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1.
A novel diamine 4,4′-(3-(tert-butyl)-4-aminophenoxy)diphenyl ether (4) was synthesized from 2-tert-butylaniline and 4,4′-oxydiphenol through iodination, acetyl protection, coupling reaction and deacetylation protection. Then some polyimides (PIs) were obtained by one-pot polycondensation of diamne 4 with several commercial aromatic dianhydrides respectively. They all exhibit enhanced solubility in organic solvents (such as NMP, DMF, THF and CHCl3 etc.) at room temperature. Their number-average molecular weights are in the range of (2.1–3.7)?×?104 g/mol with PDI from 2.25 to 2.74 by GPC. They can form transparent, tough and flexible films by solution-casting. The light transparency of them is higher than 90% in the visible light range from 400 nm to 760 nm and the cut-off wavelengths of UV–vis absorption are below 370 nm. They also display the outstanding thermal stability with the 5% weight loss temperature from 525 °C to 529 °C in nitrogen atmosphere. The glass transition temperatures (T g s) are higher than 264 °C by DSC. XRD results demonstrate that these PIs are amorphous polymers with the lower water absorption (<0.66%). In summary, the incorporation of tert-butyl groups and multiple phenoxy units into the rigid PI backbones can endow them excellent solubility and transparency with relatively high T g s.  相似文献   

2.
A series of alternate block copolymers of polyphenylene vinylenes that have 1,3-dioctyloxy phenylene in the center of kinked m-terphenyl group as one of the building blocks with either one of the aromatic groups, viz., 1,4-dioctyloxy benzene, 4,6-dioctyloxy benzene and 4,4′-dioctyloxy biphenyl, was synthesized through Heck polymerization. These alternate block copolymers, viz., poly(2,5-bis(octyloxy)phenylene vinylene alt 4′,6′-bis(octyloxy)-1,1′:3′,1″-terphenylene) (P1), poly(2,4-bis(octyloxy)phenylene vinylene alt 4′,6′-bis(octyloxy)-1,1′:3′,1″-terphenylene) (P2) and poly(4,4′-bis(octyloxy-3,3′-biphenylene vinylene alt 4′,6′-bis(octyloxy)-1,1′:3′,1″-terphenylene) (P3), were characterized for their thermal and optical properties. The synthesized polymers had good solubility in organic solvents and were stable up to 350 °C. The molecular weights of the synthesized polymers were in the range 4370–10,900 Da with polydispersity range 1.52–1.65, which were measured by the gel permeation chromatography technique. The optical properties of these polymers showed absorptions in solution at around 400, 329, and 345 nm for P1, P2, and P3 polymers, respectively. The photoluminescence emission maxima of the polymers were at around 461 nm with a shoulder 439 and 424 nm for P1, P2, and P3, respectively. Photoluminescence emission of films of these polymers showed minimum redshift (20 nm) when compared with spectra of their solutions. The optical and photoluminescence emission properties of these polymers were found to vary on the backbone structure.  相似文献   

3.
Three d 10 coordination polymers formulated as [Zn(L1)2(mip)] n (1), [Zn(L1)(2,6-ndc)] n (2) and [Cd(L2)0.5(bpdc)] n (3) (L1 = 1,1′-(1,3-propanediyl)bis(thiabendazole), L2 = 1,1′-(1,6-hexanediyl)bis(thiabendazole), H2mip = 5-methylisophthalic acid, 2,6-H2ndc = 2,6-naphthalenedicarboxylic acid, H2bpdc = 4,4′-biphenyldicarboxylic acid) were hydrothermally synthesized. Complexes 13 were characterized by elemental analysis, IR spectroscopy, X-ray powder diffraction analysis, and single crystal X-ray diffraction. Complexes 1 and 2 present different chain structures, both of them are extended into 2D supramolecular architectures via C–H···O hydrogen bonds, while 3 is a three-fold interpenetrating three-dimensional framework with binodal 4,4-connected mog topology. The thermal stability, UV–visible spectroscopy and luminescence properties of complexes 13 were also examined. Furthermore, complex 3 exhibits relatively positive catalytic activity towards the degradation of methyl orange in a Fenton-like process.  相似文献   

4.
Novel bioengineering copolymers were synthesized by radical copolymerization of N-isopropylacrylamide (NIPA) and 3,4-2H-dihydropyran (DHP) with 2,2′-azobisisobutyronitrile as an initiator in acetone solution at 70 °C under nitrogen atmosphere. Structure, tacticity and compositons of the copolymers prepared in a wide range of monomer feed were confirmed by FTIR, 1H{13C} NMR-DEPT and elemental analyses. The monomer reactivity ratios (r 1 and r 2) were detected using known two methods: r 1 (NIPA)?=?1.25 and r 2?=?0.035 (DHP), and r 1 (NIPA) ?=?0.97 and r 2?=?0.022 (DHP) by Kelen-Tüdös and Jaacks methods, respectively. It was demonstrated that the studied monomer pair has a tendency to form H-bonding beween amide/ether groups through ?NH...O< complexation which played an important role in the stereoselective chain growth, and significant decrease of allyl degradative chain transfer reactions. This phenomenon is also confirmed by the observed relatively high molecular weights of copolymers (M v ). The synthesized water-soluble stimuli-responsive poly(NIPA-co-DHP)s exhibit thermal stability, higher glass-transition temperature, polyelectrolyte, pH- and temperature-sensitive behavior and can be attributed to the class of bioengineering functional copolymers useful for various bio- and gene-engineering, and drug delivery applications.  相似文献   

5.
A series of thermally stable poly(arylene ether ketone)s (PAEKs) bearing benzimidazole structure in the main chains, named poly(arylene ether ketone‐benzimidazole)s (PAEK‐BIs), were directly synthesized by polycondensation of dimethyl bisphenol, dibenzimidazole bisphenol, and difluorobenzophenones. By systematically varying the amount ratio of two kind of bisphenols, the content of benzimidazole moiety in the backbone was controlled straightforwardly. The prepared amorphous polymers were characterized in terms of Fourier transform infrared spectroscopy, proton nuclear magnetic resonance, thermal, dielectric, and gas transport properties. Evaluation of solubility reveals that PAEK‐BIs with >60% content of benzimidazole units could be soluble in commonly used organic solvents. Also polymers containing content‐tunable benzimidazole show high glass‐transition temperatures (Tg's, 157–319°C) and excellent thermal stability (e.g., temperature of 5% weight loss, above 438°C in air). Dielectric constants of PAEK‐BIs measured at 25°C are all less than 2.66 in the frequency range of 0.1–50 kHz. For dense films, the ideal gas selectivity and permeability coefficients could be compared with that of commercial Ultem 1000 membrane, which indicate that the PAEK‐BIs are potential to be used for gas separation membrane material. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41289.  相似文献   

6.
Hydroxyl terminated polylactide polymers with number of average molecular weights (M n ) varying from 1625 to 3459 g mol?1 were synthesized by ring opening bulk polymerization of lactide in the presence of zinc acetate being a potent catalyst. The use of 1,4 butanediol (BDO) initiator leads to hydroxyl terminated polylactides, thus excellent precursors for shape-memory biodegradable polyurethanes. Different reaction conditions employed for the synthesis of hydroxyl terminated polylactide polymers via activated monomer mechanism may result in differences in M n , percentage mass conversion and percentage degree of crystallinity (%χ c ) of the product. Influence of process parameters, i.e. catalyst concentration, initiator concentration, reaction temperature and time on characteristics of hydroxyl terminated polylactides was studied. These polymers were characterized by Nuclear Magnetic Resonance (1H-NMR) spectroscopy, Fourier transforms infrared (FTIR) spectroscopy, gel permeation chromatography (GPC) and X-ray diffraction (XRD) techniques. FTIR and 1H-NMR confirmed the formation of hydroxyl terminated polylactides. M n was determined by 1H-NMR, GPC and end group analysis. %χ c was calculated from XRD spectra. Maximum mass conversion, M n and %χ c were observed at 5 mol% SnOct2 and 5 mol% BDO concentration. At optimum temperature of 145 °C, these characteristics improved linearly with polymerization time up to 6 h and declined thereafter.  相似文献   

7.
It has been found that the temperature dependence of the intensity of the polarized V v and depolarized H v components of light scattering by a boron oxide melt in the range of 300–450°C is characterized by the existence of hysteresis: the specific feature of the change in the polarized V v component is the formation of a minimum, while the specific feature in the behavior of the depolarized H v component is associated with the appearance of a maximum in the sample heating mode; the cooling mode is accompanied by a monotonic change in the intensity of the light-scattering components. It has been found also that in the process of a low-temperature stabilization of the melt at 300°C, the polarized V v component after reaching its minimum values increases up to the initial level, while the depolarized H v component after passing its maximum decreases to the values smaller than the initial one. The characteristic time of the change in the intensity of the V v component at 300°C is determined; its value was found to be ~100 min. It has been shown that an insignificant change in the melt synthesis conditions affects the detected features of the intensity change in the range of 300–450°C.  相似文献   

8.
A new monomer containing sulfone and imide linkages, bis{4-[4-(p-phenoxyphenylsulfonylphenoxy)benzoyl]-1,2-benzenedioyl}-N,N,N′,N′-4,4′-diaminodiphenyl ether (BPSPBDADPE), was prepared by the Friedel–Crafts reaction of bis(4-chloroformyl-1,2-benzenedioyl)-N,N,N′,N′-4,4′-diaminodiphenyl ether with 4,4′-diphenoxydiphenyl sulfone. Novel copolymers of poly(ether ketone ketone) and poly(ether ketone sulfone imide) were synthesized by electrophilic Friedel–Crafts solution copolycondensation of terephthaloyl chloride with a mixture of DPE and BPSPBDADPE. The polymers were characterized by different physico-chemical techniques. The polymers with 10–25?mol% BPSPBDADPE are semicrystalline and had increased T gs over commercially available PEEK and PEKK (70/30) due to the incorporation of sulfone and imide linkages in the main chains. The polymer IV with 25?mol% BPSPBDADPE had not only high T g of 194?°C but also moderate T m of 338?°C, having good potential for melt processing and exhibited high thermal stability and good resistance to common organic solvents.  相似文献   

9.
A series of new fluorinated aromatic poly(ether imide)s (PEIs) were prepared from highly contorted 2,2′-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride and various trifluoromethyl-containing bis(ether amine)s via chemical or thermal imidization. All the PEIs showed good solubility in a variety of organic solvents and could afford flexible, colorless, and transparent thin films via solution-casting. They showed cut-off wavelengths of Uv-vis absorptions below 380 nm and very low yellowness index (b* < 7.0). They also showed high thermal stability with the 10% weight loss temperature from 503 to 585 °C of in nitrogen or air atmosphere. The glass transition temperatures (T gs) are recorded in the range of 194–254 °C by DSC. For a comparative study, another series of non-fluorinated PEIs derived from the same biphenyl-2,2′-diol bis(ether anhydride) with various bis(ether amine)s without the trifluoromethyl substituents were also synthesized and characterized.  相似文献   

10.
A cathode material for lithium-ion batteries–LiNi1/3Co1/3Mn1/3O2–was prepared by solution combustion synthesis and characterized by XRD, SEM, and galvanostatic charge/discharge cycling. The sample calcined at 950°C for 10 h showed best charge/discharge performance. An initial discharge capacity (C) of 150.5 mA h g–1 retained 95.7% of its value after 75 charge/discharge cycles at Ic = 14 mA g–1 (0.2C rate), Id = 70 mA g–1 (0.5C rate).  相似文献   

11.
Three supramolecular coordination polymers, namely [Ni(L1)(DCTP)(H2O)] n (1), [Cu(L2)(DCTP)] n (2), [Co(L3)(DCTP)] n (3) (L1?=?1,5-bis(5,6-dimethylbenzimidazole)pentane, L2?=?1,4-bis(5,6-dimethylbenzimidazole)butane, L3?=?1,4-bis(benzimidazole)-2-butylene) have been hydrothermally synthesized and characterized by single crystal X-ray structure determination, FT-IR, elemental analysis, X-ray powder diffraction (XPD), and thermogravimetric analysis (TGA). CP 1 exhibits 2D 63 honeycombed network structure, which is further extended into a 3D Moganite (mog) supramolecular framework by classical O–H?O hydrogen-bonding interaction. CPs 2 –3 present 2D (4,4) layers, and 3D supramolecular frameworks that are formed by ππ stacking interactions. Furthermore, the catalytic activities of CPs 1–3 for the degradation of methyl orange in a Fenton-like process has been investigated, and CPs 1–3 show strong photoluminescence properties at room temperature in solid state.  相似文献   

12.
Anhydrous ammonium pentaborate NH4B5O8 has been synthesized by thermal dehydration of larderellite NH4[B5O7(OH)2] · H2O at a temperature of 290°C for 7 h. The crystal structure has been determined from the X-ray powder diffraction data: a = 7.58667(5) Å, b = 12.00354(8) Å, c = 14.71199(8) Å, R p = 6.23, R wp = 7.98, R B = 12.7, R F = 8.95, and β-KB5O8 structure type. The double interpenetrating framework is formed by pentaborate groups, each consisting of a boron-oxygen tetrahedron and four triangles, in which all oxygen atoms are bridging. The thermal behavior of the NH4B5O8 compound has been investigated using thermal X-ray diffraction. As for other pentaborates of this type, the thermal expansion of the NH4B5O8 compound is anisotropic and reaches a maximum along the a axis. The thermal expansion coefficients are as follows: α a = 39 × 10?6, α b = 6 × 10?6, α c = 20 × 10?6, and α V = 65 × 10?6 °C?1.  相似文献   

13.
Dianhydrogossypol (4,4′-dihydroxy-5,5′-diisopropyl-7,7′-dimethyl-bis(3H-naphtho[1,8-bc]furan-3-one)) was made by refluxing gossypol in m-xylene. Proton NMR spectroscopy was used to confirm that complete conversion was achieved over a time period of several hours. Single crystals of the compound were obtained by slow evaporation from dichloromethane. Diffraction studies indicate that this crystal form is tetragonal with a I41/a space group and with cell dimensions of a = b = 33.8265(4) Å, c = 9.1497(2) Å, V = 10469.4(3) Å3 at 100 K. The structure was solved by direct methods and was refined to an R1 value of 0.0415 on 6,408 independent reflections. Dianhydrogossypol exists as a pair of enantiomers within this structure. The two fused planar ring systems are oriented at a 117° angle to each other (i.e., close to perpendicular), and the isopropyl groups are oriented with the ternary carbon hydrogen atoms pointed inward toward the center of the molecule. Repeating groups of four molecules (of the same chirality) pack to form a helical structure that is supported by intermolecular hydrogen bonds. Each helix is surrounded by four neighboring helices that are composed of molecules of the opposite chirality. The helices form the walls of empty channels that are 5–6 Å wide. As has been found for some gossypol crystal forms, the open-channel structure of dianhydrogossypol might be useful for scavenging or carrying small molecules. Additional NMR studies confirm that dianhydrogossypol can be converted directly to gossypol lactol ethers in the presence of anhydrous alcohols.  相似文献   

14.
The density d at a temperature of 25°C is measured by the hydrostatic weighing method, the Vickers microhardness H V is determined, and the fluctuation free volume fraction f g is calculated for glasses in the SrO-B2O3-SiO2 system with a constant strontium oxide content in the range from 35 to 45 mol %. It is demonstrated that the quantities H V and f g decrease and the density d increases with an increase in the SrO content.  相似文献   

15.
Ryan Selhorst  Eric Fossum 《Polymer》2013,54(2):530-535
A series of poly(arylene ether)s carrying a pendant diethyl sulfonamide group was prepared by the meta activated nucleophilic aromatic substitution reaction of a new aryl difluoride monomer, N,N-diethyl-3,5-difluorobenzene sulfonamide. The synthesis of N,N-diethyl-3,5-difluorobenzene sulfonamide was achieved via the one-step reaction of diethyl amine with commercially available 3,5-difluorobenzenesulfonyl chloride. Model reactions and NMR data indicated that the fluoride atoms were sufficiently activated by the sulfonamide group, located in the meta position, to provide access to high molecular weight poly(arylene ether)s. The corresponding poly(arylene ether)s, were prepared by reaction of N,N-diethyl-3,5-difluorobenzene sulfonamide with bisphenol A, bisphenol AF, 4,4′-biphenol, hydroquinone, resorcinol, and 4,4′-dihydroxydiphenyl ether. The polymers were characterized via NMR spectroscopy, size exclusion chromatography, thermogravimetric analysis, and differential scanning calorimetry. The sulfonamide based poly(arylene ether)s displayed moderate thermal stability with 5% weight loss temperatures ranging from 366 to 385 °C, but possessed relatively low glass transition temperatures, 72–142 °C.  相似文献   

16.
A comparative study of the oxidative destruction of the monomer face-centered cubic (FCC) lattice and various polymer [dimeric (D), orthorhombic (O), tetragonal (T), and rhombohedral (R)] phases of C60 in an atmosphere of oxygen has been performed in the temperature range of 100–500°C with the use of a flow microunit connected to a gas chromatograph. From direct measurements of the content of CO2 in the gaseous products of destruction, the temperature dependences of oxidation rates are measured for the materials under study. It has been established that, with respect to stability against oxidative destruction, different forms of C60 may be arranged as follows: the monomer FCC phase of C60 > D > O > T > R. The reasons behind this tendency are discussed.  相似文献   

17.
Two d10 metal-organic coordination polymers, [Cd2(4-cpa)4(bmip)2]n (1) and [Zn(4-cpa)2(4,4′-bpy)]n (2), [4-cpa = 4-chlorophenylacetate, bmip = 1,3-bis(2-methylimidazoly)propane, 4,4′-bpy = 4,4′-bipyridine], were hydrothermally synthesized and characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis (TGA), powder X-ray diffraction and single-crystal X-ray diffraction. Single-crystal X-ray diffraction studies indicated that both 1 and 2 display analogous wave-like infinite chain structures. The two coordination polymers are further extended into 3D supramolecular structures through π···π stacking interactions and C–H···O hydrogen bonds for 1 and π···π stacking interactions, C–H···π stacking interactions and C–H···O hydrogen bonds for 2. Both 1 and 2 emit the intense blue luminescence at room temperature. The 4-Hcpa ligand and complexes 1 and 2 have been screened for their herbicidal activities against Brassica napus L. and Echinochloa crusgalli L. The results are compared with the activity of quizalofop-P-ethyl. Both compounds exhibit high catalytic properties on degradation of methyl orange in Fenton-like process.  相似文献   

18.
Two Zn(II) coordination polymers, formulated as {[Zn(L1)0.5(btc)0.5(H2O)]·H2O} n (1) and {[Zn(L2)(1,4-ndc)]·2H2O} n (2) [L1 = 1,4-bis(2-methylbenzimidazole-1-ylmethyl)benzene, L2 = 1,4-bis(2-methylbenzimidazole)butane, H4btc = butane-1,2,3,4-tetracarboxylic acid, 1,4-H2ndc = 1,4-naphthalenedicarboxylic acid] have been synthesized and structurally characterized by single crystal X-ray diffraction. Complex 1 features a 3D (3,4)-connected network with the topology of fsh-3,4-P21/c. Complex 2 is a 2D (4,4) grid with sql topology and further extends into a 3D supramolecular framework by ππ stacking interactions. In addition, the thermal stability, fluorescence, and catalytic properties of two complexes for degrading methyl orange dye in a Fenton-like process were investigated.  相似文献   

19.
A new biphenol, 3‐pentadecyl 4,4′‐biphenol, was synthesized starting from 3‐pentadecylphenol and was polycondensed with 4,4′‐difluorobenzophenone, 1,3‐bis(4‐fluorobenzoyl)benzene and bis(4‐fluorophenyl)sulfone to obtain poly(arylene ether)s with biphenylene linkages in the backbone and pendent pentadecyl chains. Inherent viscosities and number‐average molecular weights (Mn) of the poly(arylene ether)s were in the range 0.50 ? 0.81 dL g?1 and 2.2 × 104 ? 8.3 × 104, respectively. Detailed NMR spectroscopic studies of the poly(arylene ether)s indicated the presence of constitutional isomerism which existed because of the non‐symmetrical structure of 3‐pentadecyl 4,4′‐biphenol. The poly(arylene ether)s readily dissolved in common organic solvents such as dichloromethane, chloroform and tetrahydrofuran and could be cast into tough, transparent and flexible films from their chloroform solutions. The poly(arylene ether)s exhibited Tg values in the range 35–60 °C which are lower than that of reference poly(arylene ether)s without pentadecyl chains. The 10% decomposition temperatures (T10) of the poly(arylene ether)s were in the range 410–455 °C indicating their good thermal stability. A gas permeation study of poly(ether sulfone) containing pendent pentadecyl chains revealed a moderate increase in permeability for helium, hydrogen and oxygen. However, there was a large increase in permeability for carbon dioxide which could be attributed to the internal plasticization effect of pendent pentadecyl chains. © 2016 Society of Chemical Industry  相似文献   

20.
A series of well-defined novel amphiphilic temperature-responsive graft copolymers containing PCL analogues P(αClεCL-co-εCL) as the hydrophobic backbone, and the hydrophilic side-chain PEG analogues P(MEO2MA-co-OEGMA), designated as P(αClεCL-co-εCL)-g-P(MEO2MA-co-OEGMA) have been prepared via a combination of ring-opening polymerization (ROP) and atom transfer radical polymerization (ATRP). The composition and structure of these copolymers were characterized by 1H NMR and GPC analyses. The self-assembly behaviors of these amphiphilic graft copolymers were investigated by UV transmittance, a fluorescence probe method, dynamic light scattering (DLS) and transmission electron microscopy (TEM) analyses. The results showed that the graft copolymers exhibited the good solubility in water, and was given the low critical temperature (LCST) at 35(±1) °C, which closed to human physiological temperature. The critical micelle concentrations (CMC) of P(αClεCL-co-εCL)-g-P(MEO2MA-co-OEGMA) in aqueous solution were investigated to be 2.0 × 10?3, 9.1 × 10?4 and 1.5 × 10?3 mg·mL?1, respectively. The copolymer could self-assemble into sphere-like aggregates in aqueous solution with diverse sizes when changing the environmental temperature. The vial inversion test demonstrated that the graft copolymers could trigger the sol-gel transition which also depended on the temperature.  相似文献   

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