最新刊期
卷 ， 期 6 ， 2012
- 摘要：Size exclusion chromatography (SEC) equipped with light scattering (LS) and refractive index (RI) detectors was employed to determine the compositions of complicated binary mixtures.The principle of absolute quantification of size exclusion chromatography was deduced for LS and RI detectors according to signals of both detectors and the injected mass.It is founded that the response factor of RI detector is only decided by the refractive index increment () of the injected sample,while the response factor of LS detector is determined by both and the weight average molar mass (Mw) of the sample.By a theoretical analysis we conclude that the response factors of both LS and RI detectors are linear functions with the composition of a binary polymer blend.Six pairs of binary mixtures with weak interactive effect were employed to test the linear relationship.The experimental results show an excellent accordance with the theory.At last,the linear relationships between the response factors and the composition was utilized for the compositional analysis of binary mixtures.With a careful analysis,it is discovered that the compositions determined by LS detector are more accurate than the ones by RI detector in some cases.For RI detector,seven error points are out of the range from -10% to 10%,while only two error points are out of this range for LS detector.Specially,four bad points for RI detector are much more than one point for LS detector for the case at the low composition W =10%.For another case in the mixture of two kinds of polystyrene,the number of bad points for RI detector reaches four in the five compositions while none yields for LS detector.This SEC-LS method is effective for the compositional analysis of binary mixtures and can be derived to more complicated industrial mixtures.关键词：Size exclusion chromatography;Light scattering;Refractive index;Composition of binary mixture;Absolute quantification
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发布时间：2021-03-19 - 摘要：The porcine pancreatic lipase (PPL) was used to replace the traditional catalysts to catalyze L -lactide (L -LA) graft copolymerization onto chitosan under single-mode microwave irradiation,in order to prepare chitosan-graft-poly(L-lactide) copolymers (CS-g-PLLA).The effects of reaction temperature and catalyst dosage on the reaction were investigated.The physical properties and cell affinity of the copolymer were further discussed by differential thermogravimetry (DTG),X-ray diffraction (XRD) and 3T3 fibroblast incubation,taking pure chitosan as references.The results showed that the grafting reaction could be carried out by PPL catalyzing under normal atmospheric pressure.The reaction temperature and amount of PPL influenced the grafting degree greatly.The copolymer with high grafting degree (178.8%) could be achieved at low reaction temperature (50℃) under single-mode microwave radiation.Compared with pure chitosan,the thermal stability and crystallinity of copolymers decreased because grafting PLLA would destroy the high crystallinity of chitosan.The copolymer offered an excellent substrate for cell adhesion and proliferation,demonstrating that it could be applied as scaffold material in tissue engineering.The above results proved that the enzyme might be an ideal catalyst to prepare derivates of polysaccharose for application in biomaterials.关键词：Graft copolymerization;Enzymatic polymerization;Microwave irradiation;Chitosan;Poly(L-lacitde)
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发布时间：2021-03-19 - 摘要：A novel pH-responsive and biodegradable triblock copolymer,poly(ethylene glycol)-poly(L-glutamic acid)-poly(L-Alanine acid) (PEG-PLGA-PLAA),was prepared by N -carboxyl anhydride ring-opening polymerization and acidic hydrolysis.It was found that this amphiphilic copolymer can self-assemble into micelles in aqueous solution.The PLAA,PLGA and mPEG segments serve as a hydrophobic core,a pH-responsive shell and a hydrophilic corona,respectively.The morphology and properties of the micelles such as pH sensitivity,zeta potential,secondary structure and mean diameter were investigated.Doxorubicin (DOX) was encapsulated into the micelles to explore the release profiles,which exhibited in vitro pH-dependence.In acidic environment,with the formation of -helix secondary structure of poly(L-glutamic acid) segments,the PLGA segments in the triblock copolymers shrank and relocated in the micelles to trigger the release of drugs.As a result,these DOX-loaded polymeric micelles showed rapid release of DOX from the micelles in weakly acidic environments (pH=5.5) but very slow release under physiological condition (pH=7.4).关键词：Poly(aspartic acid);Drug delivery;DOX;Micelle;pH-Responsive
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发布时间：2021-03-19 - 摘要：Fe3O4 magnetic nanoparticles with mean diameter of about 6 nm coated by PEG4000 were prepared by a precipitation method with ferric chloride and ferrous sulfate as starting materials and ammonia for alkalinizing,and the Fe3O4-PEG4000 magnetic nanoparticles obtained were further modified by citric acid through ultrasonic treatment.Afterwards,NH2 end group surface functionalized Fe3O4 magnetic nanoparticles Fe3O4@SiO2-NH2were prepared through Stober method using silane coupling agent.Further,positively charged ionic polyurethane (IPU) was grafted onto the surface of Fe3O4@SiO2 nanoparticles by polymerization of NH2 end group,presynthesized ionic diol,PEG200 and toluylene-2,4-diisocyanate (TDI).Finally,Fe3O4/CdTe/polyurethane (Fe3O4/CdTe/IPU) nanocomposites were prepared by electrostatic interaction of positively charged IPU and thioglycolic acid coated CdTe quantum dots(QDs).The structure of Fe3O4/CdTe/IPU nanocomposites was characterized and verified by XRD,FTIR,TGA,TEM,VSM,UV and PL analyses.It was found through XRD spectra that Fe3O4/CdTe/IPU nanocomposites were a mixture of cubic-structural Fe3O4 nanoparticles,amorphous SiO2 and cubic-structural CdTe QDs.According to the FTIR analyses,the chemical bonds of SiO2,IPU and Fe3O4 indicated that SiO2 and IPU were grafted onto the surface of Fe3O4 nanoparticles.The results of TGA indicated that the coating amount of IPU was about 40% (W/W).TEM analyses showed that the SiO2 coated Fe3O4 nanoparticles were well dispersed which had a relatively uniform diameter of about 20 nm,and the CdTe QDs were arranged around the magnetic nanoparticles.The hysteresis loops proved the superparamagnetic properties of the as-prepared magnetic nanoparticles and nanocomposites.The UV and PL spectra suggested the nanocomposites revealed the properties of the QDs,and the UV irradiation images showed that the QDs moved and aggregated with magnetic nanoparticles in the magnetic field.关键词：Anocomposites;Fe3O4;Polyurethane;Quantum dot;Magnetic
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发布时间：2021-03-19 - 摘要：A novel pyridine-containing aromatic diamine monomer,4-［4-phenyl］-2,6-bis［4-(2-aminophenoxy)phenyl］pyridine (p,o-PAPP) was successfully synthesized respectively by nucleophilic substitution reaction,modified Chichibabin reaction and catalytic reduction with hydrazine monohydrate,2-hydroxyacetophenone and benzaldehyde.The aromatic diamine was employed to prepare a series of pyridine-containing polyimides by polycondensation with various aromatic dianhydrides in N,N -dimethylformamide (DMF) via the conventional two-step method.The inherent viscosities of the resulting poly(amic acid)s (PAAs) and polyimides (PIs) were in the range of 0.59~0.73 and 0.52~0.63 dL/g,respectively.The structure and performance of polymers were characterized by FTIR,solubility testing,DSC,XRD,TGA,UV-Vis and fluorescence spectroscopy.The results showed that there were characteristic peaks of polyimide around 1780,1720 and 1380 cm-1 in the FTIR spectra.The obtained PIs exhibited high solubility in common organic solvents,such as m-cresol,DMF, N,N -dimethylacetamide (DMAc),dimethylsulfoxide (DMSO), N -methylpyrrolidone (NMP),tetrahydrofuran (THF) and chloroform (CHCl3).Meanwhile,flexible PI films were obtained,which had excellent thermal stability with the glass transition temperature (Tg) of 162.2~195.2℃ and the temperature at 10% weight loss of 444.2~467.5℃ in nitrogen atmosphere.The protonated polymer showed UV-Vis absorption in the region 200~360 nm and displayed strong fluorescence intensity (460 nm) in THF solution.关键词：Polyimide;Diamine;Fluorescence;Pyridine;Design
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发布时间：2021-03-19 - 摘要：Compatibilization between polyethylene (PE) and wood-flour was achieved by means of direct reactive extrusion of glycidyl methacrylate (GMA),PE,wood-flour and other additives.Impact cracking surfaces of the PE/wood-flour composites (WPCs) were observed via scanning electron microscope (SEM).Fourier transform infrared (FTIR) spectra of wood-flour extracted from the WPCs were measured.Heat distortion temperatures (HDTs) and mechanical properties of the WPCs were tested.The effect of comonomer styrene (St) and anti-crosslinking agent triphenyl phosphite (TPP) on the reactive compatibilization was also evaluated.Experimental results indicated that some of PE chains in the WPCs were bonded onto the surface of wood-flour after reactive extrusion resulting in the improvement of compatibility between PE and wood-flour.Both increased grafting ratio of GMA,and more bonded PE chains on the surface of wood-flour were evidenced due to the addition of St.However,the addition of TPP reduced the grafting ratio of GMA.Mechanical properties and HDTs of the WPCs were obviously improved after direct reactive extrusion.At 1.5 wt% of GMA and 0.3 wt% of DCP in the extrusion composition of WPC,the tensile strength,flexural strength,elongation at break,notched impact strength and HDT of WPC respectively increased by 67%,23%,32%,43% and 7.7 K comparing to those of the WPC without reactive extrusion.The addition of St was able to inhibit the cross linking reaction of PE,however,there was no significant changes observed for its mechanical properties and HDT.When both St and TPP were added in the WPC ,the composites HDT decreased while elongation at break and notched impact strength were improved.关键词：Polyethylene;Wood-flour;Composite;Glycidyl methacrylate;Styrene;Reactive compatibilization
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发布时间：2021-03-19 - 摘要：By means of encapsulation method,poly(vinyl alcohol) (PVA) dispersed liquid crystal films (PDLCs) have been prepared with 4-pentyl-4'-cyanobiphenyl (5CB) as a liquid crystal (LC) phase and N,N'-didodecyl-N,N,N',N',N- pentamethyl-1,4,7-triazaheptane diiodide as a Gemini surfactant.The effects of Gemini surfactant with a concentration slightly larger than its critical micelle concentration (CMC) on the microstructures and electro-optical properties of PDLCs have also been investigated.The addition of Gemini surfactant slightly enhances the compatibility between PVA and LC.The PDLC films still retain high degree of phase separation, i.e. ,0.85,in comparison with 0.92 for PDLCs without any surfactant.The LC phases are uniformly dispersed in PVA matrix,but the size of LC droplets decreases greatly from 2~30 m without surfactant to 2~5 m with the addition of Gemini surfactant.Moreover,the configuration of LC director changes to be radial from bipolar.Additionally,the addition of Gemini surfactant increases the contrast and the response speed of PDLCs,and retains a low driving voltage of 4.6 V.The transparency under zero voltage,switch-on time and switch-off time are 51.8%,18 ms and 14.2 ms for the PDLCs without surfactant,10.2%,1.5 ms and 10.5 ms for the PDLCs with Gemini surfactant,respectively.关键词：Polymer dispersed liquid crystal;Gemini surfactant;Microstructure;Electro-optical properties
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发布时间：2021-03-19 - 摘要：Narrow disperse or monodisperse poly(DVB-co-EGDMA-co-MAA) microspheres with carboxyl groups were prepared by free-radical precipitation polymerization in neat acetonitrile,using 2,2'-azobisisobutyronitrile (AIBN) as initiator,methylacrylic acid as functional monomer,and highly hydrophobic divinylbenzene-55 (DVB-55) and polarity ethylene glycol dimethacrylate (EGDMA) as mixed crosslinker.The results showed that the feed radio of DVB-55 to EGDMA determined the particle size,size distribution,yield,thermal stability and loading capacity of the functional groups.The particle size of microspheres was in the range of 0.6~3.8 m,and monodisperse microspheres could be obtained when the ratio of DVB-55 to EGDMA was no less than 1∶1. Thermogravimetric analysis showed good thermal stability,enhancing with the percentage of DVB-55 in the mixed crosslinker.Moreover,with increasing the amount of DVB-55 in the mixed crosslinker,the measured values of the loading capacity of the accessible carboxylicacid group on the surface of the microspheres decreased,as well as the yield of microspheres.It was confirmed that the composition of the cross-linking monomers affected the particle size,size distribution and yield of microspheres.The studies on the compatibility between the two cross-linkers showed that the core of the polymer beads would contain more DVB units slightly,while the outer layer would contain preferentially the more abundant cross-linker added in the pre-polymerization mixture.关键词：Precipitation polymerization;Microsphere;Divinylbenzene-55;Ethylene glycol dimethacrylate;Methylacrylic acid
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发布时间：2021-03-19 - 摘要：The present paper focuses on improving the water-holding ability of sulfonated poly(ether ether ketone) (SPEEK) (degree of sulfonation,DS = 55.1%) membranes.Functionalized silica (silica sol (SiO2) and silica powder with sulfonic acid groups (SiOx-S)) were chosen as the hygroscopic additive,respectively.SPEEK/SiO2、SPEEK/SiOx-S composite membranes were obtained by casting a homogeneous mixture of SiO2 (or SiOx-S) and SPEEK in N,N-dimethylacetamide onto glass plate and then evaporating the solvent at 60℃.The decrease in both the swelling degree and the methanol permeability and the improvement in the conductivity at a high temperature and a low humidity of the membranes were a dose-dependent result of addition of the SiO2 and SiOx-S powders.Pure SPEEK membranes swelled 52.6% at 80℃,whereas the SPEEK/SiO2 (15 wt%) and SPEEK/SiOx-S (15 wt%) membranes swelled only 26.2% and 27.3% at the same temperature,respectively.From room temperature to 80℃,SPEEK/SiO2 (20 wt%) and SPEEK/SiOx-S (20 wt%) membranes had methanol permeability of about two order of magnitude lower than that of Nafion 115.At 120℃ and 40% relative humidity (RH),the conductivity of pure SPEEK membranes is only 2.610-4 Scm-1,and that of SPEEK/SiO2 (20 wt%) membranes is about 2.010-3 Scm-1,while that of SPEEK/SiOx-S (20 wt%) composite membranes reaches 1.010-2 Scm-1,which is close to that of Nafion 115.DMFCs single cell performance of SPEEK/SiO2 (20 wt%) and SPEEK/SiOx-S (20 wt%) membranes was better than that of pure SPEEK membranes because they had good dimensional stability and no separation of catalyzers and membranes in membrane electrode assembles.关键词：Sulfonated poly(ether ether ketone);Composite membrane;Functionalized silica;Direct methanol fuel cell
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发布时间：2021-03-19 - 摘要：The functional core-shell poly(styrene-acrylamide) latex microspheres with different diameters were prepared by one-step emulsion polymerization method by adjusting the dosage of the initiator.The core-shell structures and the diameters of latex microspheres were characterized by transmission electron microscope.The diameters of the as-prepared microspheres were 195,217,234 and 255 nm,respectively.The chemical composition of the microspheres was characterized by IR spectra,which testified that the polystyrene was wrapped by polyacrylamide successfully.The photonic crystals films of the as-prepared core-shell microspheres were fabricated by vertical deposition self-assembly method.The morphology of the as-prepared photonic crystals films were characterized by scanning electron microscope.The photonic stopbands were measured by reflectance and transmittance spectra.The results demonstrate that the polymer microspheres are in a face-centered cubic arrangement with a close-packed plane (111) oriented parallel to the substrate,and the stopbands of the photonic crystals can be varied when the diameters of the microspheres are different.In this work,photonic crystals films with different stopbands were obtained,and the stopbands occurred at 473,515,574 and 630 nm,respectively.The corresponding colors of the films were blue,green,yellow and red,respectively.It is very important for the development and application of photonic crystals.关键词：Emulsion polymerization;Core-shell stucture;Polymer microspheres;Vertical deposition self-assembly;Photonic crystals
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发布时间：2021-03-19 - 摘要：In order to improve the biocompatibility of graphene oxide (GO) and enhance its application in preparing biomaterials,four-arm star polyethylene glycol (sPEG) was used to modify GO under the assistance of toluene-2,4-diisocyanate (TDI).Polyethylene glycol-modified graphene oxide (GO-TDI-sPEG) obtained by this facile method possesses high sPEG grafting density,which could be stably suspended in aqueous solutions.Fourier transform infrared spectroscopy (FTIR),Raman spectroscopy (Raman),X-ray diffraction (XRD),atomic force microscopy (AFM),transmission electron microscopy (TEM) and thermogravimetric analysis (TGA) were used to characterize the resultant material.The appearance of the characteristic absorptions at 2861 and 1093 cm-1 in FTIR spectrum,as well as the AFM and TEM micrographs indicated that sPEG was successfully grafted onto GO.No diffraction peak could be found in XRD figure of GO-TDI-sPEG,which indicated that the layers of GO-TDI-sPEG were fully exfoliated after modification.The TGA test results showed that the thermal stability of the modified GO had been greatly increased and the grafting degree of sPEG in GO-TDI-sPEG was about 12.1 wt%.关键词：Graphene oxide;Four-arm star polyethylene glycol;Toluene-2,4-diisocyanate;Covalent functionalization
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发布时间：2021-03-19 - 摘要：Nanocomposites composed of hydrogenated nitrile rubber/magnesium methacrylate/organic montmorillonite (HNBR/PMgMA/OMT) were prepared by in situ polymerization and mixing intercalation.The structure,morphology and properties of the nanocompostie were investigated by XRD,SEM,TEM,etc.The nano-micro coexistence structure was formed by PMgMA ion clusters and MgMA monomer.MgMA significantly enhanced the properties of HNBR composites.HNBR/PMgMA/OMT nanocomposites have favorable processing,mechanical properties and resistant aging properties in different media.TEM images revealed that MgMA can help OMT in exfoliating and dispersing,while the composition of MgMA/OMT facilitated the peeling and dispersion of OMT.OMT in the vulcanizates formed a microstructure mainly caused by exfoliation and intercalation,and also by the coexistence of de-intercalation and un-intercalation.SEM results indicated that the interface bonding can be significantly improved with a mixing ratio of MgMA/OMT as 20/10,therefore,the tensile strength,elongation at break and permanent deformation reached 30.2 MPa,520% and 30%,respectively; meanwhile,the hot air,oil and water resistant properties were also improved apparently.An aging coefficient of 0.61,0.63 and 0.84 was attained after aging at 165℃ in air,water and oil,respectively,for 14 days.And the resistant aging property of medium is higher than that of the HNBR composite reinforced by carbon black and MgMA,respectively.The improvement of aging resistance in different media is mainly due to the better dispersed layer structure of organic montmorillonite.关键词：Hydrogenated nitrile rubber;Magnesium methacrylate;Organic montmorillonite;Nanocomposite;Aging resistance
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发布时间：2021-03-19 - 摘要：A novel fluorescence resonance energy transfer (FRET)-based ratiometric sensor is reported for detecting Hg2+ in water.The polymeric nanoparticles were prepared by one-step polymerization of methyl methacrylate (MMA) and polyethyleneimine (PEI) using tert -butyl hydroperoxide (TBHP) as the initiator.For the nanoparticles,the hydrophilic polyethyleneimine (PEI) chain segments served as the shell and the hydrophobic copolymer of methyl methacrylate (MMA) and the cross-linker constituted the core of the nanoparticles.A hydrophobic fluorescent dye nitrobenzoxadiazolyl derivative (NBD) was embedded in the nanoparticles during the polymerization and used as the donor of the energy transfer process.A spirolactam rhodamine derivative SRHB was synthesized,and then introduced into the particles and used as an ion-recognition element.The presence of Hg2+ in the water dispersion of nanoparticles induced the ring-opening reaction of the spirolactam rhodamine moieties and led to the occurrence of the FRET process,affording the nanoparticle system a ratiometric sensor for Hg2+.The nanoparticle sensor can selectively detect the Hg2+ in water with the detection limit of 1?10-6 mol/L.Additionally,the FRET-based system exhibited large wavelength shift (ca., 150 nm) between the donor excitation peak (430 nm) and the acceptor emission peak (579 nm),which eliminates any influence of excitation backscattering effects on the fluorescence assay.It has been found that the FRET-based system with smaller nanoparticle as the scaffold exhibited higher energy transfer efficiency and was more preferred for the accurate ratiometric detection.This approach may provide a new strategy for ratiometric detection of analytes in environmental and biological applications.关键词：FRET;Ratiometric sensing;Mercury ion;Polymer particle;Rhodamine
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发布时间：2021-03-19 - 摘要：Epoxy/thermoplastic blends have been extensively studied because of the importance in toughening application and the fundamental academic interests.Morphological structure formation through reaction-induced phase separation in the diglycidyl ether of bisphenol A (DGEBA) and polysulfone (PSF) blends are investigated with various amounts of PSF and different kinds of curing agents.The fractured surfaces are studied with the scanning electron microscope, on the cross section or normal to the film surface of the sample film.Several morphological structures are observed at different PSF concentrations.Sea-island and inter-connected nodular structures are respectively obtained at lower and higher PSF concentrations.At appropriately middle PSF compositions, usually around 0.15 weight fractions for the samples, an unusual three-layered structure is formed.The upper and lower layers are similar, with PSF-rich particles sparsely dispersing in the epoxy-rich matrix; most of the PSF-rich domains are located in the middle layer, where bicontinuous structure is formed.It is found that the three-layered structure is developed from an initially bicontinuous structure, which will retract (PSF-rich network shrink) toward the middle region of the sample film with the proceeding of reaction and phase separation.Driving force for this phenomenon is the change of the Gibbs free energy, shift of the coexistence curve, volume fraction decrease of the PSF-rich network and the dynamic asymmetry between the components.At middle PSF compositions, the layered structure can be formed at various curing temperatures.When different curing agents are used, reaction rate will change, however, the reaction rate is not an essential cause for the formation of the layered structure.When the curing agent has a higher reactivity with the epoxy (for the DGEBA, 2-ethyl-4-methylimidazole (2E4MZ) and PSF system), reaction kinetics may be better competitive with the phase separation kinetics, and the thickness ratio of the middle layer will increase, compared with the DGEBA, 4,4'-diaminodiphenyl sulfone (DDS) and PSF system.However, better compatibility on the molecular level is introduced when the medium reactive curing agent, 4,4'-diaminodiphenyl methane (DDM) is used to react with the DGEBA.The consequence is that the components are more dynamically symmetric during the phase separation, and the bicontinuous structure may not (or need not) develop to become a layered structure.关键词：Epoxy;Layered structure;Dynamic asymmetry;Compatibility;Curing agent
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发布时间：2021-03-19 - 摘要：A series of hydrophilic cationic polyurethane foams (defined as modified PUFs) were prepared by using N-methyl diethanolamine (defined as N-MDA) as the reactant and treating the foams by hydrochloric acid.The catalytic activity of N-MDA was effectively inhibited by using the mixture of phosphoric acid and acetic acid as the acidic inhibitor and the PUFs were successfully prepared at high amount of N-MDA.The structures and properties of the resulting samples were analyzed by IR spectrometer,contact angle measuring instrument,electronic stripping tester,conductivity meter and zeta potential meter.With increasing the amount of N-MDA,the cation content and hydrophilicity of the samples increased gradually,but the elastic resilience,tensile strength and elongation at break increased first and then decreased.Furthermore,The modified sample was used as a novel microorganism immobilized carrier for adsorbing activated sludge.The results indicated that the modified PUF displayed a higher adsorption rate for activated sludge than the unmodified one (defined as contrast PUF).And its highest adsorption capacity for activated sludge could reach 180 g/L,more than two times of the capacity (80 g/L) of the contrast PUF.The adsorbing processes of these two carriers were explained based on the hydrophilicity of their backbone surfaces and the electrostatic attraction between the carrier and activated sludge.The improved adsorption property should make the modified PUF suitable for application in microbial immobilization.关键词：Polyurethane foam;Hydrophilicity;Cation;Immobilized carrier
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发布时间：2021-03-19 - 摘要：Starting from the long-tail in molecular liquid velocity correlation function,the same long-tail in the stress correlation function of molecular liquid is obtained by computer simulation.By using the scaling picture,it is shown that the long-range correlations in a polymer chain and the long-tail in velocity/stress correlation function in the molecular liquid share the same physical mechanism.Both of the velocity/stress correlation function and the bond vector correlation function have analogous characteristics.Instead of the exponential decay predicted by the classic model of the random walk,the new power-law decay of bond-vector correlation function in polymer chains is clearly explained.The bond vector correlation functions for chains in good and theta solvents are decayed as a power law with exponent 2v -2 and -3/2,respectively.关键词：Correlation function;Power-law decay;Exponential decay;Long-tail
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发布时间：2021-03-19
Research Article
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