisted of outer skin, inner skin, and the core. The skin‐core structure and surface feature of the fibers were greatly affected by the coagulating conditions. At the same time, the results of WAXD and ultrasonic orientation measurement demonstrated that the crystallinity and orientation of the fibers also varied with the change of bath conditions. The tests of mechanical properties showed that the tensile strength, elongation at break, and maximum draw ratio of the p‐POD fibers were determined by their solid‐phase structures, which were largely influenced by coagulation conditions. According to the structure analysis and the mechanical tests, the optimal coagulation parameters were chosen to obtain p‐POD fibers with denser and more regular structure and better mechanical properties. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

New copolymer of poly(N‐vinylcarbazole) and poly(p‐phenylenevinylene) for optoelectronic devices

A novel diblock copolymer based on poly(N‐vinylcarbazole) PVK and poly(p‐phenylenevinylene) (PPV) precursor was synthesized by oxidative cross‐linking. The grafting of PPV with PVK moieties was elucidated by infrared absorption analysis. A structural study by X‐ray diffraction and a morphological study of the copolymer by scanning and transmission electron microscopy reveal a multiscale one‐dimensional self‐organization both at the molecular and at the sub‐micrometric level. The resulting copolymer exhibits original optical properties compared to those of PVK and PPV ones and presents an improved thermal behavior. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2839–2847, 2013     

Synthesis and characterization of poly(1,4‐phenylenevinylene) derivatives containing liquid crystalline oxadiazole groups

Two novel poly(1,4‐phenylenevinylene) (PPV) derivatives containing liquid crystalline oxadiazole side chains were prepared by a dehydrochlorination process. The homopolymer poly(2‐methoxy‐5‐((2‐methoxy‐phenyl)‐5‐hexyloxy‐phenyloxy‐1,3,4‐oxadiazole)‐1,4‐phenylenevinylene) (HO–PE₆) is insoluble in common solvents, whereas the copolymer poly(2‐methoxy‐5‐((2‐methoxy‐phenyl)‐5‐hexyloxy‐phenyloxy‐1,3,4‐oxadiazole))‐(2‐methoxy‐5‐(2′‐ethylhexyloxy))‐1,4‐phenylenevinylene) (CO–PE₆) is soluble in common solvents such as chloroform, THF, and p‐xylene. The molecular structure of CO–PE₆ was confirmed by FTIR, ¹H‐NMR, UV–vis spectroscopy, and polarized light microscopy. CO–PE₆ showed a maximum emission at 556 nm in chloroform and at 564 nm in solid film, when excited at 450 nm. The maximum electroluminescence emission of the device indium–tin oxide (ITO)CO–PE₆/Al is at 555 nm. The turn‐on voltage of LEDs based on CO–PE₆ and MEH–PPV is 6.5 and 8.5 V, respectively. The electron mobility of CO–PE₆ is higher than that of MEH–PPV based on the results of current–voltage and electrochemical behavior of both MEH–PPV and CO–PE₆. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 396–403, 2004     

Blue light‐emitting poly(p‐phenylenevinylene) derivative with oxadiazole and carbazole pendant groups

A blue light‐emitting statistical poly(p‐phenylenevinylene) (PPV) copolymer with hole‐transporting carbazole and electron‐transporting oxadiazole pendant groups attached to the kinked m‐terphenyl unit was prepared by Heck coupling between 1,4‐divinylbenzene and dibromides. The latter were synthesized through pyrylium salts. The polymer had optical band gap of 2.89 eV and emission maximum at 446 nm in THF solution and 434 nm in thin film. It showed a pure blue emission with no aggregates or excimers formed even in solid state because of the long and bulky pendant groups. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3842–3849, 2006     

New poly(1,3,4‐oxadiazole)s bearing pentadecyl side chains: Synthesis and characterization

The 4‐[4′‐(Hydrazinocarbonyl)phenoxy]‐2‐pentadecylbenzohydrazide was polycondensed with aromatic diacid chlorides viz., terephthalic acid chloride (TPC), isophthalic acid chloride (IPC), and a mixture of TPC : IPC (50 : 50 mol %) to obtain polyhydrazides which on subsequent cyclodehydration reaction in the presence of phosphoryl chloride yielded new poly(1,3,4‐oxadiazole)s bearing flexibilizing ether linkages and pentadecyl side chains. Inherent viscosities of polyhydrazides and poly(1,3,4‐oxadiazole)s were in the range 0.53–0.66 dL g^?1 and 0.49–0.53 dL g^?1, respectively, indicating formation of medium to reasonably high molecular weight polymers. The number average molecular weights (M_n) and polydispersities (M_w/M_n) of poly(1,3,4‐oxadiazole)s were in the range 14,660–21,370 and 2.2–2.5, respectively. Polyhydrazides and poly(1,3,4‐oxadiazole)s were soluble in polar aprotic solvents such as N,N‐dimethylacetamide, 1‐methyl‐2‐pyrrolidinone, and N,N‐dimethylformamide. Furthermore, poly(1,3,4‐oxadiazole)s were also found to be soluble in solvents such as chloroform, dichloromethane, tetrahydrofuran, pyridine, and m‐cresol. Transparent, flexible, and tough films of polyhydrazides and poly(1,3,4‐oxadiazole)s could be cast from N,N‐dimethylacetamide and chloroform solutions, respectively. Both polyhydrazides and poly(1,3,4‐oxadiazole)s were amorphous in nature and formation of layered structure was observed due to packing of pentadecyl chains. A decrease in glass transition temperature was observed both in polyhydrazides (143–166°C) and poly(1,3,4‐oxadiazole)s (90–102°C) which could be ascribed to “internal plasticization” effect of pentadecyl chains. The T₁₀ values, obtained from TG curves, for poly(1,3,4‐oxadiazole)s were in the range of 433–449°C indicating their good thermal stability. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci 124:1281–1289, 2012     

Synthesis and properties of photoluminescent copolymer containing 1,3,4‐oxadiazole and carbazole rings

The luminescent copolymer 2‐phenyl‐5‐[3′‐(methacrylamido)phenyl]‐1,3,4‐oxadiazole and vinylcarbazole (PMAPO–VCZ), combining hole‐facilitating moiety, carbazole ring, and electron‐facilitating moiety, 1,3,4‐oxadiazole, as side groups, was synthesized by a radical polymerization of the olefinic monomer PMAPO and VCZ. For comparison, the homopolymer P‐PMAPO was also synthesized by similar procedures. The solubility, thermal, and optical properties of the copolymers were investigated. The synthesized copolymer was soluble in common organic solvents but the homopolymer of PMAPO was dissolved only by hot THF. Thermogravimetric analysis and differential scanning calorimetry measurements showed that the copolymer and homopolymer exhibit good thermal stability up to 360 and 340°C with glass‐transition temperatures higher than 105 and 65°C, respectively. The photoluminescence properties were investigated. The results showed that the copolymer emits blue and blue‐green light and the emission spectra of monomer and polymers exhibit obvious solvent effect. With the increase of polarity of solvents, the fluorescence spectra distinctly change, appearing with a red shift at room temperature. The concentration‐dependent emission spectra change significantly with the increase of concentration. In addition, when N,N‐dimethylaniline (DMA) was gradually added to the solution of copolymers, the emission intensity of fluorescence was dramatically increased. However, when the concentration of DMA was increased beyond a certain level, the emission intensity of fluorescence gradually decreased. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2777–2783, 2004     

Substituent effect on the optoelectronic properties of poly(p‐phenylenevinylene) based conjugated‐nonconjugated copolymers

Two classes of light emitting Poly(p‐phenylenevinylene) (PPV) based conjugated‐nonconjugated copolymers (CNCPs) have been synthesized. The conjugated chromophores containing 2‐methoxy‐5‐(2′‐ethylhexyloxy)‐1,4‐phenylenevinylene (MEHPV) and 2,5‐dimethyl‐1,4‐phenylenevinylene (DMPV) moieties are rigid segments and nonconjugated portion containing hexyl units are flexible in nature. All copolymers were synthesized by well‐known Wittig reaction between the appropriate bisphosphonium salts and the dialdehyde monomers. The resulting polymers were found to be readily soluble in common organic solvents like chloroform, THF and chlorobenzene. The effect of chromophore substituents on the optical and redox properties of the copolymers has been investigated. Color tuning was carried out by varying the molar percentage of the comonomers. The UV‐Vis absorption and PL emission of the copolymers were in the range 314–395 nm and 494–536 nm respectively. All the polymers show good thermal stability. Polymer light‐emitting diodes (PLEDs) were fabricated in ITO/PEDOT:PSS/emitting polymer/cathode configurations of selected polymers using double‐layer, LiF/Al cathode structure. The emission maxima of the polymers were around 499–536 nm, which is a blue‐green part of the color spectrum. The threshold voltages of the EL polymers were in the range of 5.4–6.2 V. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and optical properties of poss‐based oxadiazole nanohybrids with three‐dimensional molecular conjugated structure

A series of oxadiazole‐containing molecular hybrid materials with three‐dimensional structure ( P1–P3 ) was prepared by Heck reaction based on the octavinylsilsesquioxane. All resultant hybrid materials are soluble in common organic solvents and possess good film‐forming property. Their structures and properties were characterized and evaluated by FTIR, ¹H‐NMR, ¹³C‐NMR, ²⁹Si‐NMR, MALDI‐TOF, UV–vis, photoluminescence (PL), cyclic voltammetry, and elemental analysis (EA). The results showed that the substituted arm numbers of hybrids ( P2 and P3 ) with pushing electron groups were efficiently controlled. Moreover, the hybrids possessed a steady blue emission and good electron‐injecting property in film. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40246.     

Synthesis,photo‐, and electroluminescent properties of the soluble poly[(2,5‐diphenylene‐1,3,4‐oxadiazole)‐ 4,4′‐vinylene]

A novel soluble conjugated polymer, poly[(2,5‐diphenylene‐1,3,4‐oxadiazole)‐4,4′‐vinylene] (O‐PPV), containing an electron‐transporting group on the main chain of PPV, was synthesized according to HORNER mechanism. The oligo‐polymer with M_w = 1000 and T_d = 270°C is soluble in chloroform and tetrahydrofuran. The photoluminescent (PL) properties were investigated using different concentrations of solid‐state O‐PPV/PEO blends absorption and selective excitation measurements. The results show that PL arises from interchain charge‐transfer states in solid‐state O‐PPV. Compared with the analogous single‐layer device constructed with PPV (ITO/PPV/Al), which emits two peaks at λ = 520 nm and 550 nm (shoulder), the electroluminescence (EL) spectrum of the device [ITO/O‐PPV (80 nm)/Al] is a broad peak at λ_max = 509 nm. The quantum efficiency (0.13%) of the device ITO/O‐PPV/Al is much higher than that of the device ITO/PPV/Al, due to the introduction of the electron‐transporting group–oxadiazole units in the main chain of PPV. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 3535–3540, 1999     

Influences of hybrid carbon nanofillers on structures and electrical properties of sulfonated poly(1,3,4‐oxadiazole)‐based composite films

Sulfonated poly(1,3,4‐oxadiazole) (sPOD)‐based composite films, including 10 wt % hybrid carbon nanofillers composed of different weight ratios of multiwalled carbon nanotube (MWCNT) and graphene sheets, were manufactured via an efficient ultrasonication‐assisted solution mixing and casting. Fourier transform infrared (FTIR) spectra of the composite films confirmed the existence of specific interactions between sPOD backbone and MWCNT or graphene sheet. Transmission electron microscopic (TEM) images of cross sections of the composite films showed that 2‐dimensional (2D) graphene sheets formed an anisotropically oriented structure in the sPOD matrix film, but they are randomly dispersed owing to the introduction of 1‐dimensional (1D) MWCNT. Accordingly, the electrical resistivity of the composite films decreased largely from ～10³ Ω cm to ～10¹ Ω cm with the increment of the relative MWCNT content in hybrid carbon nanofillers due to the synergistic bridging effect. Thus, sPOD‐based composite films with 10 wt % hybrid carbon nanofillers exhibited high performance in electric heating by attaining rapid temperature responsiveness, high electric power efficiency, and stable maximum temperatures under given applied voltages. It was also revealed that the hybrid composite films were operationally stable over a long‐term stepwise electric heating experiment. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44499.     

Benzotrifluoromethyl group‐substituted poly(para‐phenylenevinylene): Effect on solubility,optical, and electronic properties

A new organosoluble benzotrifluoromethyl group containing poly(p‐phenylenevinylene) (BTFM‐PPV) has been synthesized via Gilch polymerization. The polymer is soluble in common organic solvents such as tetrahydrofuran, chloroform, dichloromethane, toluene, and xylene. BTFM‐PPV exhibited fluorescence emission peak with a very high blue shift at 474 nm with an excitation wavelength at 420 nm compared with many other PPV derivatives reported earlier. Incorporation of fluorated bezotrifluoromethyl pendent group in the PPV backbone lowers the HOMO and LUMO energy levels of BTFM‐PPV (2.48 eV) which retarded the hole injection and increase the electron injection in the device. The current–voltage (I–V) characteristic of the polymer was measured by fabricating the polymer as ITO/BTFM‐PPV/Al diode. The device performance was markedly improved by incorporation of 4‐fluoro‐3trifluoromethylphenyl units into the polymer main chain. The turn on voltage of the device observed from the I–V measurements was 7 V. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Ultraviolet resistance modification of poly(p‐phenylene‐1,3,4‐oxadiazole) and poly(p‐phenylene terephthalamide) fibers with polyhedral oligomeric silsesquioxane

Octa‐ammonium chloride salt of polyhedral oligomeric silsesquioxane (POSS) was synthesized by a hydrolysis reaction and introduced into poly(p‐phenylene‐1,3,4‐oxadiazole) (p‐POD) and poly(p‐phenylene terephthalamide) (PPTA) fibers by a finishing method to enhance the UV resistance. The effects of the POSS concentration, treatment temperature, and time on the tensile strength of the fibers were investigated. The surface morphology, mechanical properties, crystallinity, degree of orientation of fibers, and intrinsic viscosity of the polymer solution were characterized in detail. The results indicate that the tensile strength retention and intrinsic viscosity retention of the fibers treated with POSS were much higher than those of the untreated fibers after the same accelerated irradiation time; this demonstrated that this treatment method was feasible. We also found that the efficacy of the protection provided by POSS was more beneficial to p‐POD than PPTA because of the different structure. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42643.     

Synthesis and optical and thermal properties of poly[methyl(2,9‐diphenyl‐ 7,8‐benzophenanthryl)silylene‐co‐1,4‐bis(methylphenylsilyl)phenylene]

Poly[methyl(2,9‐diphenyl‐7,8‐benzophenanthryl)silylene‐co‐1,4‐bis(methylphenylsilyl)phenylene] (PMBS‐co‐BSP) was synthesized by the condensation reaction of dichloromethyl(2,9‐diphenyl‐7,8‐benzophenanthryl)silane and 1,4‐bis(chloromethylphenylsilyl)benzene with sodium in toluene. Optical and thermal behavior of the polymer was investigated. Because of the introduction of substituted benzophenanthryl groups into the Si atoms of the polymer, the UV absorption wavelength of the PMBS‐co‐BSP red‐shifted significantly in the UV region, and a strong photoluminescence band was observed in the visible region other than the near‐UV photoluminescence typical of normal polysilane. The photochemical behavior was examined both in solution and in thin film by fluorescence and UV spectroscopy. Irradiation of the PMBS‐co‐BSP with a low‐pressure mercury lamp in solution resulted in homolytic scission of silicone–silicone bonds; the fluorescence emission intensities decreased gradually with increasing UV irradiation time and the maximum emission wavelength blue‐shifted significantly. Irradiation of thin solid films of the PMBS‐co‐BSP in air led to the formation of photoproducts containing Si? OH and Si? O? Si groups. The PMBS‐co‐BSP began to weigh less at about 300 °C and the weight loss of the polymer at 700 °C was calculated to be 75% of the initial weight in N₂. Copyright © 2006 Society of Chemical Industry     

Photoisomerization behavior of bisbenzylidene and 1,3,4‐oxadiazole‐based liquid crystalline polyesters

Photoisomerization behavior of bisbenzylideneacetone/cycloheptanone and 1,3,4‐oxadiazole containing nematic liquid crystalline polyesters under UV irradiation was investigated. Solubility, carbonyl group absorption band in FTIR, optical microscopy observation, as well as DSC analysis through existence of liquid crystallinity after irradiation were proved this phenomenon. Fluorescence spectra revealed blue‐emission maxima with Stokes shift in the range of 46–49 nm. Band gap energy calculated from absorption spectra are in the range of 3.18–3.41 eV. Structure–property relationships were probed by correlating the spacer length with development of mesophase formation, thermal, and optical properties. Optical property of polymers disclosed photoisomerization processes. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Nonlinear optical studies on new conjugated poly{2,2l‐(3,4‐ dialkoxythiophene‐2,5‐diyl) bis[5‐(2‐thienyl)‐1,3,4‐oxadiazole]}s

Three new donor–acceptor type poly{2,2^l‐(3,4‐ dialkoxythiophene‐2,5‐diyl)bis[5‐(2‐thienyl)‐1,3,4‐oxadiazole]}s ( P1, P2, and P3 ) were synthesized starting from thiodiglycolic acid and diethyl oxalate through multistep reactions. The polymerization was carried out using chemical polymerization technique. The optical and charge‐transporting properties of the polymers were investigated by UV‐visible, fluorescence emission spectroscopic and cyclic voltammetric studies. The polymers showed bluish‐green fluorescence in solutions. The electrochemical band gaps were determined to be 2.03, 2.09, and 2.17 eV for P1 , P2, and P3, respectively. The nonlinear optical properties of new polymers were investigated at 532 nm using single beam Z‐scan and degenerate four‐wave mixing (DFWM) techniques with nanosecond laser pulses. The polymers exhibited strong optical limiting behavior due to “effective” three‐photon absorption. Values of the effective three‐photon absorption ( 3PA ) coefficients, third‐order nonlinear susceptibilities (χ⁽³⁾), and figures (F) of merit were calculated. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010