Temperature-induced nucleation of poly(p-phenylene vinylene-co-2,5-dioctyloxy-m-phenylene vinylene) crystallization by HiPco single-walled carbon nanotubes

Hybrid systems of the conjugated organic polymer poly(p-phenylene vinylene-co-2,5-dioctyloxy-m-phenylene vinylene)(PmPV) and HiPco single-walled carbon nanotubes (SWNTs) are explored using spectroscopic and thermal techniques to determine specific interactions. Vibrational spectroscopy indicates a weak interaction, and this is further elucidated using differential scanning calorimetry (DSC), confocal laser scanning microscopy, temperature-dependent Raman spectroscopy, and temperature-dependent infrared spectroscopy of the raw materials and the composite. An endothermic transition is observed in the DSC of both the polymer and the 0.1% HiPco composite in the region of 50 degrees C. Also observed in the DSC of the composite is a double-peaked endotherm at -39 and -49 degrees C, which does not appear in the polymer. The Raman spectroscopy of the polymer upon increasing the temperature to 60 degrees C shows a diminished cis-vinylene mode at 1575 cm(-1), with an increase in relative intensity of the trans-vinylene mode at 1630 cm(-1). Partially irreversible change in isomerization suggests increased order in the polymer. This change in the polymer is also manifest in the Raman composite spectrum upon increase of the temperature to 60 degrees C, where the spectrum becomes abruptly dominated by nanotubes. Raman spectroscopy of the composite shows no change at -35 degrees C; however, infrared absorption measurements suggest that the transition at -35 degrees C derives from the polymer side chains. Here the composite at -35 degrees C shows a change in the absorbance of the polymer side chain aryl-oxide linkage at 1250 cm(-1) and alkyl-oxide stretch at 1050 cm(-1). Infrared spectra thus suggest that the transitions in the lower temperature region around -35 degrees C are side chain-induced, while Raman spectra suggest that the transition at 60 degrees C is backbone-induced. Furthermore, temperature cycling induces an irreversible decrease in the mean fluorescence intensity of the polymer, coupled with a further reduction in the mean fluorescence intensity of the composite. This suggests that an increase in crystallization of the composite is supported and enhanced by an increase in ordering of the polymer. Implications are discussed.     

Interactions of 2,5- and 3,5-dimethylphenols with co-exchanged montmorillonite

The influence of different steric and electronic properties of 2,5- and 3,5-dimethylphenols (2,5 and 3,5-DMP) on the type of interactions with Cobalt-exchanged montmorillonite (Co-MMT) was studied. The results of X-ray diffraction (XRD), IR-spectroscopy and thermal (TG, DTG) analysis show that phenol derivatives are intercalated into the interlayer space of montmorillonite. Thermal decomposition in the temperature interval 20–700 °C of Co-MMT with 3,5-DMP proceeds in four steps while Co-MMT with 2,5-DMP decompose only in three steps. These differences are connected with different acid–base interactions of individual phenol derivatives in the interlayer space of montmorillonite, which is in agreement with the results of IR-spectroscopy.     

Laser pyrolysis micro-spectroscopy for modelling fire-induced degradation of ethylene-vinyl acetate systems

A recently developed laser pyrolysis (LP)-Raman/ATR micro-spectroscopic method was applied for analyzing the degradation of polymer systems. The concept behind the method is to combine the micro-scale modelling of fire circumstances with analytical monitoring of the chemical changes in the solid phase of the sample. Samples were irradiated with the infrared beam of a CO₂ laser. The chemical changes were determined by micro-Raman/ATR spectroscopy methods in 200 ms intervals. The applicability of the method is demonstrated here through the pyrolysis of EVA and EVA composites containing metal-modified clays. Rapid depth profiling of few milligrams of sample is feasible with Raman detection, while the ATR sensor is applicable for analysis of fluorescent samples such as Fe coated sepiolite. The acceleration effect of montmorillonite and sepiolite minerals on the degradation of EVA is more pronounced if their surface is coated with Fe atoms. The effects of laser and the cone heater on the ratio of characteristic Raman bands of the polymer are compared and found to be in good correlation.     

Solid-state NMR spectroscopy as a tool supporting optimization of MALDI-TOF MS analysis of polylactides

We report systematic structural studies of poly(l-lactide) (PLLA) employing matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) and solid-state NMR spectroscopy. (13)C cross polarization magic angle spinning (CP/MAS) NMR data for 1,8-dihydroxy-9-anthracenone (DT), 2,5-dihydroxybenzoic acid (DHB), 2-(4-hydroxyphenylazo)-benzoic acid (HABA), and trans-3-indoleacrylic acid (IAA), four matrices commonly used in MALDI-TOF analysis of polymers, were analyzed to test the influence of crystallization conditions (solvent, inorganic salt) on sample morphology. (13)C principal elements of chemical shift tensor (CST) and line-shape analyses were employed to study of the nature of hydrogen bonding and to evaluate the crystallinity and amorphicity of the pure polymer. NMR parameters for PLLA were compared with data for polylactide crystallized with the four matrices under different conditions with the addition of two inorganic salts as cationization agents. This study revealed that the semicrystalline structure of the polymer does not change when it is embedded in the matrix.     

含噁二唑单元共轭聚合物合成与性质研究

单体 2 ,5 双 (4 溴苯 ) 1,3,4 二唑 (M Ⅰ )与 1,4 二乙烯基 2 ,5 二正丁氧基苯 (M Ⅱ ) ,在钯催化下通过Heck偶合反应合成得到共轭聚合物 ;单体和聚合物进行了1 H NMR ,1 3C NMR、质谱、FT IR、UV、荧光光谱、GPC、元素分析、热分析等测试 ;二唑 (OXD)基团是一种很好的生色团 ,对氧和热特别稳定 ,二唑环的亲电子性能使其特别适合于作为电子传输层 ,聚合物能发射很强的绿色荧光 ,它将是一类潜在的光电高分子材料     

Molecular mechanics of photopolymerization of 2,5-distyrylpyrazine in solid state

The molecular mechanics of photopolymerization of 2,5-distyrylpyrazine in the solid-state α form is investigated by a combination of Raman and electronic spectroscopic techniques. A stepwise photoreaction is used to stabilize an intermediate oligomer structure. For this purpose, the 476.5-nm argon-ion laser line is used to convert the monomer to the oligomer. The Raman phonon spectra reveal a homogeneous mechanism, with considerable lattice rearrangement, for the oligomerization process, which is also found to produce lattice strain. Further photoreaction of the oligomer is carried out with light of wavelength ≤400 nm from a 200-W mercuryxenon lamp as well as with the 355- and 417-nm laser lines from a Nd: Yag laser system. The Raman phonon spectra, monitored during the conversion of the oligomer to the polymer, show that initially the process starts homogeneously, with considerable lattice rearrangment. Then it turns heterogeneous, with a phase separation accompanied by a gradual ordering of the polymer product lattice. The electronic absorption spectra of the monomer are characterized and related to the stepwise photo process discussed above. Although the emission spectra show a monotonic change during the photoreaction, energy transfer from the oligomer to the monomer and from the polymer to the oligomer obscures and quantitative characterization by emission spectroscopy.     

导电高聚物聚2，5－二甲基苯胺的化学合成与特性

报道了聚２，５－二甲基苯胺（ＰＤＭｅＡｎ）的化学合成，并用标准四探针方法测定其电导率，以ＦＴＩＲ、ＵＶ－Ｖｉｓ吸收光谱、元素分析和ＣＶ法对其性质进行了研究，ＰＤＭｅＡｎ的结构与聚苯胺和聚２，５－二甲氧基苯胺的结构类似，是由其单元通过氮原子（Ｎ）在对位上键合而成，本征态的ＰＤＭｅＡｎ能溶于多种有机溶剂，如ＣＨ２Ｃｌ２、ＣＨＣｌ３、ＤＭＳＯ、ＤＭＦ等。     

Interfacial effects in organophilic montmorillonite–poly(ϵ‐caprolactone) nanocomposites

In the last few years much progress has been made in the development of hybrid polymer–inorganic filler nanocomposites. Nevertheless, many questions remain. The comprehension of the structure and the interactions at the polymer–nanofiller interface are crucial to foresee and control the properties of nanocomposites. Because of the high surface ratio of the inorganic nanofiller, the interface is expected to have a prevailing role in determining the nanocomposite properties. In this study we use X‐ray photoelectron spectroscopy (XPS) as a tool for the surface characterization of an organophilic montmorillonite/poly(ε‐caprolactone) exfoliated nanocomposite. The XPS core levels of the nanocomposite have been compared with those obtained from its precursors, and analyzed as reference compounds to evaluate eventual differences attributable to the polymer–nanofiller interfacial interactions. The XPS investigation has allowed us to propose a qualitative model of possible interface interactions between poly(ε‐caprolactone) and the organo‐modified montmorillonite. The model is substantiated by Fourier transform infrared spectroscopy (FTIR). © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3907–3919, 2004     

Laser desorption/fourier transform mass spectra of poly(phenylene sulfide), polyaniline,poly(vinyl phenol), polypyrene,and related oligomers: Evidence for carbon clusters and feasibility of physical dimension measurement

Laser desorption/Fourier transform mass spectra of poly(phenylene sulfide), polyaniline, poly(vinyl phenol), polypyrene, poly(p-phenylene), poly(1-methyl-2,5-pyrrolylene), poly(1-phenyl-2,5-pyrrolylene), and poly(2,5-thienylene) are compared. Poly(phenylene sulfide) fragments at C? S bonds during analysis, but rearrangement is minor. Evidence is found for dibenzothiophene moieties within the polymer chains. Unambiguous determination of the structure of polyaniline is not possible. Rearrangement appears to accompany chain scission. Completely aromatic polymers do not undergo similar reactions during analysis. Species with more carbons than can be accounted for by an integer multiple of six-membered rings arise from side reactions during dehydrocoupling of aromatic monomers. Carbon clusters, which are observed in the spectra of some aromatic polymers, appear to arise from laser volatilization and multiphoton ionization of large polynuclear components that are formed during synthesis. Negative ions of about 40–120 carbons and positive ions with about 120–400 atoms are detected. The results also suggest that the physical dimensions of some polymer molecules might be measured by Fourier transform mass spectrometry.     

新型共轭高分子聚[吡咯2,5-二(3-甲氧基-4-羟基苯甲烯)]的合成与表征

本文采用两步法合成了一种新型共轭高分子聚 [吡咯 2 ,5 二 (3 甲氧基 4 羟基苯甲烯 ) ],其前聚物聚 [吡咯 2 ,5 二 (3 甲氧基 4 羟基苯甲烷 ) ]可溶于一般的极性有机溶剂 .通过红外、核磁、紫外光谱分析鉴定了产物及其前聚物的结构 .利用DSC与TGA测试分析了所合成聚合物的热学性质 .紫外光谱表明在聚合物链中引入醌式吡咯环结构有利于降低产物的能隙 ,其能隙为 1 14eV ,属窄能隙类共轭聚合物 .经碘掺杂后产物的电导率在半导体的范围内     

Polymer-clay nanocomposites: chemical grafting of polystyrene onto Cloisite 20A

An account of the experiments on preparing polystyrene(PS) nanocomposites through grafting the polymer onto organophilic montmorillonite is reported.Cloisite 20A was reacted with vinyltrichlorosilane to replace the edge hydroxyl groups of the clay with a vinyl moiety.Because the reaction may liberate HC1,it was performed in the presence of sodium hydrogencarbonate to prevent the exchange of quaternary alkylammonium cations with H~+ ions.Only the silanol groups on the edge of the clay react with vinyltrichlorosilane.The radical polymerization of the product with styrene as a vinyl monomer leads to chemical grafting of PS onto the montmorillonite surface.The homopolymer formed during polymerization was separated from the grafted organoclay by Soxhlet extraction.Chemical grafting of the polymer onto Cloisite 20A was confirmed by infrared spectroscopy.The prepared nanocomposite materials and the grafted nano-particles were studied by XRD.Exfoliated nanocomposites may be obtained for 0.5 wt%-l wt%clay content.The nanocomposites were studied by thermogravimertic analysis(TGA) dynamic thermal analysis(DTA) and dynamic mechanical analysis (DMTA).     

Alkyl-substituted poly(2,5-benzophenone)s synthesized via Ni(0)-catalyzed coupling of aromatic dichlorides and their miscible blends

High molecular weight poly(2,5-benzophenone) derivatives were prepared by Ni(0)-catalyzed coupling of 4′-substituted 2,5-dichlorobenzophenones. Monomers were synthesized by the Friedel–Crafts reaction of 2,5-dichlorobenzoyl chloride and alkyl-substituted benzenes in the presence of aluminum chloride. The resulting polymers are soluble and show no evidence of crystallinity by DSC. Number average molecular weights are in the range of 9.2 × 10³–11.7 × 10³ g/mol by multiple angle laser light scattering (MALLS). Molecular weights obtained by MALLS are only slightly lower (∼90%) than those obtained by GPC (polystyrene standards). These polymers exhibit high thermal stability with glass transition temperatures ranging from 173 to 225°C and weight loss occurring above 450°C in nitrogen and 430°C in air. Additionally, the polymers were blended and the resulting polymer films appear to be miscible by DSC results. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2611–2618, 1998     

Synthesis and characterization of novel renewable polyesters based on 2,5‐furandicarboxylic acid and 2,3‐butanediol

Novel polyesters from 2,5‐furandicarboxylic acid or 2,5‐dimethyl‐furandicarboxylate and 2,3‐butanediol have been synthesized via bulk polycondensation catalyzed by titanium (IV) n‐butoxide, tin (IV) ethylhexanoate, or zirconium (IV) butoxide. The polymers were analyzed by size exclusion chromatography, nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy (FTIR), matrix‐assisted laser ionization‐desorption time‐of‐flight mass spectrometry, electrospray ionization time‐of‐flight mass spectrometry, electrospray ionization quadruple time‐of‐flight mass spectroscopy, thermogravimetric analysis, and differential scanning calorimetry. Fully bio‐based polyesters with number average molecular weights ranging from 2 to 7 kg/mol were obtained which can be suitable for coating applications. The analysis of their thermal properties proved that these polyesters are thermally stable up to 270–300 °C, whereas their glass transition temperature (T_g) values were found between 70 and 110 °C. Furthermore, a material was prepared with a molecular weight of 13 kg/mol, with a T_g of 113 °C. This high T_g would make this material possibly suitable for hot‐fill applications. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Studies on structure property relationship in a polymer–clay nanocomposite film based on (PAN)8LiClO4

A new combination of ionically conducting polymer–clay nanocomposites based on (PAN)₈LiClO₄ + x wt % montmorillonite (unmodified) clay has been prepared using the standard solution cast process. X-Ray diffraction (XRD) analysis reveals strong interaction of polymer salt complex (PS) with the montmorillonite matrix evidenced by changes in d₀₀₁ spacing of the clay and enhancement in the clay gallery width on composite formation possibly due to intercalation of polymer–salt complex into nanometric clay galleries. Evidences of such an interaction among polymer–ion–clay components of the composite matrix has also been observed in the Fourier transform infrared (FTIR) spectrum results. FTIR results clearly indicated cation (Li⁺) coordination at nitrile (CN) site of the polymer backbone along with appearance of a shoulder suggesting strong evidence of polymer–ion interaction. Addition of clay into the PS matrix has been observed to affect ion–ion interaction resulting from ion dissociation effect at low clay loading in the PNC films. Complex impedance spectroscopy (CIS) analysis has provided a response comprising of a semicircular arc followed by a spike attributed respectively, to the bulk conduction and electrode polarization at the interfaces. Electrical transport appears to be predominantly ionic (t_ion = 0.99) with significant improvement in the electrical conductivity and thermal stability properties. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2577–2592, 2008     

Thermal stability of polypropylene-clay nanocomposites subjected to laser pulse heating

Polypropylene based nanocomposites filled with montmorillonite nanoclay prepared by twin screw extrusion have been studied for thermal stability at high heating rates. In contrast to traditional thermal stability and flammability studies of polymer nanocomposites using heating rates on the order of tens of degrees per minute, this study achieves heating rates that are six orders of magnitude higher. This was accomplished using laser pulse heating. The results show that the nanoclay increases thermal stability of the polymer, as measured by a decrease in the mass loss for a laser pulse at a given energy and intensity. Electron microscopy and various spectroscopic techniques show that a silicate-rich char layer may provide the mechanism for protection of the polymer and decreased degradation rates. The results of the study are compared to the typical results found in traditional thermal stability testing.     

基于2，3-萘-18-冠-6单元的共轭高分子对金属离子的荧光传感器

能发射蓝绿色荧光的共轭高分子由单体1,4-二溴-2,3-萘-18-冠-6(M-2)与1,4-二乙烯基-2,5-二丁氧基苯(M-3)通过Pd催化的Heck偶联反应合成制得。通过荧光和紫外-可见光谱探讨了高分子对金属离子的响应性质,其中Hg²⁺能使高分子荧光淬灭、吸收增强,但As^Ⅲ、Pb²⁺和K⁺对高分子的荧光光谱改变很小。结果表明以2,3-萘-18-冠-6作为荧光团和识别位点的共轭高分子可作为有效识别Hg²⁺的荧光化学传感器。     

New crystalline polymers: poly(2,5‐dialkyl‐1,4‐phenylene oxide)s

New heat‐reversibly crystalline poly‐(alkylated phenylene oxide)s are described. the oxidative polymerization of 2,5‐dimethylphenol catalyzed by (1,4,7‐triisopropyl‐1,4,7‐triazacyclononane) copper dichloride produced poly(2,5‐dimethyl‐1,4‐phenylene oxide), which showed heat‐reversible crystallinity with a high melting point at ca. 300°C, although the isomeric polymer, poly(2,6‐dimethyl‐1,4‐phenylene oxide), never recrystallizes once melted. The polymerization of 2,5‐diethylphenol and 2,5‐dipropylphenol gave the polymers consisting of 1,4‐phenylene oxide units; the latter polymer possessed heat‐reversible crystallinity, however, the former one did not.     

Application of thermal analysis methods for characterization of polymer/montmorillonite nanocomposites

Thermal analysis is a useful tool for investigating the properties of polymer/clay nanocomposites and mechanisms of improvement of thermal properties. This review work presents examples of applications of differential scanning calorimetry (DSC), modulated temperature differential scanning calorimetry (MT-DSC), dynamic mechanical thermal analysis (DMA), thermal mechanical analysis (TMA), thermogravimeric analysis (TG) and thermoanalytical methods i.e. TG coupled with Fourier transformation infrared spectroscopy (TG-FTIR) and mass spectroscopy (TG-MS) in characterization of nanocomposite materials. Complex behavior of different polymeric matrices upon modification with montmorillonite is briefly discussed.     

Functionalization of montmorillonite by acrylamide polymers containing side-chain ammonium cations

Stable polyacrylamide (polyAA)–montmorillonite adducts were prepared by two distinct processes: (1) free radical copolymerization of AA with alkaline clay previously treated with 2-(N-methyl-N,N-diethyl ammonium iodide)ethylacrylate (QD1) and (2) direct interactions of alkaline montmorillonite with various preformed copolymers of AA with QD1. The structure of the adducts as determined by Fourier transform infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry and X-ray diffraction was shown to consist of AA macromolecules inserted between lamellar layers whose spacing was larger than in the polymer-free clay. The polymer was strongly attached to the inorganic surfaces, probably due to cooperative formation of electrostatic bonding. The thermal stability of the organic polymers in the resulting complexes was substantially enhanced while the mobility of macromolecules decreased.     

Synthesis and cleavage of core‐labile poly(alkyl methacrylate) star polymers

Core‐cleavable star polymers were synthesized by the coupling of living anionic poly(alkyl methacrylate) arms with either dicumyl alcohol dimethacrylate (DCDMA) or 2,5‐dimethyl‐2,5‐hexanediol dimethacrylate (DHDMA). This synthetic methodology led to the formation of star polymers that exhibited high molecular weights and relatively narrow molecular weight distributions. The labile tertiary alkyl esters in the DCDMA and DHDMA star polymer cores were readily hydrolyzed under acidic conditions. High‐molecular‐weight star polymer cleavage led to well‐defined arm polymers with lower molecular weights. Hydrolysis was confirmed via ¹H NMR spectroscopy and gel permeation chromatography. Thermogravimetric analysis (TGA) of the star polymers demonstrated that the DCDMA and DHDMA star polymer cores also thermally degraded in the absence of acid catalysts at 185 and 220 °C, respectively, and the core‐cleavage temperatures were independent of the arm polymer composition. The difference in the core‐degradation temperatures was attributed to the increased reactivity of the DCDMA‐derived cores. TGA/mass spectrometry detected the evolution of the diene byproduct of the core degradation and confirmed the proposed degradation mechanism. The DCDMA monomer exhibited a higher degradation rate than DHDMA under identical reaction conditions because of the additional resonance stabilization of the liberated byproduct, which made it a more responsive cleavable coupling monomer than DHDMA. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3083–3093, 2003