New Poly(azomethine‐urethane)s including melamine derivatives in the main chain: Synthesis and thermal characterization

Up to date, only a few kinds of poly (azomethine‐urethane)s (PAMUs) derived from aromatic hydroxy compounds were obtained and studied with thermal degradation steps. Novel PAMUs were prepared using the hydroxy‐functionalized Schiff bases derived from melamine and toluene‐2,4‐diisocyanate. Schiff base prepolymers were synthesized by the condensation reaction of melamine with 4‐hydroxybenzaldehyde and 2‐hydroxy‐1‐naphtaldehyde. Characterization was made by UV–Vis, FTIR, NMR, and SEC techniques. Thermal characterizations of the novel PAMUs were carried out by TG‐DTA and DSC techniques. Thermal decomposition steps at various temperatures were also clarified and the physical changes of the synthesized PAMUs with exposing to the thermal degradation steps were displayed. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

树枝状聚（胺-酯）的功能化及其荧光性能研究

以乙二胺(EDA)、三羟甲基丙烷三丙烯酸酯(TMPTA)和苯甲醛(BZA)为原料,合成了聚(胺-酯)-苯甲醛树枝状大分子(PAE-BZA),产率为60.82%,色谱纯度为65.27%。用IR、1HNMR和13CNMR表征了它的结构;并测定了PAE-BZA的荧光性能;考察了不同浓度PAE-BZA、不同溶剂及n(Sn2+)/n(PAE-BZA)对其荧光性能的影响。结果表明,丙酮为溶剂时,0.5 mmol/L PAE-BZA荧光强度最强;以丙酮、甲醇、DMSO、DMF和乙醇等为溶剂,PAE-BZA在乙醇中的荧光强度最强。随着n(Sn2+)/n(PAE-BZA)增加,PAE-BZA的荧光强度先减弱后增强,且Sn2+与PAE-BZA络合顺序是由外围的N原子逐步向内部的N原子络合。     

Preparation of needle-like poly(azomethine) crystals by means of reaction-induced crystallization of oligomers

Needle-like poly(azomethine) crystals were successfully prepared by the polycondensation of 1,4-phenylenediamine and 1,4-terephthalaldehyde in liquid paraffin at 180 °C. The favorable polymerization concentration for the preparation of the well-defined needle-like crystals was 2.0×10⁻² mol l⁻¹. The average length and width of the needle-like crystals were 7.7 and 0.6 μm, respectively. These crystals possessed high crystallinity and good thermal stability. The extended polymer chains were aligned along the long axis of the needle-like crystal. The morphological observations indicated that the needle-like crystals were formed through the spiral growth of the oligomer lamellae caused by the screw dislocation.     

Synthesis and characterization of novel poly(arylenevinylene) derivative

The new poly(arylenevinylene) derivative composed naphthalene phenylene vinylene backbone was developed. The theoretical calculation showed that the model compound of the obtained polymer was highly distorted between the stryl and naphthalene units as well as between the backbone and fluorene side units. The polymer was synthesized by the palladium catalyzed Suzuki coupling reaction with 2,6‐(1′,2′‐ethylborate)‐1,5‐dihexyloxynaphtalene and 1,2‐bis(4′‐bromophenyl)‐1‐(9″,9″‐dihexyl‐3‐fluorenyl)ethene. The structure of the polymer was confirmed by ¹H NMR, IR, and elemental analysis. The weight–average molecular weight of the polymer is 29,800 with the polydispersity index of 1.87. The new polymer showed good thermal stability with high T_g of 195°C. The bright blue fluorescence (λ_max = 475 nm) was observed both in solution and film of new polymer with naphthalene phenylene vinylene backbone. Double layer LED devices with the configuration of ITO/PEDOT/polymer/LiF/Ca/Al showed a turn‐on voltage at around 4.5 V, the maximum luminance of 150 cd/m², and the maximum efficiency of 0.1 cd/A. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and physicochemical characterization of poly(azomethine)esters containing aliphatic/aromatic moieties: Electrical studies complemented by DFT calculation

A conducting poly(azomethine)ester was prepared by solution phase polycondensation of a preformed Schiff base, 4‐((4‐(4‐(4‐hydroxybenzlideneamino) phenoxy)phenylimino)methyl)phenol and isophthaloyl chloride (I). Different aliphatic/aromatic moieties were incorporated for examining their effect on the electronic properties of material. The resulting polymers (10^?4 to 25 S cm^?1) were doped with silver (10^?6 to 10^?2 S cm^?1) and blended with polyaniline (10^?1 to 13.4 S cm^?1) to enhance their electrical conductivity. Polymer/polyaniline blends had superior conductivity even at low polyaniline concentration relative to the silver‐doped chains. The data obtained experimentally were complemented by density function theory at the 6–31G/B3LYP level. The results showed that ΔE along with lowest unoccupied molecular orbital and highest occupied molecular orbital electron density accounts for the electrical properties. Spectroscopic (¹HNMR, FTIR) and elemental analysis were used for structural elucidation. Structure–property relation in term of WXRD, SEM‐EDX, atomic force microscope, LLS, and thermal behavior was studied. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40698.     

New cardo silylated poly(azomethine)s containing 9,9′‐diphenylfluorene units as materials with Brønsted acid‐dependent fluorescence

Aromatic poly(azomethine)s have been studied due to their attractive properties such as high thermal stability, semiconducting behavior and the ability to coordinate species with their imine units (C?N). In this paper, the synthesis and characterization of two novel silylated poly(azomethine)s containing cardo units are reported. These materials were highly soluble in organic solvents such as chloroform and m‐cresol and were thermally stable, and PAzMC1 exhibited a high glass transition temperature value (287 °C), while that for PAzMC2 was not observed. UV–visible spectrophotometry revealed absorption bands related to the aromatic backbone of both PAzMCs, 300–285 nm in tetrahydrofuran and 310–301 nm in dimethylsulfoxide, and bands attributed to the conjugated imine unit at around 350 nm. In order to investigate the phenomenon of the emission of fluorescence promoted by dopant agents with regard to potential optoelectronic applications, the materials were doped with H₂SO₄ and their optical and electrochemical properties investigated. Thus, the absorption band of the imine group was suppressed due to the nitrogen atoms being protonated. Fluorescence spectroscopy analysis developed in dilute solutions of polymers showed no emission from the undoped polymers, whereas the acid‐doped species emitted fluorescence in the UV and violet regions (322 nm). Cyclic voltammetry measurements were carried out and HOMO–LUMO energies were estimated. This study provides a starting point for the development of new poly(azomethine)s with doping‐dependent emission. © 2019 Society of Chemical Industry     

Complexation between poly(methacrylic acid) and poly(vinylpyrrolidone)

The complexation between poly(methacrylic acid) (PMAA) and poly(vinylpyrrolidone) (PVP) in aqueous phase was studied by various fluorescence techniques, including fluorescence anisotropy measurements, fluorescence probe studies, and nonradiation energy transfer. It was demonstrated that the complexation of PMAA with PVP occurs within a pH range of 1 to 5 and along with complexation, the conformation of PMAA changed from a hypercoiled to a loosely coiled form. The complex ratio between the two polymers is 2:1 (PMAA/PVP, in monomer unit). Salt effect studies showed that the complexation occurred due to formation of hydrogen bonds between the two polymers. Based on these conclusions and the “connected cluster model” for PMAA at low pH, a “ladder with connected cluster” model was proposed for the structure of PMAA/PVP complex formed at low pH. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 620–627, 2001     

Synthesis and characterization of fluorinated poly(azomethine ether)s from new core-fluorinated azomethine-containing monomers

In this work, we describe the design and synthesis of novel core-fluorinated Schiff base monomers and conjugated polymers based on them. The new fully aromatic highly fluorinated poly(azomethine ether)s (PAMEs) were prepared by polycondensation of core-fluorinated azomethine-containing compounds. The structure of the monomers and polymers were confirmed by FTIR, ¹H, ¹³C, and ¹⁹F NMR spectroscopic analysis. The influence of synthesis condition on the properties of PAME compounds was investigated. Application of polarization microscopy with a temperature control thermal stage revealed thermotropic liquid crystalline (LC) behavior in the synthesized materials. Transition temperatures and a range of the existence of the LC phase were studied by a combination of the optical microscopy and DSC analysis. According to the TGA analysis, all the synthesized PAMEs show high thermal stability and thus offer a wide range of thermal processibility (up to 410–477 °C), which makes them prospective materials for many modern applications.     

Synthesis and Characterization of Conductive Blends of Polyaniline with Poly(azomethine ester)s

Polyaniline (PANI) doped with HCl was blended with different poly(azomethine ester)s (10% by weight of PANI) and compressed into pellets. The blends were studied by Fourier Transform Infra-Red (FT-IR) and thermo gravimetric analysis (TGA). Electrical conductivities of the blends determined by four-point probe method, in the temperature range 32°C to 80°C, vary from 24.4 × 10^?3 to 3.15 × 10^?3 Scm^?1. The TGA measurements show that weight loss occurred below 80°C is only about 2%.     

Theoretical analysis on the geometries and electronic structures of coplanar conjugated poly(azomethine)s

In this study, theoretical analysis on the geometries and electronic properties of various conjugated poly(azomethine)s is reported. The theoretical ground-state geometry and electronic structure of the studied poly(azomethine)s are optimized by the hybrid density functional theory (DFT) method treated in periodic boundary conditions at the B3LYP level of theory with 6-31G basis set. The geometry and electronic structure of poly(1,4-phenylenemethylidyneitrilo-1,4-phenylene-nitrilomethylidyne) (PPI) are compared with those of poly(p-phenylene vinylene) (PPV) or polyazine (PAZ). The theoretical results suggest the non-coplanar conformation of PPI but PPV and PAZ with a coplanar conformation. The electronic properties of PPI are in the intermediate between PPV and PAZ. The non-coplanar conformation of PPI could be released if the phenylene ring is replaced by the five-member ring of 3,4-ethylenedioxythiophene (PEEI), pyrrole (PYYI), thiophene (PTTI), furan (PFFI), or thiadiazole (PThThI). The theoretical E_g of PEEI, PYYI, PFFI, and PTTI are in the range of 1.11-1.67 eV, which is due to the coplanar configuration or donor-acceptor intrachain charge transfer. However, the large bond length alternation or lack of charge transfer characteristic makes the PThThI with a larger E_g of 2.47 eV than others. The trend on the IP or EA of the studied conjugated poly(azomethine)s are consistent with the electronic characteristic of the aromatic ring. The upper valence bandwidth of the studied five-member ring based poly(azomethine)s except PThThI is in the range of 562-613 meV, which is larger than that of PPI (247 meV) or PPV (373 meV). The results suggest that the electronic properties of conjugated poly(azomethine)s could be varied through various ring structure. The proposed new coplanar conjugated poly(zomethine)s can be potentially used as transparent conductors or thin film transistors.     

Synthesis and characterization of thermotropic liquid crystalline poly(azomethine ether)s

Two series of monomers, namely 4,4′-diformyl-α,ω-diphenoxydecane and 4,4′-diformyl-3,3-methoxy-α,ω-diphenoxydecane, were prepared from 1,10-dibromodecane with p-hydroxybenzaldehyde and 4-hydroxy-3-methoxybenzaldehyde (vanillin), respectively. The poly(azomethine ether)s were prepared by solution polycondensation using 4,4′-diformyl-α,ω-diphenoxydecane, 4,4′-diformyl-3,3-methoxy-α,ω-diphenoxydecane with various diamines. The monomers and polymers were characterized by intrinsic viscosity, FT-IR, ¹H, and ¹³C NMR spectroscopy. The thermogravimetric analysis reveals that the polymers are stable up to 320-500 °C and decomposed with good char yield. The thermotropic liquid crystalline properties of the polymers were examined by differential scanning calorimetry (DSC) and their textures observed under hot stage optical polarized microscopy (HOPM). All the polymers were exhibited thermotropic liquid crystalline properties except tetramethylene diamines-based polymers.     

Manufacture of modified poly(vinyl acetal) showing fluorescence and molecular recognition

Poly(vinyl acetal) from poly(vinyl alcohol) and 4-dimethylaminobenzaldehyde (DMAB) is synthesized. Fluorescence behavior of the polymer is investigated in acetic acid glacial (HAc), dimethylsulfoxide (DMSO), and dimethylformamide (DMF) solvents. Fluorescence emission intensities of the polymer solutions are different with the change of concentration. The result suggests that the maximum fluorescence emission intensities of the polymer solutions depend on the optimal concentration of the polymer. It has been found that the fluorescence intensity of DMAB is dramatically lower than that of the polymer in the same chromophore concentration, and such phenomenon is termed as structural self-quenching effect (SSQE). The strong fluorescence of the polymer can be quenched by adding electron-deficient monomers which have no chromophore moieties such as lactic acid, adenine, etc., and their Stern–Volmer constants are determined. It is observed that the higher the electron deficiencies of the quenchers, the higher the Stern–Volmer constants, which means stronger quenching effect. The result indicates that the polymer can recognize these biologic small molecules. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2385–2390, 1999     

Investigation on the microstructure and the electric property of poly(propylene)/chlorinated poly(propylene)/poly(aniline) composites

The article presents results of studies on composites made from poly(propylene) (PP) modified with poly(aniline) (PANI) doped with dodecylbenzene sulfonic acid (DBSA) and chlorinated poly(propylene) (CPP). The volume resistivity of PP/CPP/PANI composites was detected, and the results show that the volume resistivity decreases with increasing CPP content, and there exists a minimum volume resistivity. Effects of CPP on the microstructure and crystalline structure of the PP/CPP/PANI composites and the relationship between the effects and the electric property were carefully analyzed by scanning electron microscope (SEM) and wide angle X‐ray diffraction (WAXD). The method that the specimens of SEM are polished is appropriate to investigate the morphology of conducting polymer composites. The obtained results illuminate that the area of conducting parts and insulating parts obtained from the digital analysis of the SEM image is obviously influenced by the CPP content, the parameters of the lamellar‐like structure are immediately related to CPP content and denote the dispersion of PANI‐DBSA, and the percent crystallinity and mean crystal size of PP are directly correlated with the CPP content. The increasing area of conducting parts, the increasement of layer distance, the decreasement of size and layer number of the lamellar‐like structure of PANI‐DBSA, and the increasement of the percent crystallinity and mean crystal size of PP are beneficial to the improvement of the conductive property of PP/CPP/PANI composites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

An inelastic electron tunnelling spectroscopy (IETS) study of poly(vinylacetate) poly(methyl methacrylate) and poly(vinylalcohol) adsorbed on aluminium oxide

IETS is used to investigate the adsorption of poly(vinylacetate) (PVA), poly(methylmethacrylate) (PMMA), and poly(vinylalcohol) (PVOH) on aluminium oxide. These polymers are of interest in the field of adhesion science, and until now synthetic macromolecules have not been studied in this way. Both commercially available polymers and those synthesized in our laboratory have been used. On the basis of IET spectra presented here, and existing i.r. spectra it is believed that PMMA and PVA undergo ester cleavage at the oxide surface leading to their subsequent adsorption. For PMMA this is thought to be via carboxylate anions generated on the polymer side groups, while PVA is expected to be adsorbed as PVOH. Bonding of PVOH to the oxide is not fully understood, but may occur by the formation of an AlOC bridge. Another possibility for the above polymers, that of intermolecular hydrogen bonding between polar polymer side groups, and adsorbed hydroxyl species present on the oxide surface, cannot be ruled out.     

Interpolymer complexes of poly(acrylamide) and poly(N-isopropylacrylamide) with poly(acrylic acid): a comparative study

The interpolymer complexation, through successive hydrogen bonding, between poly(acrylamide) (PAAm) and poly(N-isopropylacrylamide) (PNiPAAm) with poly(acrylic acid) (PAA) in aqueous solution has been viscometrically and potentiometrically investigated. The stoichiometry of the complexes formed was determined. By comparing the strength of the two complexes the very important contribution of the hydrophobic interaction in their formation has been indicated.     

新型聚三唑酯和聚三唑醚树脂的合成及性能

合成了三种含酯基和三种含醚键的炔单体,通过核磁共振氢谱(¹H NMR)、红外光谱(FT-IR)、质谱(MS)、液相色谱(LC)对其结构进行了表征。用这六种炔单体与叠氮单体反应制备了一系列新型聚三唑酯树脂(PTAE)和聚三唑醚树脂(PTAO)。利用差示扫描量热分析(DSC)、FT-IR、动态力学热分析(DMA)、力学试验机和热失重分析(TGA)表征了树脂的固化行为、固化树脂的力学性能、耐热性和热稳定性。结果表明PTAE和PTAO树脂易溶于有机溶剂,可低温(60℃)固化,固化树脂的弯曲强度超过了100 MPa,可达158 MPa,玻璃化转变温度(T _g)超过180℃,高者达251℃,热分解温度可达360℃。     

Blends of poly(ethylene terephthalate) and poly(butylene terephthalate)

Commercial grade poly(ethylene terephthalate), (PET, intrinsic viscosity = 0.80 dL/g) and poly(butylene terephthalate), (PBT, intrinsic viscosity = 1.00 dL/g) were melt blended over the entire composition range using a counterrotating twin‐screw extruder. The mechanical, thermal, electrical, and rheological properties of the blends were studied. All of the blends showed higher impact properties than that of PET or PBT. The 50:50 blend composition exhibited the highest impact value. Other mechanical properties also showed similar trends for blends of this composition. The addition of PBT increased the processability of PET. Differential scanning calorimetry data showed the presence of both phases. For all blends, only a single glass‐transition temperature was observed. The melting characteristics of one phase were influenced by the presence of the other. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 75–82, 2005     

Effect of tacticity of poly(methyl methacrylate) on the miscibility with poly(vinyl pyrrolidone)

Isotactic, atactic, and syndiotactic poly(methyl methacrylates) (PMMA) (designated iPMMA, aPMMA, and sPMMA) with approximately the same molecular weight were mixed separately with poly(vinyl pyrrolidone) (PVP) primarily in chloroform to make three polymer blend systems. Differential scanning calorimetry (DSC) was used to study the miscibility of these blends. The results showed that the tacticity of PMMA has a definite impact on its miscibility with PVP. The aPMMA/PVP and sPMMA/PVP blends were found to be miscible because all the prepared films showed composition-dependent glass-transition temperatures (T_g). The glass-transition temperatures of the aPMMA/PVP blends are equal to or lower than weight average and can be qualitatively described by the Gordon–Taylor equation. The glass-transition temperatures of the other miscible blends (i.e., sPMMA/PVP blends) are mostly higher than weight average and can be approximately fitted by the simplified Kwei equation. The iPMMA/PVP blends were found to be immiscible or partially miscible based on the observation of two glass-transition temperatures. The immiscibility is probably attributable to a stronger interaction among isotactic MMA segments because its ordination and molecular packing contribute to form a rigid domain. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3190–3197, 2001     

Thermal characteristics of poly(vinyl alcohol) and poly(vinylpyrrolidone) IPNs

Interpenetrating polymer network (IPN) hydrogels based on poly(vinyl alcohol) (PVA) and 1‐vinyl‐2‐pyrrolidone (VP) were prepared by radical polymerization using 2,2‐dimethyl‐2‐phenylacetophenone (DMPAP) and methylene bisacrylicamide (MBAAm) as initiator and crosslinker, respectively. The thermal characterization of the IPNs was investigated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and dielectric analysis (DEA). Depressions of the melting temperatures of PVA segments in IPNs were observed with increasing VP content via the DSC. The DEA was employed to ascertain the glass transition temperature (T_g) of IPNs. From the result of DEA, IPNs exhibited two T_gs indicating the presence of phase separation in the IPN. The thermal decomposition of IPNs was investigated using TGA and appeared at near 270°C. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1844–1847, 2002     

Biodegradable polymer blends of poly(lactic acid) and poly(ethylene glycol)

Poly(lactic acid) (PLA) and poly(ethylene glycol) (PEG) were melt-blended and extruded into films in the PLA/PEG ratios of 100/0, 90/10, 70/30, 50/50, and 30/70. It was concluded from the differential scanning calorimetry and dynamic mechanical analysis results that PLA/PEG blends range from miscible to partially miscible, depending on the concentration. Below 50% PEG content the PEG plasticized the PLA, yielding higher elongations and lower modulus values. Above 50% PEG content the blend morphology was driven by the increasing crystallinity of PEG, resulting in an increase in modulus and a corresponding decrease in elongation at break. The tensile strength was found to decrease in a linear fashion with increasing PEG content. Results obtained from enzymatic degradation show that the weight loss for all of the blends was significantly greater than that for the pure PLA. When the PEG content was 30% or lower, weight loss was found to be primarily due to enzymatic degradation of the PLA. Above 30% PEG content, the weight loss was found to be mainly due to the dissolution of PEG. During hydrolytic degradation, for PLA/PEG blends up to 30% PEG, weight loss occurs as a combination of degradation of PLA and dissolution of PEG. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1495–1505, 1997