最新刊期
卷 ， 期 12 ， 2013
- 摘要：The poly(arylene ether nitrile)s containing phthalazinone moiety end-capped by hydroxyl group (PPEN-OH) were successfully synthesized by the nucelophilic displacement reaction of the bisphenol-like monomer,4-(4-hydroxyphenyl)-phthlazin-1(2H)-one (DHPZ) and 2,6-difluorobenzonitrile (DFBN) using tetramethylene sulfone as solvents and K2CO3 as catalyst at 190 ℃ with stirring for 5 h.Then the reaction of PPEN-OH and allyl bromide in the presence of tetramethylene sulfone as solvent was carried out,following the hydrosilylation of methyltrimethoxysilane with the solvents of tetrachloroethane and the catalyst of 4-Pt at 105 ℃ with stirring for 23 h to get trimethoxysilane endcapped PPEN (PPEN-Si).Then the fluorine silicone hybrid material (PPEN-b-FPSO) was prepared from triethoxy-1H,1H,2H,2H-tridecafluoro-n-octylsilane,PPEN-Si and diphenylsilanediol using N-methyl-pyrrolidone as solvents and barium-hydroxide monohydrate as catalyst at room temperature with stirring for 36 h.The effects of reaction temperature and reaction time on the yield of target product were investigated.The structures of copolymers obtained were comfirmed by FTIR,1H-NMR and19F-NMR,respectively.The film was fabricated from the SiO2 modified by (heptadecafluoro-1,1,2,2-tetradecyl) trimethoxysilane and the resulting PPEN-b-FPSO at the weight ration of 1:1.The thin film was dried under vacuum at the fixed temperature procedures.The surface morphology of the thin film was observed using scanning electron microscope.The film presented micro-nano rough microtextures.The contact angle of the film observed directly by DSA 100 was up to the maximum of 159.The adhesion of the film was one grade by QFZ adherometer.The results indicate that this hydrophobic coating is a prospective candidate for the application of aviation,building,environmental protection and so on.关键词：Hydrophobic coating;Organic inorganic hybrid material;Polyarylether nitrile;Fluorosilicone;Water contact angle
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发布时间：2021-03-19 - 摘要：Sulfonated poly(ether ether ketone) (SPEEK) membranes with different degrees of sulfonation (DS) were fabricated by sulfonation of poly(ether ether ketone) (PEEK) in the concentrated H2SO4 (ca. 98%).Their parameters were obtained and reported,such as the ion exchange capacity (IEC),area resistance,water uptake and the vanadium ion permeability.The SPEEK membrane with DS of 60% was selected for the vanadium redox flow battery test.It was observed the crystallization of SPEEK decreased,and the ion exchange capacity,water uptake,vanadium ion permeability increased with the DS of SPEEK membranes.The membrane with DS of 60%(SPEEK60) possessed lower permeability of VO2+ ions than that of Nafion117 membrane,the ion selectivity was ten times that of Nafion117 membrane.The VRB single cell with SPEEK60 membrane showed higher coulombic efficiency (CE) and energy efficiency (EE) compared to that with Nafion117.In the self-charge test,the time of SPEEK60 membrane was 2.5 times that of Nafion117 membrane.The performance of VRB with SPEEK membrane can be maintained after cycles test.The SPEEK membrane has a promising prospect for application in VRB.关键词：Ion exchange membrane;Sulfonated poly(ether ether ketone);Vanadium ion permeability;Battery efficiency
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发布时间：2021-03-19 - 摘要：A nano-Sb2O3 masterbatch (M-nano-Sb2O3) whose concentration was 80% was prepared.The masterbatch was added into poly(ethylene terephthalate) synchronized with aluminium diethlyphosphinate (AlPi).Different test methods such as limiting oxygen index (LOI),vertical burning (UL 94),cone calorimeter (CONE),scanning electron microscope (SEM) demonstrated that the LOI of PET increased from 21.0% to 34.6% and the UL 94 vertical burning rating reached V-0; the heat release rate,total smoke release and CO production were reduced; the compact degree of the char residue was remarkably improved.All these phenomena were due to the synergism between nano-Sb2O3 and AlPi.Morever,thermal gravimetric analysis (TGA),X-ray photoelectron spectroscopy (XPS) and Fourier transformed infrared spectroscopy (FTIR) pointed that the synergistic effect increased the char residue and its thermal stability,the char formation was promoted by the condensation of diethylphosphinic acid with the Sb-OH on the surface of nano-Sb2O3,and the char residue was mainly consisted of aluminum (antimony) phosphates,aluminum (antimony) pyrophosphate and organic compounds containing aryl cyclic structure.Differential scanning calorimetry (DSC) showed that the synergistic effect facilitated the crystallization of PET and its melting endotherm.Therefore,flame retardancy mechanisms in PET for AlPi in combination with nano-Sb2O3 were primarily cross-linking reactions,char formation in condensed phase and endothermic effect,meanwhile,gas phase mechanism was also involved.关键词：Poly(ethylene terephthalate);Aluminium diethlyphosphinate;Nano-Sb2O3;Flame retardancy
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发布时间：2021-03-19 - 摘要：The copolymerizations of ethylene with propylene were investigated by the vanadium (Ⅲ) catalysts bearing bidentate [N,O] ligands (2a,[PhN=C(CH3)CHC(Ph)O]VCl2(THF)2; 2b,[PhN=CHC6H4O]VCl2(THF)2; 2c,[PhN=CHC(Ph)CHO]VCl2(THF)2).Ethylene-propylene copolymers with different comonomer incorporations (P=0 mol%~20 mol%) and narrow molecular weight distributions (Mw/Mn 3.0) were obtained.The molecular weights and molecular weight distribution of copolymers were determined by gel permeation chromatograhpy (GPC).The incorporation of comonomer and microstructure of copolymers were confirmed by 13C-NMR methods.On activation with cocatalyst (Et2AlCl) and reactive agent (ETA),catalytic activity,comonomer incorporation,and molecular weights of the resultant polymers can be controlled over a wide range by tuning reaction parameters,such as concentration of Et2AlCl,dosage of ETA,temperature,feed composition and so on.Furthermore,the microstructures of polymer chains can also be adjusted by changing reaction parameters above,which were confirmed by calculating the monomer sequence distribution (xi) and continuous methylene sequence length (n0 and n2+).The reactivity ratios of copolymerization (r1r2 1.0) were evaluated by the Fineman-Ross method,indicating the insertion of comonomers will not be influnced by the kinds of the last inserted monomers,and ideal random copolymer can be obtained by catalysts 2a ~ 2c,which can also be proved by 13C-NMR and calculation of xi,n0 and n2+.关键词：Copolymerization;Sequence distribution;Reactivity ratio;Random copolymer
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发布时间：2021-03-19 - 摘要：The liquid-crystal (LC) alignment properties of surface relief gratings (SRGs) of different azo polymers and their correlations with grating parameters and polarizations of writing beams were studied.Three azo polymers with different kinds of azo chromophores and different chromophore densities were used in this study.The contrasts (Tmax/Tmin) and optical photographs of different liquid crystal cells were compared to determine the alignment properties.For the gratings with a period of 800 nm recorded by p+p interfering Ar+ laser beams on the epoxy based azo polymer containing 4-cyanoazobenzene chromophores (BP-AZ-CN) films,the ability for aligning liquid crystal increased with the increase of grating depths.For gratings of the epoxy based azo polymer containing 4-carboxylazobenzene chromophores (BP-AZ-CA) with a period of 800 nm and the gratings of the polyacrylate based azo polymer containing 4-carboxylazobenzene chromophores (PA-AZ-CA) with a period of 1200 nm,the liquid crystal showed uniform alignment when the grating depth was in a range from 16 to 100 nm.For the BP-AZ-CA gratings with a similar depth,the liquid crystal showed better alignment on the gratings with a period of 800 nm than gratings with a period of 1200 nm.Compared with BP-AZ-CA and PA-AZ-CA gratings with a period of 1200 nm,liquid crystal shows a better alignment on the PA-AZ-CA gratings.For the PA-AZ-CA gratings inscribed by RCP+LCP interfering Ar+ laser beams,no unidirectional alignment was observed even for the gratings depths over 100 nm.Above results can offer a better understanding of the effect of polymer structures and grating parameters on the liquid crystal alignment performance.关键词：Azo polymer;Liquid crystal;Alignment;Surface relief gratings;Structures
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发布时间：2021-03-19 - 摘要：Poly(styrene-co-methacrylic aicd) (PSMAI) nanofibers with carboxyl groups was prepared by a combination of the soap-free emulsion polymerization method and electrospinning technique,which were employed as solid support to immobilized horseradish peroxidase (HRP) enzyme through the amide bond formation between COOH of PSMAI-cell and NH2 of HRP molecules.Scanning electron microscopy(SEM) was used to evaluate the morphology and diameter of the nanofibers.Surface carboxyl of these fibers was confirmed by FTIR spectroscopy.The parameters about immobilizing HRP on the PSMAI nanofibers were studied and influence on the activity of the HRP was discussed.This study showed that soap-free emulsion polymerization method is an ideal technology to modify the polystyrene and ultimately achieve enzyme immobilization on electrospun PSMAI nanofibers surface.The immobilized HRP showed better resistance to pH and temperature than that of free form,and the storage stabilities,reusability of immobilized HRPs were significantly improved.Immobilized HRP equipped in biological reactor is applied to treat the polyphenol waste water.The catalytic removal efficiency of inmobilized HRP for removal of o-methoxyphenol (OMP) remained above 80.2% for 120 min.Immobilized HRP equipped in biological reactor is applied to treat the phenol waste water.
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发布时间：2021-03-19 - 摘要：Polypropylene (PP) and PP/halloysite nanotube nanocomposite parts of 0.7 mm thickness (-PP and -PP/HNT) were molded via micro-injection molding (MIM),and PP part of 3.5 mm thickness (m-PP) was molded via conventional injection molding (CIM).The relationship between mechanical properties and crystal structures and the influence of HNT on mechanical properties and thermal stability of the molded parts were investigated.Compared with the m-PP part,the tensile strength and storage modulus (40 ℃) of -PP part were increased by 67% and 48%,respectively,due to its significantly higher crystallinity (76.7%) and shear layer thickness percentage (57.8%).The addition of a low content (2 phr) of HNT further increased the tensile strength,storage modulus and thermal stability of -PP parts.This was mainly ascribed to the good dispersion of HNT in PP matrix.Although the contents of crystal in both -PP and -PP/HNT parts (20% and 26.3%) were significantly higher than those of m-PP part,the elongations at break of the former two parts were obviously lower than those of the latter one.This indicated that the effect of toughness decrease caused by molecular orientation was stronger than the toughening effect of the crystal for both -PP and -PP/HNT parts.关键词：Micro-injection molding;Halloysite nanotube (HNT);Crystal morphology;Mechanical property;Thermal stability
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发布时间：2021-03-19 - 摘要：Ultra-high molecular weight polyethylene (UHMWPE) fibers were modified by an air dielectric barrier discharge (ADBD) plasma generating device to improve the dyeing properties.The treatment process was carried out with various operating parameters such as input power and treatment time.Then the treated and untreated fibers were dyed with disperse dye to study the treatment effect.Surface topography,chemical construction,tensile strength and dyeing properties of the modified fibers were studied.It was found that the surface roughness of the fibers was improved by plasma etching which was confirmed by scanning electron microscopy (SEM) results.Fourier transform infrared spectroscopy (FTIR) analysis revealed a significant increase of oxygen-based functional groups (CO,C=O,OH,etc.) on the surfaces of UHMWPE fibers,which indicated that the chemical polarity of the modified fibers was improved after ADBD plasma treatment.Meanwhile,the plasma treatment had a strong effect on the strength of UHMWPE fibers,the strength showed a very drastic decrease at high input power and long treatment time.When the input power was 60~90 W and treatment time was less than 45 s,the strength loss was generally less than 10%.Moreover,the dyeing properties of the fibers were improved after plasma treatment,the K/S values of the fibers increased from 0.902 to 1.625,and the optimum processing parameters were 27 s and 80 W.关键词：UHMWPE fiber;ADBD plasma;Dye;Modification
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发布时间：2021-03-19 - 摘要：Enrofloxacin (ENRO) was taken as a template molecule and methacrylic acid (MAA) was taken as a functional monomer.To investigate the best imprinting ratio of ENRO and MAA,the density functional theory (DFT) of quantum chemistry was used to simulate the self-assembly system of the molecularly imprinted polymers (MIPs) formed by ENRO and MAA.The geometry optimization,the bonding situation and the binding energies of ENRO with MAA in different proportions were studied.The molecular imprinting mechanism and the interaction strength between ENRO and MAA were also discussed.The results showed that the compound of the ratio of ENRO-MAA (1:4) had the lowest binding energy and the most stable structure.In addition,the MIPs of different imprinting ratios of ENRO and MAA were prepared to study the binding capacity of the polymers.The experimental results showed that the MIPs synthesized by ENRO and MAA with the ratio of 1:4 had the best adsorption capacity.The results showed that the conclusion of experiments was consistent with the results of calculation.Quantum chemistry could be used to guide the optimization of the imprinting ratio of the MIPs.关键词：Enrofloxacin;Methacrylic acid;Molecular imprinting;Imprinting ratio;Computational Simulation;Adsorption properties
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发布时间：2021-03-19 - 摘要：Organic layered double hydroxide (LDH) modified with UV curing acrylate group was synthesized by two steps method,which was first intercalated with sodium dodecyl sulfate (SDS) and then grafted by semiadduct of isophorone diisocyanate and 2-hydroxyethyl acrylate (IPDI-HEA).The reactive groups of the LDH would join in the UV curing reaction when exposed to the UV lamp,obtaining the exfoliated polymer/LDH nanocomposites via in situ polymerization.The X-ray diffraction (XRD) and Fourier transform infrared (FTIR) analyses were used to confirm the formation of modified LDH.Transmission electron microscope (TEM) observation of UV-cured nanocomposites indicated the exfoliated microstructure of LDH in the matrix of polymer.The thermal stability and mechanical properties were also measured.The results showed that the onset decomposition temperature of nanocomposite with 5% LDH loading increased by 64.6 K compared to the pure polymer,while the residual char increased to 8.7% from 4.0%.Also the tensile strength were enhanced to 14.7 MPa compared with 8.5 MPa of the pure polymer.As a result,the combination properties of UV-cured polymer/LDH showed great enhancements in comparison with polymer without LDH addition.关键词：Layered double hydroxide;Nanocomposites;UV curing;Acrylate
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发布时间：2021-03-19 - 摘要：The kinetics of propylene polymerization with a TiCl4/Di/MgCl2(Di=internal donor) supported Ziegler-Natta catalyst was studied by measuring the number of active centers using 2-thiophenecarbonyl chloride as quenching agent.Influences of hydrogen and alkoxysilane type external donors on the number of active centers and chain propagation rate constant (kp) were investigated.The number and kp value of three groups of active centers that produce atactic,medium-isotactic and isotactic polypropylene (PP) fractions were determined.The catalyst activity was found to significantly increase with the addition of hydrogen,which was a result of simultaneous increases in the number of active centers and kp value.The three groups of active centers response to hydrogen differently.Hydrogen caused lower degree of increase in the number of active centers that produce atactic PP than the other two groups of active centers,and caused the highest degree of increase in the kp value of active centers that produce medium-isotactic PP.The hydrogen response of the active centers was also influenced by external donor.Increasing the bulkiness of alkyl groups in alkoxysilane donors leads to decreased hydrogen sensitivity,meanwhile the stereo-and regio-selectivities were evidently improved,implying that there are close relations between the hydrogen effect and the stereo-and regio-selectivities of the catalyst.A mechanistic model was proposed to explain the hydrogen effect.关键词：Propylene polymerization;Hydrogen;Supported Z-N catalyst;Active center
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发布时间：2021-03-19 - 摘要：The homogeneous-reinforced PVDF and PAN membranes,heterogeneous-reinforced PVDF and PAN membranes,include 6 wt%~18 wt% of PVDF casting solution and 10 wt% of PAN casting solution and matrix membranes (preparations of porous PVDF hollow fiber membrane through the melt spinning and stretching process and PAN braided tube through the 2D braided method) were prepared through the co-extrusion process.The requirement of the interfacial bonding state between the surface separation layer and the matrix membrane is higher than the tensile strength due to the techniques of aeration and backwashing in the MBR filtration process.Therefore,it will provide a better choice of membrane for the MBR system and a new characterization method of the interface bonding state of the reinforced membrane through the solubility parameter method and ultrasonic vibration analysis.The effect of ultrasonic oscillations on the membrane interface bonding state was studied.The results of this study showed that:The solubility parameter method results showed the interface bonding state of homogeneous-reinforced membranes was more stable than the heterogeneous-reinforced membranes'.The interface bonding state of homogeneous-reinforced membranes was significantly more stable than the heterogeneous-reinforced membranes'.In the same disturbance shocks environment,the change of water flux of homogeneous-reinforced membranes was slow than that of the heterogeneous-reinforced membranes.It was because of the poor interface bonding state between the surface separation layer and reinforced matrix membrane of the heterogeneous-reinforced membranes.The interface bonding state of the reinforced membranes prepared using PVDF matrix membrane was more stable than that of the reinforced membranes prepared using PAN braided tube.关键词：PVDF;PAN;Reinforced membranes;Ultrasonic;Interface bonding
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发布时间：2021-03-19 - 摘要：A new kind of conjugated poly(carbazole)s with carbazole as the main chain was designed and synthesized via click polymerization of 3,6-diazido-9-hexyl carbazole and 3,6-diethynyl-9-hexyl carbazole.The two monomers with azide and ethynyl functional groups were synthesized according to the report literatures with some modifications which not only considerably improved the yield but also simplified the synthetic procedures.The chemical structure of these two monomers was fully characterized by 1H-NMR,FTIR and microanalysis.Due to incorporation of the long alkyl carbon chain,the monomers have good solubility in most common organic solvents.Addition polymerization of 3,6-diazido-9-hexyl carbazole and 3,6-diethynyl-9-hexyl carbazole with Cu(I) as catalyst was investigated in various conditions.After optimization on the polymerization condition of solvents and temperature,well-defined conjugated poly(carbazole)s possessing carbazole as the backbone with extremely high molecular weights were obtained in high yield under mild reaction conditions.The size exclusion chromatography analyses of these poly(carbazole)s indicated that the molecular weight can be achieved as high as 100000~130000.Moreover,the purity of the synthesized polymers is very high,and no detectable by-product could be observed on the size exclusion chromatograms.The thermal and photophysical properties of these novel conjugated poly(carbazole)s were also studied in solution and in film.Thermal analysis indicate that the polymers have excellent thermal stability with Td=359 ℃ and exhibit a glass transition temperature (Tg) of 105 ℃.These poly(carbazole)s exhibited blue-violet light emissions under irradiation with 365 nm UV light indicated that the triazoles moieties did not impede the fundamental photophysical properties of the carbazole units in the main chains.关键词：Carbazole;Click polymerization;Addition polymerization;Conjugated polymer
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发布时间：2021-03-19 - 摘要：Molecular dynamics simulation is used to study the transport of charged tube-like nanoparticles (NPs) through a fluidic channel.Herein,the effect of NP size,charge nature and external electric field (E) on the transport dynamics is considered.With the increase of E,the NP flux increases remarkably,where some of them exhibit nonmonotonous variations that are different from the flux behaviors of spherical NPs.The translocation time yields to a power law decrease with E,which is in agreement with the prediction of Langevin dynamics.Under a given E,the flux of tube-like NPs is several times and even an order smaller than that of spherical NPs,and inversely the translocation time is several times larger.Compared to spherical NPs,the tube-like NPs should always sacrifice some rotational freedom to enter the channel,thus they have smaller flux and longer translocation time.These results enrich the understanding of the NP shape effect,which has implications in the design of high efficient nanocarriers.关键词：Nanoparticle;Water;Transport;Channel;Molecular dynamics
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发布时间：2021-03-19
Research Article
- 摘要：A new azide polymerpoly(azidoethyl acrylate) was synthesized with acrylic acid and 2-chloride ethanol as the raw materials through a three-step process involving esterification,radical polymerization,and azide reaction.The new substance can meet the requirements of insensitive and better compatibility in polymer bonded explosives and solid rocket propellant binder.The azidation rate was determined by elemental analysis,and poly(azidoethyl acrylate) with azidation rate of 98.67% was obtained under this reaction condition.The structure of the preparation product was characterized by FTIR,UV-Vis and 1H-NMR methods.The results of GPC declared the number-average molecular weight Mn=1.14105,molecular weight distribution index Mw/Mn=3.2,which implied the better mechanical properties and processability of preparation product.The glass-transition temperature of poly(azidoethyl acrylate) was evaluated by DSC method and the thermal stability was tested by DTA and TGA methods.The results indicated that poly(azidoethyl acrylate) showed a single glass-transition temperature at -11.77 ℃ and exhibited good resistance to thermal decomposition up to 220 ℃.Moreover,the compatibilities of poly(azidoethyl acrylate) with the energetic components of TNT-based melt cast explosives were studied by using the DTA method.The result indicated that poly(azidoethyl acrylate) can be safely used in melt cast explosives of TNT and HMX,just not suitable for RDX explosives.关键词：Poly(azidoethyl acrylate);Free radical polymerization;Azidation;Compatibility
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发布时间：2021-03-19 - 摘要：A novel polyhedral oligomeric silsequioxane/carboxymethyl cellulose (POSS/CMC) hybrid hydrogel was first fabricatied by the aggregation of POSS-NH2 nanoparticles and the formation of POSS-CMC hybrid block copolymers,which was driven by the hydrogen bonding interactions between the amino groups of POSS-NH2 and the carboxyl groups of CMC.Novel double network POSS/CMC/PNIPAm hybrid hydrogel was further designed and fabricated by the synthesis of the second net work of poly-N-isopropylacrylamide.The structure and morphology of the obtained POSS nanoparticles and POSS/CMC/PNIPAm hybrid hydrogel were respectively characterized by Fourier transformation infrared spectroscopy (FTIR),atom force microscopy (AFM),scanning electronic microscopy (SEM),rheometry and so on.Meanwhile,the mechanical and swelling properties of double network POSS/CMC/PNIPAm hybrid hydrogel were also studied.The results presented that the obtained POSS-NH2 nanoparticles had a diameter of 4 nm.Double network POSS/CMC/PNIPAm hybrid hydrogel had been successfully fabricated,and it had good mechanical properties,swelling ratio and more rapid temperature response than PNIPAm hydrogel.关键词：Hybrid hydrogel;Double network;CMC;Poly-N-isopropylacrylamide;POSS
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发布时间：2021-03-19
Research Bulletin
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