Morphology,deformation behavior and thermomechanical properties of polypropylene/maleic anhydride grafted polypropylene/layered silicate nanocomposites

Nanocomposites polypropylene (PP) with 3 and 7 wt % of clay were prepared by melt mixing. Four types of maleic anhydride grafted PP (MAPP) in broad range of MA groups content (0.3–4 wt %) and molecular weights (MW) were used as polar compatibilizers. The effect of the MAPP kind on both the clay dispersion and miscibility with PP was studied. The mixed intercalated/exfoliated morphologies of nanocomposites in the presence of all studied compatibilizers were revealed by XRD and TEM. The oligomer compatibilizer with 4 wt % of MA groups increases the intercalation ability of polymer into clay galleries but this one has limited miscibility with PP and worsens crystalline structure of polymer matrix. The MAPPs with 0.3–1.3% of MA are characterized by the lower intercalation ability but well cocrystallize with PP. Maximum reinforcing effect is attained using high MW MAPP with 0.6% MA and for nanocomposite with 7 wt % (3.8 vol %) of clay it averages almost 1.7 times relative to neat PP and 1.3 times relative to noncompatibilized composite. Dynamic storage moduli of nanocomposites compatibilized by MAPPs with 0.3–1.3% of MA containing 7 wt % of clay increase up to 1.4–1.5 around 30–75°C and over the whole temperature range remain higher compared with both neat PP and uncompatibilized composite. On the contrary, the oligomer MAPP with 4 wt % of MA groups decreases the thermal–mechanical stability of nanocomposite at high temperature compared with both PP and uncompatibilized composites. The study of nanocomposites flammability showed that creating complex composites containing both layered silicate and relatively small amount of magnesium hydroxide can be a successful approach to reduce the combustibility of PP‐based nanocomposites. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Preparation and mechanical properties of polypropylene-clay hybrids using a maleic anhydride-modified polypropylene oligomer

Polypropylene-clay hybrids (PPCH) were prepared using a maleic anhydride-modified PP oligomer (PP-MA) as a compatibilizer. PP was melt-blended with organophilic clay which was intercalated with PP-MA. In these PPCHs, the particles of silicate layers were dispersed at the nanometer level. The particles became smaller and were dispersed more uniformly, as the ratio of PP-MA to the clay was increased. The dynamic storage moduli of the PPCHs were higher than that of PP up to 130°C. For example, the modulus of the PPCH with 5 wt % clay and 22 wt % PP-MA was 1.8 times higher compared to that of PP at 80°C. As the dispersibility of the clays was improved, the reinforcement effect of the clays increased. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 87–92, 1998     

Cocontinuous phase morphology of asymmetric compositions of polypropylene/high‐density polyethylene blend by the addition of clay

A novel method of developing cocontinuous morphology in 75/25 and 80/20 w/w polypropylene/high density polyethylene (PP/HDPE) blends in the presence of small amount (0.5 phr) of organoclay has been reported. SEM study indicated a reduction in average domain sizes (D) of disperse HDPE when PP, HDPE, and the organoclay were melt‐blended simultaneously at 200°C. However, when the two‐sequential heating protocol was employed, (that is, the organoclay was first intercalated by HDPE chains at 150°C, followed by melt blending of PP at 200°C), very interestingly a cocontinuous morphology was found even for very asymmetric blend compositions. WAXD study revealed the intercalation of both PP and HDPE chains inside the clay galleries, when PP/HDPE and clay were melt‐mixed together at 200°C. However, when the two‐sequential heating protocol was used the organoclay platelets were selectively intercalated by the HDPE chains. Addition of SEPS in the blend decreased the D of HDPE domains in both the blending methods. Thus, the observed cocontinuous morphology in asymmetric composition of PP/HDPE blend in presence of clay is because of the barrier effect of the clay platelets in the HDPE phase that restrict the phase inversion into the domain/matrix morphology. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation of polypropylene–clay nanocomposites by the co‐intercalation of modified polypropylene and short‐chain amide molecules

The effect of short‐chain amide (AM) molecules on the intercalation of montmorillonite clay has been investigated by the melt blending of polypropylene (PP) with clay in the presence of AM molecules such as 13‐cis‐docosenamide (erucamide). Polypropylene–clay nanocomposites (PPCNs) were prepared by the co‐intercalation of maleic anhydride grafted polypropylene (PP–MA) and an AM compound. The resulting nanocomposite structures were characterized with X‐ray diffraction (XRD) and transmission electron microscopy, whereas the thermal characterization of the PPCNs was conducted by thermogravimetric analysis. XRD results showed that the AM molecules intercalated into clay galleries and increased the interlayer spacing, a result confirmed by surface energy (contact angle) and melt flow index measurements. This additive allowed the formation of an intercalated nanocomposite structure, but an exfoliated PPCN structure was also formed with the use of AM with a PP–MA‐based compatibilizer. A new preparation method for PPCNs was, therefore, developed by the co‐intercalation of AM and PP–MA; this resulted in a significantly improved degree of intercalation and dispersion. The enhanced thermal stability of PPCN, relative to pure PP, further demonstrated the improved clay dispersion in the nanocomposite structures prepared by this method. A possible mechanism for the co‐intercalation of AM and PP–MA into the clay galleries is proposed, based on hydrogen bonding between these additives and the silicate layers. Consideration is also given to possible chemical reactions and physical interactions in this rather complex system. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Study on dispersion and intercalation of organoclay in PP and PP‐g‐MA matrices

Understanding the complex mechanism of dispersion and intercalation of the clay tactoids can allow us to control the final morphology, homogeneity, and the macroscopic properties of clay nanocomposites. The objective of this work is a multiscale study of the dispersion state of PP/organoclay and PP‐g‐MA/organoclay composite. The microscopic investigation, WAXS diffractograms, rheological analysis, and mechanical properties were used to characterize the dispersion of organoclay in PP and PP‐g‐MA matrices during melt blending in two different shear rates. The morphological results show a system of aggregating intercalated clay particles which disperse by increasing mixing time with a strain‐controlled process and a very quick intercalation process in early mixing times for PP‐g‐MA/organoclay nanocomposite, while PP/organoclay samples only form microcomposites. The relative network modulus of these intercalated particles as a function of mixing time was obtained; and the tensile modulus of nanocomposite samples were compared with Halpin‐Tsai model prediction. POLYM. COMPOS., 2009. © 2009 Society of Plastics Engineers     

Effect of organoclay structure characteristics on properties of ternary PP‐EP/EVA/nanoclay blend systems

In this study, the effect on the degree of organoclay exfoliation in polypropylene‐ethylene (PP‐EP)/Ethylene vinyl acetate (EVA)/organoclay blend system was studied while varying organoclay structural characteristics. Cloisite 6A, Cloisite 15A, Cloisite 20A, Cloisite 25A, Cloisite 30B, Cloisite 93A, and Cloisite 10A were used because they have different type of modifier. Ternary PP‐EP/EVA/organoclay system was obtained with each type of clay and results were organized to analyze the effect of type of clay chemical modification (C20A, C15A, and C6A), steric effect caused by surfactant structure (C15A and C10A), length of substitute groups on the surfactant (C20 and C25A), and surfactant polarity (C30B and C93A). Samples were characterized by: wide angle X‐ray diffraction, scanning transmission electron microscopy (STEM), dynamic mechanical analysis, and capillary rheometry. Results showed that clay galleries can be saturated with chemical modifier complicating the polymer chain intercalation into the clay galleries. Some clay modifier substituent groups could cause certain steric effect promoting less exfoliated platelets structures. Finally, longer chains in the modifier substituent group can promote a better intercalated–exfoliated structure. Among all the studied organoclays, best results were obtained in the ternary system when using C20A, which modifier has two hydrogenated tallows. In this case, interlayer spacing was increased more noticeable after ternary system was formed. This was corroborated with the obtained increase in viscosity and the intercalated–exfoliated structure observed by STEM. POLYM. COMPOS., 35:2241–2250, 2014. © 2014 Society of Plastics Engineers     

Influence of polarity on the preferential intercalation behavior of clay in immiscible polypropylene/polystyrene blend

The immiscible polypropylene (PP)/polystyrene (PS) blend was prepared via melt compounding and the preferential intercalation behavior of clay was investigated by wide angle X‐ray diffraction (XRD) and transmission electron microscope (TEM). It was found that the clay platelets initially located in the PS phase in PP/PS/Clay composites and PS chains intercalated into the clay layers. However, all clay migrated from the PS phase to the modified PP phase after introducing polar maleic anhydride group (MAH) to PP chains. Interestingly, most of clay migrated from the modified PP phase to the modified PS phase again when PS matrix was modified with sulfonic group, and some enriched in the interphase region. The interaction energy density (B) of the blends was determined by combining the melting point variation with the ternary interaction model for heat of mixing. It was found that the value of B decreased with the introduction of polar group (MAH or sulfonic group), indicating that the polarization of PP and PS can enhance interaction between clay platelet and polymer component. Different interaction between clay platelet and polymer component leads to the preferential intercalation behavior. The higher polarity of the polymer generates higher interaction between clay and polymer component as well as results in stronger preferential intercalating ability. Moreover, the results of FTIR spectra after extraction of all samples gave additional explanation of the preferential intercalation behavior of clay in the immiscible PP/PS blends. On the basis of the results of the measurement mentioned above, a possible mechanism was proposed. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

The influence of layered compounds on the properties of starch/layered compound composites

Glycerol‐plasticized starch films were modified by addition of various layered compounds as fillers, two being of natural origin (kaolinite, a neutral mineral clay, and hectorite, a cationic exchanger mineral clay) and two synthetic (layered double hydroxide, LDH, an anionic exchanger, and brucite, having a neutral structure). The effects of the filler type and the plasticizer were analyzed by X‐ray diffraction, dynamic mechanical analysis and thermogravimetry. The storage modulus was higher for kaolinite > brucite > hectorite than for LDH starch composites. However, only the hectorite filler presented a shift of the interplanar basal distance to higher values, which represents the intercalation of glycerol molecules between the clay layers. The glycerol intercalation is minimized in plasticized–oxidized starch films where the oxidized starch chains are preferentially intercalated. Copyright © 2003 Society of Chemical Industry     

Effects of clay contents on the dynamic mechanical and rheological properties of polypropylene/MAH‐g‐POE/clay composites

A series of polypropylene/maleic anhydride grafted polypropylene octane elastomer (MAH‐g‐POE)/clay (PPMC) nanocomposites were prepared with a novel compatilizer MAH‐g‐POE and different contents of octadecyl amine modified montmorillonite, and the effects of clay contents on the dynamic mechanical and rheological properties of these PPMC composites were investigated. With clay content increasing, the characteristic X‐ray diffraction peak changed from one to two with intensity decreasing, indicating the decreasing concentration of the intercalated clay layers. The gradual decrease of crystallization temperature of PPMC composites with the increase of clay loading should be attributed to the preferred intercalation of MAH‐g‐POE molecules into clay interlayer during blending, which is also reflected by scanning electron microscopy observations. By evaluating the activation energy for the glass transition process of MAH‐g‐POE and polypropylene (PP) in the PPMC composites, it is found that clay intercalation could cause the restriction effect on the glass transition of both MAH‐g‐POE and PP, and this restriction effect appears stronger for PP and attained the highest degree at 5 wt % clay loading. The melt elasticity of PP could be improved apparently by the addition of MAH‐g‐POE, and 5 wt % clay loading is enough for further enhancing the elastic proportion of PP. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Polyolefin‐based nanocomposite: The effects of processing aids

PP/organoclay nanocomposites were prepared using different processing aids (EMCA and PPG), and their effects on the thermal and mechanical properties were evaluated by WAXD, TEM, SEM, DSC, and mechanical tests. This study helps to clarify the effects of processing aids on the organoclay surface and on the intercalation and exfoliation processes. Nanocomposites with elongated intercalated and partially exfoliated structures were obtained, mainly when C‐15A was used. The results for the mechanical properties showed that the processing aids increased the impact strength significantly (up to three times that of neat PP) but reduced the flexural modulus of PP nanocomposites. PPG, which is polar promoted wetting MMT surface, thus increasing its interlayer distance, mainly for PP/C‐20A nanocomposites. However, it reduced the interfacial adhesion between the clay and the matrix. Nanocomposites impact strength was improved, especially when the C‐15A organoclay was used, while were achieved better results with the C‐20A organoclay when EMCA was used. The larger the amount of processing aid added, the higher the impact strength, but the lower the flexural modulus of the nanocomposites. PPG caused debonding of the clay particles and increased the number of microvoids, generating more mechanisms to aid in the energy dissipation of the systems. EMCA promoted debonding of clay particles with the formation of fibrils, indicating stronger interactions between the clay and matrix. A slight nucleation effect for PP crystallization was observed, mainly when EMCA was used. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Thermal degradation of organic matter in the interlayer clay–organic complex: A TG-FTIR study on a montmorillonite/12-aminolauric acid system

The storage of natural organic matter within the interlayer space of layered silicate is an important type of clay–organic association in sediment. However, the role of the interlayer space of clay minerals in the thermal degradation of organics and the generation of hydrocarbons has not been well understood. In this study, an interlayer clay–organic complex was synthesized using montmorillonite (Mt) and 12-aminolauric acid (ALA). An Mt–ALA complex in which Mt and ALA were simply mixed was also prepared for comparison. Thermogravimetry coupled with Fourier transform infrared spectroscopy (TG-FTIR) was applied to monitor the thermal events and the corresponding products during the thermal degradation of the Mt–ALA complexes. In the absence of Mt, ALA decomposed at 467 °C via the cleavage of CC bonds, producing aliphatic hydrocarbon, N-containing compounds, and carboxylic acid. The decomposition temperatures of organic matter in the mixed Mt–ALA complex and the interlayer Mt–ALA complex decreased to 402 and 342 °C, respectively. The most characteristic products of the interlayer Mt–ALA complex were NH₃ and saturated hydrocarbons. The Brønsted acid sites in the interlayer space of Mt, arising from the dissociated interlayer water, initiated the deamination of ALA via the Hoffmann elimination pathway and significantly promoted the cracking of hydrocarbons via a carbonation mechanism. Lewis acid sites had little effect on the thermal degradation of ALA. This work indicated that the interlayer space of clay minerals provided the storage space for organic matter. Moreover, the active sites within the interlayer space strongly promoted the thermal degradation of organics.     

Crystal structure and orientation of uniaxially and biaxially oriented PLA and PP nanoclay composite films

Cast films of poly(lactic acid) (PLA) and polypropylene (PP) with 2.5 and 5 wt % organo modified nanoclay were prepared and then uniaxially and biaxially hot drawn at T = 90 and 155°C, respectively, using a biaxial stretcher. The orientation of PLA and PP crystal unit cells, alignment of clay platelets, as well as the extent of intercalation and exfoliation were studied using wide angle X‐ray diffraction (WAXD). The measurement of d‐spacing of the 001 plane (normal to platelets plane) of the clay tactoids indicated the intercalation of the silicate layers for the PLA nanocomposite films, whereas the PP nanofilled films showed only dispersion of the nanoparticles (i.e., neither intercalation nor exfoliation were observed). The intercalation level of the clay platelets in PLA was almost identical for the uniaxially and biaxially drawn films. Our finding showed that the crystallite unit cell alignments are appreciably dependent on uniaxial and biaxial stretching. Moreover, the incorporation of clay to some extent influenced the orientation of the crystal unit cell axes (a, b, and c) of the oriented films. The silicate layers revealed a much higher orientation into the flow direction in the uniaxially stretched films compared to the biaxially drawn samples. In addition, the orientation of the 001 plane of nanoclays was significantly greater in the PLA compared to the PP nanoclay composite films probably due to a better intercalation and stress transfer in the former. Morphological pictograms illustrating the effects of uniaxial and biaxial stretching on the clay orientation are proposed. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of hydroxy-aluminium species on the sorption and interlayering of albumin onto montmorillonite

Proteins interact with soluble OH–Al species or Al precipitation products forming organo-mineral complexes with different chemical and physico-chemical properties. We studied the effect of pH, cation saturating the clays, presence of OH–Al species and order of component (OH–Al species, albumin and montmorillonite) addition on the amounts of proteinic molecules adsorbed on montmorillonite and the possible interlayering of OH–Al–protein complexes. Albumin molecules were very well intercalated into the interlayers of Na-montmorillonites, but very poor or no intercalation was observed for Mg-saturated montmorillonite and for an Al(OH)_x-montmorillonite (chlorite-like) complex.We have found that the amount of albumin sorbed on the external and interlamellar spaces of montmorillonite in the presence of OH–Al species was influenced by the sequence of addition of albumin (Alb), OH–Al species (Al) and montmorillonite (Mt). Complexes were prepared by mixing: (i) Al+Mt before Alb; (ii) Al+Alb before Mt; and (iii) Alb+Mt before Al. When albumin was added to montmorillonite before OH–Al species (Alb+Mt before Al complexes) proteinic molecules were able to penetrate more easily into the interlayers of montmorillonite. On the contrary, when OH–Al species were initially added to the clay (Al+Mt before Alb complexes), they were previously interlayered and consequently prevented the intercalation of the proteinic molecules. Finally, when OH–Al species and proteins were added to the clay as a mixture (Al+Alb before Mt complexes), large OH–Al–protein polymers formed, which were only partially intercalated into the interlamellar spaces of the clay. In all the complexes, the amounts of proteinic molecules sorbed usually increased by increasing the pH.     

Synthesis and characterization of poly(propylene)/montmorillonite nanocomposites by simultaneous grafting‐intercalation

A novel process for the preparation of poly(propylene)/montmorillonite (PP/MMT) nanocomposites was developed via simultaneous solution grafting‐intercalation in the presence of a reactive ammonium cation that can be grafted onto poly(propylene). Partially introducing this reactive cation into long alkyl ammonium modified MMT interlayers can transfer a conventional microcomposite into intercalated/exfoliated nanocomposites, which was evidenced by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). The PP chains were tethered onto the clay surface through the bridge of the reactive ammonium cations, which can be characterized by FTIR. The bridged chemical bonding also results in a good interface adhesion between PP and MMT, as confirmed by SEM investigation. The enhanced thermal properties of PP/MMT nanocomposites were characterized by thermogravimetric analysis. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1018–1023, 2004     

Exfoliation of layered silicate facilitated by ring-opening reaction of cyclic oligomers in PET-clay nanocomposites

Ethylene terephthalate cyclic oligomers (ETCs) have been successfully polymerized to a high molecular weight poly(ethylene terephthalate) (PET) employing the advantages of the low viscosity of cyclic oligomers and lack of chemical emissions during polymerization. Using ring-opening polymerization of ETCs with organically modified montmorillonite (OMMT), we intend to ascertain the possibility of preparing high performance PET/clay nanocomposites. Due to the low molecular weight and viscosity, ETCs are successfully intercalated to the clay gallerys, what is evidenced by XRD showing a down-shift of basal plane peak of layered silicate along with TEM investigation. Subsequent ring-opening polymerization of ETCs in-between silicate layers yielded a PET matrix of high molecular weight along with high disruption of layered silicate structure and homogeneous dispersion of the latter in the matrix. Although co-existence of exfoliation and intercalation states of silicate layers after polymerization of ETCs rather than perfect exfoliation was observed, a dramatic increase in d-spacing along with fast polymerization presents us a great potential of cyclic oligomer process in producing a thermoplastic polymer-clay nanocomposites of extremely well-dispersed silicate nanoplatelets and the corresponding high performances.     

Morphology and mechanical properties of polypropylene/organoclay nanocomposites

Polypropylene (PP) nanocomposites were prepared by melt intercalation in an intermeshing corotating twin‐screw extruder. The effect of molecular weight of PP‐MA (maleic anhydride‐ modified polypropylene) on clay dispersion and mechanical properties of nanocomposites was investigated. After injection molding, the tensile properties and impact strength were measured. The best overall mechanical properties were found for composites containing PP‐MA having the highest molecular weight. The basal spacing of clay in the composites was measured by X‐ray diffraction (XRD). Nanoscale morphology of the samples was observed by transmission electron microscopy (TEM). The crystallization kinetics was measured by differential scanning calorimetry (DSC) and optical microscopy at a fixed crystallization temperature. Increasing the clay content in PP‐ MA330k/clay, a well‐dispersed two‐component system, caused the impact strength to decrease while the crystallization kinetics and the spherulite size remained almost the same. On the other hand, PP/PP‐MA330k/clay, an intercalated three‐component system containing some dispersed clay as well as the clay tactoids, showed a much smaller size of spherulites and a slight increase in impact strength with increasing the clay content. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1562–1570, 2002     

Intercalation behavior of hydroxylated dendritic polyesters in polymer clay nanocomposites prepared from aqueous solution

Second and fourth generations of hydroxylated dendritic polyesters based on 2,2-bis-methylopropionic acid (bis-MPA) with an ethoxylated pentaerytriol (PP50) core were combined with unmodified sodium montmorillonite clay (Na⁺MMT) in water to generate a broad range of polymer clay nanocomposite films from 0 to 100% wt/wt. X-ray diffraction (XRD) and transmission electron microscopy (TEM) were used to investigate intercalation states of the clay galleries. Intercalation was the dominant state in these nanocomposites. Significant exfoliation was only observed within 0–5% wt/wt of mineral composition range. It was shown that interlayer spacing changed within the composition range 5–95% wt/wt from 0.5 nm to up to 3.5 nm in a step-like fashion with 0.5 nm increments which corresponded to a flattened conformation of confined hyperbranched polymers (HBP). Second and fourth generations exhibited the same layer-by-layer intercalation of completely flattened HBPs. No dependence of interlayer spacings on generation number was found. XRD and TEM revealed the presence of mixed intercalated populations with interlayer spacings at multiples of 0.5 nm.     

Morphological aspects of injected polypropylene/clay nanocomposite materials

Polypropylene (PP) clay nanocomposites were injection‐molded using two different coupling agents based on maleic anhydride‐grafted PP (MA‐g‐PP) and two clay loadings. The morphological aspects of these materials were studied by depth profiling. Molecular chain and clay orientations were characterized using attenuated total reflectance‐infrared analysis and transmission electron microscopy (TEM). Both clay platelets and PP molecular chain orientations were found to decrease from the surface toward the core of the injection–molded specimens. Clay intercalation, characterized by both complementary X‐ray diffraction and TEM, was found to be significantly influenced by both the characteristics of the coupling agent used and the type of residual stresses generated at each layer across the thickness of the injection‐molded parts. The use of low‐molecular weight (M_w) MA‐g‐PP led to a uniform intercalation but with no further exfoliation. The use of higher molecular weight MA‐g‐PP led to a heterogeneous intercalation with some signs of exfoliation. The crystallization behavior of PP clay nanocomposites studied by differential scanning calorimetry showed an increase in the level of crystallinity from the surface to the core of the specimens; these results were also confirmed by scanning electron microscopy. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Nitrile rubber/organomontmorillonite nanocomposites produced by solution and melt compounding: Effect of the polarity of the quaternary ammonium intercalants

A comparative study of the development of nitrile rubber (NBR) based nanocomposites was performed; two organomontmorillonites (Cloisite 15A and Cloisite 30B) and two procedures for clay dispersion (melt blending and solution intercalation) were used. The nanocomposites were cured with a system based on dicumyl peroxide in the presence of m‐phenylenebismaleimide as a coagent for curing. The dispersion of the organoclay inside the NBR matrix was investigated with transmission electron microscopy and X‐ray diffraction. All the cured systems displayed a combination of intercalated, partially exfoliated clay platelets and confined, deintercalated clay; the degree of dispersion depended on the amount of clay, the type of intercalant, and the intercalation procedure. The highest amount of intercalated/exfoliated clay was obtained with a previous dispersion of the clay (Cloisite 30B) in an NBR solution. All the nanocomposites presented outstanding tensile strength and creep response, and this indicated a reinforcing effect of the layered silicates. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Turn‐on chemosensors for silver ions based on oligomers with diaza‐16‐crown 6‐ether receptors and aromatic fluorophore end groups

The reaction of N‐(2,4‐dinitrophenyl)pyridinium chloride ( 1 ), diaza‐18‐crown 6‐ether (DA18C6) and 2,5‐bis(aminophenyl)‐1,3,4‐oxadiazole ( 2 ) caused the opening of the pyridinium ring and yielded an ionic oligomer (oligomer‐1) comprising a 5‐DA18C6‐penta‐2,4‐dienylideneammonium chloride main chain and 2‐(4‐aminophenyl)‐5‐phenyl‐1,3,4‐oxadiazole or 2‐(4‐N‐phenylpyridinium)‐5‐phenyl‐1,3,4‐oxadiazole end groups. Accordingly, the reaction of 1 , DA18C6 and 2,7‐diaminofluorene ( 3 ) yielded oligomer‐2. The structures of oligomer‐1 and oligomer‐2 were determined by comparing their ¹H NMR spectra with those of model compounds, which were synthesized by the 1:1 reaction of 1 with 2 or 3 . Oligomer‐1 and oligomer‐2 exhibited weak bluish‐green photoluminescence (PL) before the inclusion of Ag⁺ in the DA18C6 receptor, after which they exhibited strong bluish‐green PL. These observations can be explained by the occurrence of photoinduced electron transfer in the oligomers. Copyright © 2011 Society of Chemical Industry