A multifunctional poly(aryl ether) with oligoaniline and fluorene pendants: Synthesis,electrochromic performance,and tunable fluorescent properties

A novel multifunctional poly(aryl ether) with both pendant oligoaniline and fluorene groups (PAE‐p‐OF) was synthesized by nucleophilic polycondensation and characterized by ¹H NMR, Fourier‐transform infrared spectra, and gel permeation chromatography. The polymer showed excellent solubility in common organic solvents and good thermal stability. Electrochemical and photophysical properties were also investigated using cyclic voltammetry, UV–vis, and fluorescence spectroscopies. The obtained PAE‐p‐OF exhibits satisfactory electrochromic properties with high contrast value, acceptable coloration efficiency, and moderate switching times. Moreover, the fluorescence intensity of PAE‐p‐OF was modulated by controlling oxidation degree of oligoaniline moiety, due to the energy migration occurring between oligoaniline and fluorene groups. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Novel electroactive poly(arylene ether sulfone) copolymers containing pendant oligoaniline groups: Synthesis and properties

We present a series of novel poly(arylene ether sulfone) copolymers containing pendant oligoaniline groups. A novel monomer containing oligoaniline, 2,6‐difluorobenzoyl aniline tetramer (DFAT), was synthesized by reaction of 2,6‐difluorobenzoyl chloride and parent aniline tetramer and incorporated into the aforementioned copolymers via direct copolymerization with 4,4′‐dichlorodiphenyl sulfone (DCDPS), and 4,4′‐isopropylidene diphenol (BPA) using N,N′‐dimethylacetamide as solvent. The structures of these copolymers were confirmed by FTIR, ¹H NMR, and GPC. Spectral analysis of the copolymers in different oxidation states was investigated via UV‐visible spectra. The copolymers exhibited outstanding thermal stability and good solubility in various organic solvents. Their electroactivity, explored with cyclic voltammetry, was found to increase as the content of oligoaniline in the polymer increased. The electric and dielectric properties of the copolymers were also studied in detail. The electrochromic performance of the copolymers was investigated by electrochromic photographs and transmittance spectra; the color of the copolymer thin films changes from grey (at 0.0 V), to green (at 0.4 V), to blue (at 0.6 V) and to pearl blue (at 1.0 V) and the maximum transmittance change (ΔT) at 700 nm is 42.6% (90.7% ? 48.1%). © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis, characterization and hydrolytic stability of poly (amic acid) ammonium salt

A series of new poly (amic acid) ammonium salt (PAAS) precursors were prepared by incorporating different amounts of triethylamine (TEA) into terpolymer polyamic acid (PAA), which was synthesized by pyromellitic dianhydride (PMDA), 4,4’-oxydianiline (ODA) and p-phenylenediamine (PDA) in dimethylacetamide (DMAc). Then, the PAAS films were made by casting their solutions onto glass plates followed by the evaporation of the solvent. The chemical structure of PAAS films was confirmed by ¹H NMR and FTIR spectroscopy. Mechanical properties, intrinsic viscosities and solubility of PAAS precursors were examined, respectively. It was found that the intrinsic viscosity of PAA solution obviously decreased with storage time during 30 days, while no distinct changes were observed in the intrinsic viscosity of the PAAS (the mole ratio of TEA/repeating unit of PAA = 2/1) solution after 90 days. The results suggested that hydrolytic stability of the PAAS films was significantly improved as compared with that of PAA film due to the polyelectrolyte structure of PAAS. Moreover, the thermal and mechanical properties of polyimide (PI) films prepared from PAAS precursors were also investigated, respectively.     

Synthesis and imidization of poly(amic methyl ester)s

The synthesis and characterization of a series of poly(amic methyl ester)s from five aromatic dianhydrides and a diamine, 4,4′-oxydianiline (ODA), are described. These poly(amic ester)s are obtained by the low-temperature polycondensation from dianhydrides derived diesterdiacyl chlorides and ODA in DMAc solution with the inherent viscosities in the 0.5–0.9 dL/g range. These precursors are readily soluble in aprotic solvents. A detailed thermal study of the imidization process is presented, based on dynamic and isothermal TGA measurements, FTIR spectroscopy, and dynamic mechanical analysis. © 1997 John Wiley & Sons, Inc.     

Miscibility behavior and reequilibration of binary poly(amic acid) mixtures

Five poly (amic acid) solutions based on PMDA-PDA, PMDA-ODA, PMDA-6F, ODPA-ODA, and 6FDA-ODA were prepared in N-methylpyrrolidone at a polymer concentration of ca. 10 wt %. From these five poly (amic acid) solutions, six different binary blends were prepared: PMDA-PDA/PMDA-ODA, PMDA-PDA/PMDA-6F, PMDA-ODA/6FDA-ODA, PMDA-ODA/ODPA-ODA, PMDA-PDA/ODPA-ODA, and PMDA-PDA/6FDA-ODA. These blends were then characterized with respect to miscibility in the ternary state (polyamic acid-1/polyamic acid-2/N-methylpyrrolidone), the condensed state (ca. 70 wt % polymer), and the fully imidized state. All blends except for PMDA-PDA/PMDA-6F yielded homogeneous mixtures in the ternary solution of 10 wt % polymer concentration. The PMDA-PDA/PMDA-6F mixture eventually became homogeneous after 10 days of mixing at room temperature. Upon solvent evaporation (condensed state) and full cure (imidized state) two blends incorporating ODPA-ODA as one of the components exhibited apparent miscibility as evidenced by optical microscopy. The remaining blends exhibited large-scale phase separation upon solvent evaporation with no significant differences in the overall morphology between the condensed and imidized state. However, as in the case of the PMDA-PDA/PMDA-6F ternary system, the morphology in the condensed and imidized state was strongly dependent on the mixing time of the precursor poly(amic acid) components; the phase-separated domain size decreased with increasing mixing time, eventually leading to complete miscibility. These results are discussed with respect to the proposed “polymer-monomer” reequilibration reaction as well as its implications with respect to the preparation of polyimide molecular composites.     

Synthesis and properties of poly(phenylacetylenes) having o-silylmethyl groups

Novel phenylacetylene (PA) monomers, which have o-silylmethyl groups of different bulkinesses, i.e., o-Me₃SiCH₂PA, o-Et₃SiCH₂PA, and o-t-BuMe₂Si-CH₂PA, polymerized with W and Mo catalysts in high yields. The MoCl₅-Ph₄Sn catalyst achieved the highest weight-average molecular weights (M _w 7 × 10⁵ ? 12 × 10⁵), and the M _w increased as the ortho-substitutent became bulkier (e.g., M_w of o-t-BuMe₂SiCH₂PA: 12 × 10⁵). These monomers polymerized in a living fashion by the MoOCl₄-n-Bu₄Sn-EtOH catalyst. The resulting polymers were soluble in common solvents such as toluene and chloroform. In the UV-visible spectra, a tendency was observed that absorption maxima shifted to longer wavelengths as the substituents became bulkier. Membranes of the polymers were fairly permeable to gases (e.g., oxygen permeability coefficients 30-80 barrers). Though o-(Me₃Si)₂CHPA also polymerized with W and Mo catalysts, the product polymer was partly insoluble in any solvent. © 1995 John Wiley & Sons, Inc.     

聚酰胺酸酯的合成及性能研究

围绕刚性主链、高尺寸稳定性聚酰亚胺的制备,对聚酰胺酸酯的合成及酰亚胺化特性进行了研究。将制得的均苯二乙酯二酰氯与醚二胺进行聚合得到聚酰胺酸酯并与传统的预聚体——聚酰胺酸进行比较,得出聚酰胺酸酯性能较好,而酰亚胺化的温度要求较高。共聚中分别与间苯二胺或对苯二胺和醚二胺进行共聚,讨论了不同的二胺在共聚中的影响。     

Synthesis of poly(oligoaniline)s with structures controlled over three different oxidation states

We synthesize poly(oligoaniline)s consisting of multiple oligoaniline units linked by alkane spacers with their structures and properties controlled over three different oxidation states. tert‐Butoxycarbonyl (t‐BOC)‐protected diamino‐oligoanilines are synthesized and polymerized with diisocyanatoalkanes to produce t‐BOC‐protected prepolymers. We obtain the unprotected poly(oligoaniline)s in leucoemeraldine base, emeraldine base, and emeraldine salt oxidation forms by using different deprotection conditions for each of them. Distinct routes to each oxidation form of poly(oligoaniline)s enable exploitation of the crystalline structure, electrochemical activity, or conductivity, which is expected from the oligoaniline‐based materials, as well as their excellent processability into thin films that arises from their polymeric nature. The results suggest that new functional materials based on poly(oligoaniline)s may be derived by developing efficient synthetic procedures to control the oxidation states, promising for creation of new nanostructured materials with electrochemical activities. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis and properties of poly(hydroxamic acid) from crosslinked poly(methacrylate)

Poly(hydroxamic acid) chelating ion-exchange resin was prepared from crosslinked poly(methacrylate) beads. The starting polymer was prepared by a suspension polymerization of methacrylate and divinyl benzene. Conversion of the ester groups into the hydroxamic acid was carried out by treatment with hydroxylamine in an alkaline solution. Hydroxamic acid capacity of the product was 2.71 mmol/g. The resin exhibited high affinity towards Fe(III) and Pb ions and its capacities for Fe(III), Pb, Cu, Ni and Co ions were pH dependent. The ability of the resin to carry out the separation of Fe(III)CuCo/Ni and PbNi ions is also reported.     

Synthesis and properties of poly(5-ethynyluridylic acid)

5-Ethynyluridine 5'-diphosphate has been synthesised from 5-ethynyluridine under carefully controlled conditions to prevent any reaction with the ethynyl group. The compound is a substrate for polynucleotide phosphorylase from Micrococcus luteus and has been polymerised to give poly(5-ethynyluridylic acid). The polymer has a stable secondary structure with a T_m of 76° accompanied by a 16% hyperchromicity in solutions of high ionic strength and forms a 1:1 complex with poly(A) with a T_m of 78°. Thus the presence of the ethynyl group in the pyrimidine ring causes the polymer to have and to form much more stable secondary structures than the corresponding unsubstituted polynucleotide poly(U).     

Synthesis and properties of a poly(diphenylacetylene) containing carbazolyl groups

1-(p-N-Carbazolylphenyl)-2-phenylacetylene (p-CzDPA) was polymerized by TaCl₅–co-catalyst systems (cocatalysts: n-Bu₁Sn, Et₃SiH, and 9BBN) to produce acetone-insoluble polymers in about 60-70% yields. Poly(p-CzDPA) was a yellowish-orange solid, most part of which was soluble in toluene, chloroform, etc., and its weight-average molecular weights were around 4×10⁵. This polymer formed a tough film by solution casting, and was thermally very stable (the onset temperature of weight loss in TGA in air 470°C). The oxygen per-meability coefficient of the polymer at 25°C was lower than two barrers. The present polymer showed photoconductivity and redox activity. © 1995 John Wiley & Sons, Inc.     

Structure evolution and properties in a rigid polyimide prepared from its flexible poly(amic acid) precursor

Soluble poly(p-phenylene biphenyltetracarboxamic acid) precursor was converted to the polyimide by thermal imidization at various conditions. The structure evolution being occurred during its thermal imidization over 25–400°C was investigated as a function of imidization temperature and time by X-ray scattering with synchrotron radiation sources of Pohang Accelerator Laboratory in Korea and with conventional radiation sources. In addition, properties in the polyimide films were investigated by dynamic mechanical thermal analysis, stress-strain analysis, prism coupling, and residual stress analysis.     

Synthesis and light emitting properties of polyacetylenes having pendent fluorene groups

Five novel fluorene‐containing polymers, poly[(9,9‐dimethylfluoren‐2‐yl)acetylene] ( PFA1 ), poly[(1‐pentyl‐2‐(9,9‐dimethylfluoren‐2‐yl)acetylene) ( PFA2 ), poly[1‐decyl‐2‐(9,9‐dimethylfluoren‐2‐yl)acetylene] ( PFA3 ), poly[1‐phenyl‐2‐(9,9‐dimethylfluoren‐2‐yl)acetylene] ( PFA4 ), and poly[1‐(3,4‐difluorophenyl)‐2‐(9,9‐dimethylfluoren‐2‐yl)acetylene] ( PFA5 ) were synthesized by the polymerization of the corresponding fluorene‐substituted acetylenic monomers ( M1–M5), using WCl₆, MoCl_5, and TaCl₅ as catalysts and n‐Bu₄Sn as a cocatalyst. The synthesized polymers were thermally stable and readily soluble in common organic solvents. The degradation temperatures for a 5% weight loss of the polymers were ∼352–503 °C under nitrogen. PFA1–PFA5 show emission peaks from 402 to 590 nm. Besides, their electroluminescent properties were studied in heterostructure light‐emitting diodes (LEDs), using PFA2–PFA5 as an emitting layer. The PFA5 device revealed an orange‐red emission peak at 602 nm with a maximum luminescence of 923 cd/m² at 8 V. A device with the ITO/PEDOT/ a mixture of PFA2 (98 wt %) and PFA5 (2 wt %)/Ca/Al showed near white emission. Its maximum luminance and current efficiency are 450 cd/m² at 15 V and 1.3 cd/A, respectively. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 519–531, 2006     

Synthesis and properties of aromatic poly(ester amide)s with pendant phosphorus groups

Two series of phosphorus‐containing aromatic poly(ester amide)s with inherent viscosities of 0.46–3.20 dL/g were prepared by low‐temperature solution polycondensation from 1,4‐bis(3‐aminobenzoyloxy)‐2‐(6‐oxido‐6H‐dibenz〈c,e〉〈1,2〉oxaphosphorin‐6‐yl)naphthalene and 1,4‐bis(4‐aminobenzoyloxy)‐2‐(6‐oxido‐6H‐dibenz〈c,e〉〈1,2〉oxaphosphorin‐6‐yl)naphthalene with various aromatic diacid chlorides. All the poly(ester amide)s were amorphous and readily soluble in many organic solvents, such as N,N‐dimethylformamide, N,N‐dimethylacetamide (DMAc), and N‐methyl‐2‐pyrrolidone (NMP). Transparent, tough, and flexible films of these polymers were cast from DMAc and NMP solutions. Their casting films had tensile strengths of 71–214 MPa, elongations to break of 5–10%, and initial moduli of 2.3–6.0 GPa. These poly(ester amide)s had glass‐transition temperatures of 209–239 °C (m‐series) and 222–267 °C (p‐series). The degradation temperatures at 10% weight loss in nitrogen for these polymers ranged from 462 to 489 °C, and the char yields at 800 °C were 55–63%. Most of the poly(ester amide)s also showed a high char yield of 35–45%, even at 800 °C under a flow of air. The limited oxygen indices of these poly(ester amide)s were 35–46. © 2002 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 459–470, 2002; DOI 10.1002/pola.10129     

Simple and easy recycling of poly(amic acid) gels through microwave irradiation

Poly(amic acid)s (PAAs), which are precursors of polyimides, often undergo gel formation during their synthesis or storage, and these insoluble gels have been discarded. In this work, we discovered that the gels could be converted to homogeneous PAA solutions by fast and simple microwave (MW) irradiation. The PAA gels were placed inside a domestic MW oven, and MW irradiation was carried out with 240 W for 2 min. The recycled PAA solutions afforded polyimide films, coatings, and powders. The polyimides prepared from the recycled PAA solutions exhibited higher glass transition temperatures (T_gs), decomposition temperatures, and char yields than comparison polyimides obtained from ordinary PAA solutions. Flexible free‐standing polyimide films were obtained by drop‐casting of the MW‐treated solutions and subsequent thermal imidization. Mechanical properties and dielectric constants were measured for the polyimide films and coatings, respectively. This new method has significant advantages for the environment, economy, and industry. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 981–987     

Synthesis and properties of poly(arylene ether)s bearing sulfonic acid groups on pendant phenyl rings

Two kinds of new aromatic poly(arylene ether)s containing sulfonic acid groups were synthesized. Polymer 1 composed of tetraphenylphenylene ether and perfluorobiphenylene units was sulfonated with chlorosulfonic acid. Sulfonation took place only at the para position of the pendant phenyl rings. The average degree of sulfonation per repeating unit (m) was controlled from 1 to 4. Sulfonated polymer 2 with m = 3 was soluble in methanol and dimethyl sulfoxide and swelled in water. Incorporating bis(3,5‐dimethylphenyl)sulfone moieties into the sulfonated polymer imparts less methanol affinity. Polymers 4 with 30–65 mol % tetrakis(sulfophenyl)phenylene ether units has high decomposition temperatures above 300 °C, hydrophilicity, and good hydrolytic stability. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3211–3217, 2001     

氨基酸酯-烷基醚混合取代聚膦腈的合成与表征

聚膦腈高聚物,因其良好的生物相容性而用作生物医用材料。若在其侧链引入对热(如烷氧基醚)或对pH值敏感和可生物降解的基团(如氨基酸酯),则可得到具有环境敏感性和可生物降解性能的高聚物,这些高聚物可望作为药物载体,用于药物的控制释放。     

Synthesis and energy-transfer properties of poly(amidoamine) dendrons modified with naphthyl and dansyl groups

Poly(amidoamine) dendrons of 1-3 generations with naphthyl groups at the periphery and a dansyl group at the focal point were synthesized and carefully characterized. Intramolecular energy-transfer properties of these flexible aliphatic-scaffold light-harvesting dendrons were investigated by UV-vis absorption and fluorescence spectroscopy. Efficient energy transfer from the naphthyl groups to the dansyl group occurred for both the first and the second generation dendrons (the energy-transfer efficiency was 94.3% and 76.9%, respectively), whereas the third generation dendron exhibited a low energy-transfer efficiency of 17.8%. The average donor-acceptor distances between the naphthyl and dansyl groups were calculated for different generation dendrons. Different degrees of the backfolding of dendritic branches were used to interpret the different donor-acceptor distances.     

Synthesis and properties of various poly(diarylacetylenes) containing siloxy and hydroxy groups

Diarylacetylene monomers ( 1b ? f) containing siloxy and either naphthyl, fluorenyl, or biphenyl groups were polymerized with TaCl₅–n‐Bu₄Sn catalyst, and 1b , 1c , and 1f provided high molecular weight polymers. Free‐standing membranes of polymers 2b , 2c , and 2f were fabricated by casting from toluene solution. Desilylation of these polymer membranes was carried out with trifluoroacetic acid to afford poly (diarylacetylenes) membranes having hydroxy groups ( 3b and 3c ). According to thermogravimetric analysis (TGA), both siloxy‐containing and hydroxy‐containing polymers exhibited high thermal stability, and the onset temperatures of weight loss in air were ～370 °C and ～430 °C, respectively. The CO₂ permeability coefficients of these membranes were in the range of 65–640 barrers. The points of 3b and 3c in the PCO₂ versus PCO₂/PCH₄ plot were located above Robeson's upper bound. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4487–4495, 2007     

Synthesis and properties of poly(aryl ether ether ketone) copolymers with pendant methyl groups

Polyether ether ketone and polyether ether ketone copolymers were prepared by the nucleophilic substitution reaction of 4,4′-difluorobenzophenone with hydroquinone and with varying mole proportions of hydroquinone and methyl hydroquinone using sulfolane solvent in the presence of anhydrous K₂CO₃. The polymers were characterised by different physico-chemical techniques. The crystallinity of the polymers was found to decrease with increase in concentration of the methyl hydroquinone units in the polymer. Thermogravimetric studies showed that all the polymers were stable upto 430 °C with a char yield above 49% at 900 °C in N₂ atmosphere. The glass transition temperature was found to increase and the crystalline melting temperature and activation energy were found to decrease with increase in concentration of the methyl hydroquinone units in the polymer.