最新刊期
卷 ， 期 5 ， 2010
- 摘要：A polyfluorene derivative containing a monomer with bis-aldehyde functional group was synthesized according to Suzuki coupling reaction.Then,a small amount of oligo(phenylenevinylene with two triphenylamine side group) (MOPV) with bis-phosphonate functional groups was grafted to the polyfluorene derivative with bis-aldehyde functional groups by using WittigHorner method.The structures,thermal,optical and electrochemical properties of MOPV,pre-grafted polymer P1 and the grafted polymer PF;g-MOPV were characterized by 1H\|NMR,GPC,DSC,TGA,UV-Vis,photoluminescence (PL) spectroscopy and cyclic voltammetry (CV),respectively.The grafted polymer exhibited better thermal properties than the pre-grafted polymer P1.The grafted polymer exihibited two PL emission bands ascribed to polyfluorene and MOPV segments,which indicated that F-rster energy transfer from polyfluorene host to MOPV guest was efficient.This is the main mechanism in the PL process.To investigate the electroluminescent (EL) characteristics of the grafted polymer,a singlelayer PLEDs device with a configuration of indium tin oxide (ITO)/poly-(ethylenedioxythiophene):poly(styrenesulfonic acid) (PEDOT∶PSS)/polymer/Ca/Al was fabricated.The grafted polymer emitted yellowish-green light with the international commission on illumination(CIE) coordinates of (0.30,0.57) and the maximum brightness of 1550 cd/m2.The MOPV segments serve as effective sites for charge trapping,which can trap both electron and hole from the polyfluorene backbone.Charge trapping rather than Frster energy transfer is the main mechanism in the EL process.
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发布时间：2021-03-19 - 摘要：The magnetic composite microspheres,which had no surface active agents on the surface and were more suitable for use of biomedicine,were prepared by a simple method——DPE method.In the preparation of 1,1-diphenylethene (DPE),methyl methacrylate (MMA) and acrylic acid (AA) took place soap-free polymerization,and the living short copolymer chains,which could chelate with Fe3O4,were prepared.Then Fe3O4were added,the living short copolymer chains were chelated to the surface of Fe3O4.The subsequent polymerization could take place on the surface of the Fe3O4,then the magnetic composite microspheres were prepared.The effects of AA,DPE,Fe3O4 and initiator were investigated in detail.With the increase of AA,DPE and initiator,the morphology of magnetic composite microspheres improved and then declined.The morphology of magnetic composite microspheres had no big change with addition of Fe3O4,but the magnetic content increased obviously.The magnetic composite microspheres,prepared in optimum conditions,were characterized by transmission electronic microscopy (TEM),thermogravimetric analysis (TGA) and vibrating sample magnetometer (VSM).The results showed that for these magnetic composite microspheres the magnetic content was about 20%,the specific saturation magnetization was about 32.2 emu/g,the average size was 265 nm and there were no any impurity on their surface.
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发布时间：2021-03-19 - 摘要：Solution polymerization and amidation reaction were used to synthesize the multifunctional comb-type amphiphilic polymer,poly(stearyl methacrylatecomethylacrylic acid)(ethanolamine-ethanediamine-folic acid) (PSM-EE-FA).A study on structure and configurations was conducted through Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (1H\|NMR).The molecular weight distribution was determined by gel\|permeation chromatograpy (GPC).It was found that the polymer was synthesized successfully,and that the number-average molar mass and the polydispersity index were 28600 and 1.375 respectively.Through the phase transfer process,the amphiphilic polymer was used to encapsulate hydrophobic CdSe/ZnS core-shell quantum dots (QDs) in chloroform to get watersoluble,targeting quantum dots (PSM-EE-FA-QDs).The watersoluble QDs solution was stable.The optical properties of PSM-QDs were determined by ultraviolet-visible (UV-Vis) and fluorescence emission spectrum.As shown in the results,the UV-Vis and fluorescence emission peaks were similar to those of the original hydrophobic QDs.However,because of the formation of the polymer layer on the surface of the QDs,the red-shifts of the peaks were observed.The resulting PSM-EE-FA-QDs retained 98% of the photoluminescence value of the original CdSe/ZnS QDs in chloroform.The quantum yield (QY) of the PSM-EE-FA-QDs was 95% of the original QDs.With the dynamic light scattering (DLS) and transmission electron microscopy (TEM) results,it was indicated that the water-soluble QDs were welldispersed within the polymer.In addition to good performance of PSM-EE-FA-QDs,the synthesis of the copolymer and the corresponding water-soluble QDs is relatively simple.
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发布时间：2021-03-19 - 摘要：The chain\|disentangled poly(ethylene terephthalate) (PET) samples were prepared by freeze-extracting PET solutions (with concentrations ranged from 0.1~10 g/dL,in three types of solvent) and were characterized by Fourier transform infrared spectroscopy (FTIR),wideangle X-ray diffraction (WAXD) and differential scanning calorimetry (DSC).WAXD curves showed that,compared with the chain interpenetrated and entangled PET sample quenched from the melt,chain\|disentangled PET samples crystallized more easily.By FTIR spectra,it was found that the level of chain disentanglement and crystallinity increased with decreasing solution concentration.But at high dilution,distances between chains became too great to crystallize during the extracting process.For a solution concentration near the overlap concentration c*,it’s advantageous not only to chain disentanglement,but also to the formation of ordered structure and crystallization.Moreover crystallization behavior of PET was affected by solvent used to prepare samples due to the influences of solvent power on the interactions between coils and then the level of chain disentanglement of these samples.When the concentrations of the solutions are lower than the overlap concentration c*,the PET samples prepared from the good solvent have more orderly structure due to much fewer interchain entanglements.While the concentrations of the solutions are higher than c*,samples prepared from the bad solvents have more orderly structure.Furthermore,The DSC and WAXD analysis results indicated the samples prepared by freezeextracting PET solutions were partially crystallized.It’s not full disorder in amorphous regions and was a metastable state between order and diorder.After the same annealling,chain\|disentangled PET samples were prone to form ordered structure and had a higher crystallinity compared with the chain\|entangled PET samples.
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发布时间：2021-03-19 - 摘要：The amphoteric copolymer P(AM-co-AA-co-DAC-co-DMC) was synthesized by dispersion polymerizationin in ammonium sulfate aqueous solutions,in which noionic monomer acrylamide (AM),anionic monomer acrylic acid (AA),cationic monomer acryloyloxyethyltrimethyl ammonium chloride (DAC) and cationic monomer methacryloyloxyethyltrimethyl ammonium chloride (DMC) were used as raw materials.The characteristics of copolymers were studied by means of FTIR,13C-NMR,transmission electron microscopy(TEM) and other methods.The effects of different dispersants,the molar ratio of anionic monomer to cationic monomer and pH on the dispersion polymerization process and the stability of the dispersion system were investigated.The results showed that when the amphoteric copolymer P(AM-co-AA-co-DAC-co-DMC) was synthesized in the ammonium sulfate aqueous solution,to obtain a relatively stable dispersion system,it should choose to use nonionic dispersion stabilizer or cationic dispersion stabilizer as polymeric stabilizer,such as polyvinylpyrrolidone (PVP),poly(methacryloyloxyethyltrimethyl ammonium chloride) (PDMC) and poly\|(acryloylxyethyltrimethyl ammonium chloride)(PDAC) should be used,and its pH should be between 2 and 4.Amphoteric nano-copolymers with more than 25% total ion exponent can be obtained under the following optimized conditions:a mass fraction of polymeric stabilizer polyvinylpyrrolidone (PVP) is 1.5%,an initiation temperature is 40℃,pH = 3,the molar ratio of ionic monomer to cationic monomer is less than 1.
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发布时间：2021-03-19 - 摘要：Under pseudo-high dilution conditions,two kinds of macrocyclic aryl ether ketone sulfone oligomers have been synthesized in high yield from phthaloyl dichloride and electron-rich aromatic hydrocarbons in the presence of Lewis base via electrophilic reaction.The presence of Lewis base NMP in this reaction is demonstrated to be advantageous for forming macrocyclic oligomers.Detailed structural characterization of the oligomers confirmed the cyclic nature by a combination of MALDI-TOF-MS,GPC,IR and 1H\|NMR analyses.The cyclic ether ketone sulfone oligomers 3a readily undergo anionic ringopening polymerization in the melt by using potassium 4,4′-biphenoxide as the initiator,producing linear,high molecular weight poly(ether ketone sulfone) with Tg of 221.8℃and excellent thermal stability.Moreover,the isothermal chemorheology of the ringopening polymerization of cyclic oligomers 3a was also investigated.The results show that the shear viscosity of the molten reactive mixture increases slowly and is lower than 10 Pa#12539;s at a constant shear rate of 0.05 rad/s in the initial stage of ring-opening polymerization,and the length of the initial stage shortens as the content of initiator increases.
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发布时间：2021-03-19 - 摘要：The relationships between the structure and the rheological behavior of poly(vinyl alcohol) (PVA) hydrogels prepared by freeze/thaw cycles were investigated as a function of polymer concentration (5 wt%～25 wt%).The degree of crystallinity and apparent dimensions of crystallite were determined by XRD.Rheological properties of PVA solutions including modulus and creep properties were characterized by controlled stress rheometer.Measurements of the shear storage and loss modulus were performed at a fixed frequency of 1 Hz and a low stress,under conditions where the deformation imposed on the gel structure is entirely reversible.The storage modulus at low frequency and low strain amplitude increases as the concentration increases,but the increase rate becomes clearly slow when the concentration is higher than 20 wt%.The storage modulus at 1 Hz was determined and related to the degree of crystallinity and concentration.Based on these measurements it was concluded that a minimum crystallinity and concentration were required for these PVA samples to exhibit gel behaviour.A more detailed comparison of XRD and rheological data led to the conclusion that the storage modulus was mainly controlled by the PVA crystallinity while the hydrogen bond interactions had a much smaller contribution,when the concentration was lower than 15 wt%.A structural parameter related to the network mesh size is derived from measurements of the dynamic storage moduli at low values of strain frequency and amplitude.The storage modulus of PVA hydrogels at different temperatures was analyzed on the basis of a theoretical model based on the scaling approach.The creep response of PVA hydrogels was investigated.With increase in concentration,these hydrogels exhibited an evolution from a linear viscoelastic response to a nonlinear viscoelastic response.
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发布时间：2021-03-19 - 摘要：A series of triblock copolymers of methyl methacrylate (MMA) and 6-O-methacryloyl-1,2;3,4-di-O-isopropylidene-D-galactopyranose (MAIPGal) were synthesized by sequential atom transfer radical polymerization (ATRP) of MMA and MAIPGal,using 4,4′-biphenol di(2-bromoisobutyrate) (BiBBP) as the initiator.The chemical composition and molecular weights of the copolymers were characterized by 1H-NMR and GPC.It was demonstrated that the block chain length of both PMMA and PMAIPGal can be tuned by the feed molar ratio and monomer conversion.After de-protecting the isopropylidene groups of PMAIPGal,amphiphilic tri-block copolymers were obtained.Their self-assembly behavior in water was investigated by TEM.We investigated the effects of polymer structure,composition and initial concentration in good solvents on the final morphologies of the aggregates.For BAB copolymers,with the hydrophobic PMMA in the center,when the hydrophilic PGA was short,they tended to form vesicle like assemblies at lower polymer concentration.Increasing the chain length of the PGA chain,large irregular micelles were obtained.For ABA copolymers,small sized micelles were the main morphologies,but they were connected with each other due to the interaction of the PGA segments.The difference of self-assembly behavior was attributed to the polymer structure,which dominates the molecular packing as well as the chain segregation of the glycopolymer chains.
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发布时间：2021-03-19 - 摘要：Double network (DN) hydrogels composing of poly(2-acrylamido-2-methylpropanesulfonic acid) (PAMPS) as the first network (FN) and poly(acrylamide) (PAM) as the second network (SeN),which were prepared by ultraviolet irradiation polymerization,were modified by poly(ethylene glycol) (PEG).By adding PEG into single network (SN) hydrogels,many tiny meshes have been made in the network structures; meanwhile the PAM particles of SeN are in different sizes.DN hydrogels modified by PEG become tougher and softer than those without PEG.The swelling behavior was measured gravimetrically at 28℃.The absorbed amount of acrylamide (AM) in SN hydrogels was measured by brominate titration.The structures of different SN hydrogels were successfully characterized by scanning electron microscopy (SEM).The compressive and tensile properties were examined by using Zwick/Roell tester.The results showed that:this PEG modified DN hydrogels exhibited higher swelling ratio than that of unmodified DN hydrogels,the former was twice times higher than the latter.Interestingly,the volume of DN hydrogels became larger with the gradual increasing amount of PEG in the hydrogels,likewise,the transmittance of DN hydrogels with various PEG amounts became lower.Modified SN hydrogels prefer to absorb AM,because the small meshes,which are in the network of hydrogels,enhance the absorbability of water and AM.Pictures of SEM demonstrate apparently that many small meshes of about 0.05～10 μm are in the network structures and the thickness of mesh walls ranges from 0.02 μm to 0.2 μm.However,in the unmodified SN hydrogels no obvious meshes were found and the thickness of mesh walls is about 3 μm.Some compressive and tensile properties were enhanced,for example when the PEG = 1.0 g,the compressive strain of modified DN hydrogels was 90%,while that of the unmodified ones was 80%.Twice times higher tensile strain than that of unmodified DN hydrogels indicated that modified DN hydrogels had become tougher and softer.
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发布时间：2021-03-19 - 摘要：A reversible additionfragmentation chain transfer (RAFT) agent,S-1dodecyl-S′-(α,α′-dimethyl-α″-aceticacid) trithioncarbonate was synthesized.The UV-initiated RAFT polymerization of polyethylene glycol dimethacrylates (PEGDMA) at room temperature was investigated by using differential scanning photocalorimetry (DPC) and dynamic mechanical analysis (DMA).The photopolymerization rate of the RAFT system was much lower than that in conventional free radical polymerization,a mild autoacceleration occurred as the addition reaction became diffusion controlled.In addition the influence of different spacer lengths between the methacrylate groups on RAFT polymerization rate and final conversion was also explored.The results show that the final conversion increases slowly and the polymerization rate decreases at first and then increases as the number of ethylene glycol units between the methacrylate groups increaseing.Comparison with three different PEGDMAs,PEGDMA with longer middle segments yields more homogeneous networks and lower crosslinking density.
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发布时间：2021-03-19 - 摘要：The carboxyl-containing polyaryletherketones (PEK-1,PEK-2 and PEK-3) with excellent thermal properties and good film formations prepared in our group were used as macromolecular ligands.Using 1,10phenanthroline (Phen) as co-ligand and samarium (Sm3+) as the central ion,a series of novel samarium coordination polymers (PEK-Sm3+-Phen) were prepared.The FTIR and UV-Vis absorption spectra suggested that both the oxygen atoms of carboxyl groups of PEK and the nitrogen atoms of Phen were coordinated with Sm3+ ions.The XRD curves indicated Sm3+ ions could distribute homogeneously within the polymer matrix due to the formation of coordination bonds between Sm3+ and the carboxyl groups of PEK.The fluorescence spectra showed that all the coordination polymers obtained could exhibit the intense characteristic emission of Sm3+ ions under UV excitation.Moreover,their emission intensities were much higher than that of the corresponding small molecular complex (Sm3+-Phen) due to the introduction of PEK with the rigid polymer chain,which could result in the stable coordination structure and the low coordination symmetry around Sm3+ ion in the PEK-Sm3+-Phen system.In addition,among the three coordination polymers obtained,PEK-1-Sm3+Phen showed the highest fluorescence intensity.The emission intensity of PEK-1-Sm3+-Phen could reach a maximum value at the Sm3+ content of 15.73 wt%.
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发布时间：2021-03-19 - 摘要：Polyesteramide (PEA(n,x/y))prepolymers with Mn from 4400 to 6400 were synthesized through melt polycondensation from adipic,butanediol and N,N′bis(2hydroxyethyl)oxalamide(0)or N,N′-bis(2-hydroxyethyl)adipamide (4)at different butanediol(x)to bisamidediol(y)molar ratios.Chain extension reaction was performed with 2,2′-(1,4-phenylene)-bis(2-oxazoline)(PBOX)and adipoyl biscaprolactamate(ABC)as combined chain extenders.High molecular weight PEA(n,x/y) with Mn up to 22500 and Mw up to 53100 was prepared.The PEA(n,x/y) prepolymers and the chain extended PEA(n,x/y) were characterized by FTIR and 1H-NMR spectroscopy,differential scanning calorimetry(DSC),and thermogravimetric analysis(TGA).1H-NMR spectra revealed that during the preparation of the PEA(n,x/y) prepolymers,some ester-amide exchange side reaction took place.DSC studies indicated that after chain extension the Tm and ΔHm of the polyesteramides decreased.TGA studies showed that after the chain extension,the thermal stability of the PEA(n,x/y)s slightly decreased,but still a little higher than that of poly(butylene adipate).
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发布时间：2021-03-19 - 摘要：A kind of radiation-protection material based on nano-poly(lead acrylate) epoxy resin was successfully prepared via graft copolymerization route induced by γ irradiation.Epoxy resin contains ether bond,so the α-H atoms of the ortho-carbon and tert-carbon atoms are relatively active.Lead acrylate contains double bond.Under the exposure of γ-rays they can become the epoxidized free radicals and acrylic lead free radicals,which lead to graft polymerization.The product was characterizedand and analyzed with Fourier transform infrared spectroscopy (FTIR),X-ray diffraction (XRD),transmission electron microscopy (TEM)and scanning electron microscopy (SEM).The stretching and bending capabilities were measured with a material allpurpose testing machine.Gamma energy spectrum measurement was carried out to evaluate its radiation-shielding properties.The results revealed that this composite material has a sea-island biphase structure.Poly(lead acrylate) particles were partially crystalline,and the particle size was about 5 nm. Graft polymerization of the two components occured at the surface of the poly(lead acrylate) particles and resulted in a network structure,which improved the mechanical properties of epoxyresin.The γ-ray mass absorption coefficient of this material with the value of 0.060 cm2/g under 1.33 MeV was higher than that of lead,so that it was a good radiation-protection material with low density of 1.37 g/cm3.The material may be applied to the field of aerospace radiation protection or radiation protection glass of electronic components packaging.
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发布时间：2021-03-19 - 摘要：Carboxymenthyl chitosan (CM-CTS)with hydroxyl,carboxyl and amino groups was chosen as doping acid to synthesis polyaniline(PANI).It was succeed to convert the produced nanofibres into hollow microspheres via changing the ratios of carboxymenthyl chitosan and aniline monomer from 0.01 to 0.5.The results of FTIR and UV-Vis absorption spectra were identical to those of the emeraldine salt state of PANI.Because ―OH in CM-CTS and N―H in PANI are easy to form hydrogen bonds,N―H peak in FTIR was depressed with the addition of doping acid.Besides,the corrosion inhibition property of PANI was demonstrated for mild steel in acidic environment using electrochemical impedance spectroscopy(EIS),potentiodynamic polarization and scanning electronic microscopy(SEM).The results revealed PANI had performed excellently as corrosion inhibitor for mild steel in 0.5 mol/L hydrochloric acid and its inhibition efficiency was up to 91.6%~92.3% even with a low concentration of 40 mg/L.The single capacitive loop in Nyquist plots revealed the charge transfer controlled the corrosion process.The value of double layer capacitance increased with the increase of PANI concentrations because PANI molecule replaced water molecule and absorbed on the surface of mild steel and inhibited the corrosion effectively.The parallel polarization curves obtained in the absence and presence of different inhibitor concentrations indicated that the addition of PANI had not changed the mechanism of either steel dissolution or hydrogen evolution reaction,contrary,it acted by simple blocking the mild steel surface.The corrosion potential in polarization shifted unobviously and it behaved as a mixed-type inhibitor.
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发布时间：2021-03-19 - 摘要：A series of novel fast responsive and electrically sensitive poly（4-acetyl acryloyl ethyl acetate-co-2-acrylamide-2-methy-1-lpropanesulfonic acid）porous hydrogels were synthesized by radical polymerization using different molecular weights PEG as porogenic agents.The SEM macrograghs revealed that macroporous structure was formed within the hydrogel as porogenic agents PEG was eluted,and the apertures ware between 30 μm and 120 μm.The hydrogel containing PEG6000 as porogenic agent exhibited the highest swelling and deswelling ratio,reached its swelling equilibrium whinin 30 s,get its equilibrium deswelling state within 40 min in NaCl solution and even faster about 12 min under an electric field.The responsive property of hydrogel accelerated as the content of AMPS increased,when the n(AAEA)∶n(AMPS)=1∶1,the hydrogel had a highest deswelling ratio between others.But the hydrophobic group will shrink and form many hydrophobic micro-area under high temperature as the AAEA content increased.This prevented the water discharged continually out of hydrogel,so when n(AAEA)∶n(AMPS)=3∶1,the hydrogel reached its equilibrium deswelling state within 4 min but its water ratio was high up to 75 percent.The high pH will accelerate the dissociation of AAEA,provide more electrified particle,quicken the water discharge and have a short time to reach equilibrium.Also,add the concentration of electrolyte and heighten the electrolysis voltage will shorten the equilibrium deswelling time.
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发布时间：2021-03-19 - 摘要：Preparation of raspberry-like polymer composite particles through adherence of smaller cationic particles of P(St-co-DMHB) (poly(styrene-co-methacryloxyethylhexadecyldimethylammonium bromide)) onto larger PMMA (poly(methyl methacrylate)) anionic particles surface was achieved by heterocoagulation based on electrostatic interaction.A series of P(St-co-DMHB) cationic particles with particle size varied from 43 nm to 105 nm were obtained through emulsion polymerization using different levels of the cationic monomer DMHB.The particles were assembled on the anionic particles surfaces respectively to result in polymer composite particles having different granulations.Light transmittance and particle size and its distribution in the heterocoagulation processes were followed in order to clarify in detail the assembling process of the small cationic polymer particles onto the larger anionic polymer particles.Transmission electron microscope was used to examine the morphologies of the cationic latex particles,the anionic latex particles and that of the composite particles after their heterocoaguculation.It was observed that the degree of coverage of the small cationic particles on the surface of the anionic large particles was adjustable in a range by varying the ratio of the anionic and the cationic latex particles.
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发布时间：2021-03-19
Research Article
- 摘要：A convenient and effective approach has been developed to prepare carbon molecular sieve (CMS) membranes derived from poly(furfuryl alcohol) with high O2/N2 separation performance in this paper.The CMS membranes is formed by coating a thin layer of viscous poly(furfuryl alcohol) liquid,which was synthesized by polymerization of furfuryl alcohol by oxalic acid catalyst,on a porous coal-based tubular support followed by controlled pyrolysis.TGA,XRD,SEM and gas permeation experiments are employed to give an insight into pyrolysis process,morphological characteristics and separation performance of CMS membranes.The results show that the CMS membranes with a continuous defect-free coating exhibit an excellent O2/N2 separation performance.The increase in the final pyrolysis temperature from 600℃ to 900℃ results in a decrease in the d-spacing of the interlayers of graphitic carbon planes and the shrinkage in size of ultramicropores,which leads to the reduction in permeabilities of O2 and N2 and improvement in O2/N2 permselectivity.It can also be found that the correlation points for all CMS membranes prepared in the present work fall above the Robeson’s upper bound limit that is uncommon for polymeric membranes.These results indicate that poly(furfuryl alcohol)based CMS membranes obtained from the novel method are of great potential for O2 and N2 separation.
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发布时间：2021-03-19 - 摘要：Three kinds of epoxybased amorphous polymers containing strong pushpull biszao chromophores were obtained.For the synthesis,three aminoazobenzene derivatives with different structures were synthesized through azo-coupling reactions between 3,5dimethylaniline and diazonium salts of 4-nitroaniline,2,4dinitroaniline and 4-aminobenzonitrile,respectively.The bisazo polymers BP-2A-35-CN,BP-2A-35-NT and BP-2A-35-2NT were synthesized through post-polymerization azocoupling reaction between a precursor polymer (BP-AN) and diazonium salts of the aminoazobenzene derivatives.The azo polymers were characterized by the spectroscopic methods and thermal analysis.Thin films of the bisazo polymers were used to fabricate surface-relief-gratings (SRGs) by exposing the thin films to an interference pattern of diode-pumped solid state laser beam (532 nm) at modest intensities (80 mW/cm2).SRGs can be observed on films of BP-2A-35-CN and BP-2A-35-NT,but no surface structure can be observed on film of the azo polymer with nitro groups at the o-positions of azo groups (BP-2A-35-2NT).The result indicates that the azobenzene chromophore shows a significant effect on the SRG formation.
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发布时间：2021-03-19
Research Bulletin
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