摘要:The alginate fiber bundles prepared by wet spinning techniques were processed through soaking in different solvents for 30 min and then dried at 60 ℃ for 3 h.The changes of the alginate fiber in different solvents were observed through an optical microscope and the alginate fiber bundles were observed through an scanning electron microscope.The changes of the surface of alginate fiber processed though different solvents and the dispersion of dried alginate fiber bundles were analyzed.The association phenomenon of hydrogen bonds in the alginate fiber and the alginate powder were analyzed through the Fourier infrared spectrum.On the basic of observation,the analysis of the Fourier infrared spectrum and the theory of moisture sorption,combining with an analysis of the difference and connection between different solvents,an interfacial theory model of producing doubling fibers in alginate fiber bundles during the drying process was discussed.Then a reasonable explanation of the experimental phenomena was given by applying this interfacial theory model.In the end,the experiment of destroying the hydrogen bonds by heating,the experiment of closing the hydroxyl and the freeze-dried experiment were used to verify the correctness of the interfacial theory model,but also can be used to solve the problem of producing doubling fiber,then expanding its scope of application.
摘要:The enzymatic degradation of poly(butylene succinate-co-1,4-cyclohexane dimethanol succinate) (PBS-co-CHDMS),poly(butylene succinate-co-butylene 1,4-cyclohexanedicarboxylic acid) (PBS-co-BCHDA) and poly(butylene succinate) (PBS) were performed with the aim to gain more underlying information about the degradation rules and differences in organic solvent.Among various hydrolytic enzymes the lipase from Pseudomonas cepacia (PC) was chosen for the studies.The rules of enzymatic degradation were investigated by molecular weight variation and MALDI-TOF-MS analysis of the degradation products.Additionally,mechanism of the combination between substrate and enzyme was studied with molecular docking.The results indicated that PBS-based copolymers showed an obvious degradation in chloroform.Compared to PBS-co-BCHDA,PBS-co-CHDMSs all showed a greater degradation rate after 60 h enzymatic degradation.Particularly maximum degradation was observed in PBS-co-10%CHDMS with a degradation ratio of ratio about 85%.The enzymatic degradation of PBS-based copolymers produced not only linear segments,but also cyclic oligomers.Furthermore,PBS-co-CHDMS produced more oligomers than PBS-co-BCHDA.According to the results of molecular docking,the free energy of binding between PC lipase and substrate in chloroform was in the order of CMSCMBSCMBCABBSB.That is,the docking of substrate containing 1,4-cyclohexane dimethanol succinate(CHDMS) in the active site of PC lipase was more stable than any other ones.
摘要:Linear-shaped hydroxyl-terminated polybutadiene (L-HTPB) was synthesized by living anionic polymerization of butadiene,using self-made alkyllithium containing tert-butyldimethylsilyloxy propyllithium as initiator and cyclohexane as solvent.On this basis,star-shaped hydroxyl-terminated polybutadiene (S-HTPB) was synthesized by living anionic polymerization of butadiene,using methyltrichlorosilane as coupling agent.The polymers were characterized by GPC and 1H-NMR.The results show that the micro-structures of polybutadienes are similar,the average functionalities of linear-shaped hydroxyl-terminated polybutadiene is more than 1.9 and the average functionalities of star-shaped hydroxyl-terminated polybutadiene is more than 2.8 that fit for design values.In addition,the microstructure of the polymer main chain could be controllable through regulating the radio of tetrahydrofuran and cyclohexane.The results show that with the increase of cyclohexane content in mixed solvents,the relative content of 1,4-units increased gradually,especially the cis-1,4-units increased with obvious trend.The content of 1,4-units is more than 90%,the content of cis-1,4-units reaches up to 70% and the content of 1,2-units is about 5.70% in the polymer main chain when cyclohexane is used as the single polymerization solvent.On the contrary,the content of 1,2-units is more than 90%,the content of cis-1,4-units tends to 0,and the sample exhibits the performance of plastics when tetrahydrofuran is used as the single polymerization solvent.
关键词:Anionic polymerization;Linear-shaped HTPB;Star-shaped HTPB;Synthesis and characterization;Microstructure
摘要:Organic hectorite was synthesized using cetyl trimethyl ammonium bromide(CTAB) as modifier and polyamide 6(PA6)/organic hectorite nanocomposites with high performance and low water absorption were prepared through melt blending method.The structures of modified and original hectorite were characterized with X-ray diffraction (XRD),energy dispersive spectrometer (EDS),scanning electron microscopy (SEM) and thermogravimetric analysis (TGA) indicating that the structure of organic hectorite became looser,as well as its interlayer spacing was increased from original value of 1.33 nm to 1.76 nm,and the grafted amount determined by elemental analysis was in good agreement with that by TGA analysis.The grafted amount was 0.78 and 0.73 mequiv/g respectively and the grafted yield was 71.04% and 66.62% respectively.The effect of organic hectorite content on crystal properties,dispersion in the matrix and mechanical properties of composites were investigated by differential scanning calorimetry(DSC),transmission electron microscopy(TEM) and mechanical property measurements,showing that hectorite did not play a role of nucleating agent in PA6 and with the increase of organic hectorite content,the degree of crystallinity of the composites were decreased.When the amount of organic hectorite was 5 phr,the dispersion of hectorite in the matrix exhibited mainly an exfoliated morphology and the tensile strength,bending strength of the PA6/organic hectorite composites reached the maximum values of 81.6 MPa and 122.1 MPa,respectively,which presented 25.54% and 23.50% improvement compared to those of the pure PA6.In addition,the organic hectorite significantly reduced water absorption rate of PA6.
摘要:Using stannous octoate (Sn(Oct)2) as catalyst and monomethoxy-poly(ethylene glycol) (mPEG) as macroinitiator,-caprolactone (CL) and -methyl--caprolactone (MCL) with different feed ratios were copolymerized by ring opening polymerization.By controlling the feed ratio and sequence of CL and MCL,four types of copolymers containing various hydrophobic CL/MCL ratio and distribution were obtained.1H-NMR and GPC were used to characterize the structures of these four copolymers.DSC,WAXD and FTIR were applied to investigate their crystallinity.By dialysis method,four types of polymeric micelles and drug-loaded (doxorubicin DOX) micelles were prepared and their self-assembly behavior was carefully studied.The loading and release profiles of DOX were also illustrated.The results indicated that the introduction of MCL decreased the crystallinity of copolymers,which led to the improvement in drug loading capacity and release speed.Confocal laser microscopy and flow cytometry were used to expose the endocytosis behavior of drug-loaded micelles with different core structures taken by HepG2 hepatoma carcinoma cells.The cytotoxicity of micelles was then examined by MTT.All the cell experiments revealed that both endocytosis of DOX-loaded micelles taken by HepG2 and toxic effects of DOX-loaded micelles on cells were mainly influenced by the core structure of micelles.
摘要:Amphiphilic block copolymers poly(ethylene glycol)-co-poly(glycidyl methacrylate) (PEG-co-P(GMA)) were synthesized via atom transfer radical polymerization (ATRP).Postpolymerization decoration of reactive epoxy groups in the P(GMA) block with N-(3-amino propyl) imidazole (API) resulted in a new kind of water soluble copolymer PEG-P(GMA-API).The weight-average molecular weight and polydispersity of PEG-P(GMA-API) were determined to be 17175 and 1.08 with 1H-NMR and GPC,respectively.The resulted copolymers could self-assemble into spherical nano-micelles directly in an aqueous medium.The critical micellization concentration (CMC) of the micelles was 410-2 g/L,which was significantly influenced by amino and imidazole groups.Dynamic light scattering (DLS) study showed the diameter of the micelles was about 40 nm and the micelle surface was always positively charged when the pH of the solution increased from 4 to 9.The resulted nano-micelles had the capacity to encapsulate hemoglobin (Hb) in aqueous solution with the encapsulation efficiency of 32.4 wt% at pH 7.4.The features of Hb-based micelles were spherical with a diameter of 40 nm,which was larger than that of blank micelles (30 nm).The Hb-based micelles displayed a reversible change in the UV-Visible absorption spectrum from the deoxy form to the oxygen-binding one,in response to the partial oxygen pressure of the atmosphere.The characteristic absorption peaks of the encapsulated Hb in different gas-binding states showed no significant change comparing with those of the free Hb.The Hb encapsulated PEG-P(GMA-API)nano-micelles showed the potential application as artificial oxygen carriers for transfusion.
摘要:Nylon short fiber (NSF) and silica were used to fill natural rubber (NR) to prepare composites compatibilized by maleated natural rubber (MNR).Influences of NSF content on dynamic rheological behavior were discussed for the un-compatibilized and the MNR compatibilized NSF/NR compounds.The compatibilized NSF/NR masterbatch was added into NR filled with 30 phr silica,and dynamic rheological behavior of the compounds was investigated with respect to NSF content.The modified two phase model was used to analyze the enhancement effect offiller phaseconstructed by introducing NSF or by introducing both NSF and silica.The changes of storage modulus E' and loss factor tan of vulcanites were studied for clarifying influence of composition on dynamic mechanical behavior.It was indicated that MNR could efficiently enhance the compatibility between NSF and rubber matrix to improve the dispersion of fiber and to construct a strongfiller phasein comparison with that in the un-compatibilized compounds.Introduction of silica greatly improves both the elastic and the viscos contributions of thefiller phasewith a markedly reduced relaxation dynamics,the reinforcing factor and strain amplification factor of NR/NSF/SiO2 compounds were higher than those of NR/NSF compounds.Storage modulus and peak value of loss factor increased and decreased,respectively,with adding of NSF in the NR vulcanites.
关键词:Natural rubber;Reinforcement;Rheology;Two phase model
摘要:The anionic copolymerization of allyl methacrylate (AMA) and methyl methacrylate (MMA) catalyzed by 1-tert-butyl-4,4,4-tris(dimethylamino)-2,2-bis[tris(dimethylamino)-phosphoranylidenamino]-2 5, 5-catenadi-(phosphazene) (t-BuP4) was studied at room temperature.The structure and properties of the polymers have been characterized by nuclear magnetic resonance spectroscopy (NMR),Flourier transform infrared spectroscopy (FTIR),gel permeation chromatography (GPC),differential scanning calorimetry (DSC) and themogravimetric analysis (TGA).The results showed that t-BuP4 displays high catalytic activity for the copolymerization of AMA with MMA,resulting linear copolymers with pendent allyl groups at back chains.Both the conversions of AMA and MMA could reach over 90% without considering the risk of gelation or crosslinking.NMR and FTIR results indicated that AMA incorporated into the copolymers by the reactions of methacrylate double bonds but not allyl groups.No cross-linking or cyclization reactions were observed during this polymerization system,which might be because the active centers catalyzed by t-BuP4 were not strong enough for the initiation of ally groups.The amount of pendant double bonds in the copolymers could be adjusted by changing AMA/MMA feed ratio.GPC results showed that the resultant copolymers have narrow polydispersity and good molecular weight control.TGA and DSC results showed that the decomposition temperatures for copolymers increased with the increasing of AMA/MMA feed ratio,but the glass transition temperatures (Tg) were changed oppositely.
摘要:Functional ionic liquids of 1-(2-hydroxyethyl)-3-methyl imidazole chloride ([HeMIM]Cl),1-ethylamine-3-methyl imidazole bromide ([AeMIM]Br) and 1-carboxy ethyl-3-methyl imidazole chloride ([CeMIM]Cl) were synthesized and characterized by FTIR and 1H-NMR.After dissolving in the ionic liquids for 3 h,the liquefied wood powder obtained was blended with phenol and formaldehyde in situ to prepare phenolic resin composites.The effects of the ionic liquid types on the dissolution rate of wood powder and the properties of phenolic resin were studiced through the tests of chemical structure,mechanical properties and morphology by FTIR,XRD,DSC and SEM.The results showed that the mechanical properties of the phenolic resin composites were improved obviously by ionic liquid and its solubility product of wood powder.The wood powder showed the highest liquefaction rate in [CeMIM]Cl,reaching 24.6% at 90 ℃.When the weight ratio of [CeMIM]Cl to wood powder was 10:1,the free formaldehyde content in the phenolic resin composites was decreased from 3.64% to 0.92%.The impact strength of phenolic resin modified with [AeMIM]Br was increased from 0.93 kJ/m2 to 6.96 kJ/m2,while the tensile strength of phenolic resin modified with [AeMIM]Br and its liquefaction of wood powder was increased from 3.28 MPa to 9.70 MPa.
摘要:As a typical elastic scattering technique,laser light scattering results cannot precisely describe the solution structure when the samples absorb incident light.Therefore,commercial laser light scattering instrument has been modified and upgraded to utilize four independent lasers,e.g.785 nm,632.8 nm,532 nm and 457 nm,respectively as the light sources.By switching the wavelengths of incident lasers to avoid the sample absorption,the instrument can be widely used in fluorescent/phosphorescence solution systems.Spherical polystyrene nanoparticles with and without fluorescent dyes are used to calibrate the modified instrument.It is found that the height of the normalized intensity-intensity time correlation function decreases with the increase of the scattering angle when the sample absorbs the incident laser light.Such a correlation function fails to describe the sample solution structure,because the corresponding hydrodynamic radius distribution shows two modes and the average characteristic line width Г versus the square of scattering vector q2 does not fit a good linear relationship any more.Therefore,another laser which is not absorbed by the sample is used to do the calibration again.The corresponding intensity-intensity time correlation functions and the fitting results can precisely describe the solution structure.Fluorescence correlation spectroscopy (FCS) is also conducted to further prove the results obtained from the modified laser light scattering instrument are precise and accurate.
摘要:Chloromethylated polysulfone (CMPSF) was first prepared.On this basis,benzene sulfonate sodium (BSS) groups and benzene sulfonate disodium (BDSS) groups were bonded on the side chains of polysulfone (PSF),and two series of sulfonated PSFs with side chains,PSF-BSS and PSF-BDSS,were obtained via nucleophilic substitution reactions with sodium 4-hydroxybenzenesulfonate and disodium 1,2-dihydroxybenzene-3,5-disufonate as nucleophilic reagents,respectively.The effects of main factors on the nucleophilic substitution reactions were examined,and the reaction conditions were optimized.In the structures of PSF-BSS and PSF-BDSS,hydrophilic and hydrophobic domains are phase-separated at nanoscale.PSF-BSS and PSF-BDSS were fully characterized by FTIR and 1H-NMR spectra.By casting film,proton exchange membranes were prepared.The basic properties of the proton exchange membranes were determined,and the effects of the two structure factors,the aromaticity of the main chain and the micro-phase separation between hydrophilic and hydrophobic domains,on the properties of the proton exchange membranes were studied.The investigation results show that in the solvent with strong polarity,the nucleophilic substitution reaction between CMPSF and hydroxy-benzenesulfonic acid sodium salt can be carried out smoothly,and PSF-BSS with a sulfonate bonding amount of 2.07 mmol/g and PSF-BDSS sulfonate with a sulfonate bonding amount of 2.11 mmol/g can be get at 100 ℃ for 40 h.The corresponding proton exchange membranes have higher proton conductivity,and for the membrane of PSF-BDSS,the proton conductivities at room temperature and at 80 ℃ are 4.7 10-2 S/cm and 8.1 10-2 S/cm,respectively.The proton exchange membranes have excellent dimensional stability (8.6% and 30% of swelling ratios at room temperature and at 80 ℃,respectively),and have fine thermal stability and oxidation stability.
摘要:Polyindole was synthesized by chemical oxidation using ferric chloride anhydrous as oxidant.Polyindole nanofibers have been successfully prepared by using electrospinning method by dissolving polyindole in acetonitrile.The heavy metal uptake performance of the polyindole nanofibers was presented by adsorption of Cd(Ⅱ) ions from aqueous solution.FTIR and NMR spectra confirm that the polymerization of indole happens at C2,C3 positions of indole unit.Electrospun polyindole nanofibers exhibit cylindrical,uniform,bead-free and random orientation observed by SEM and TEM.The average diameter of the electrospun polyindole nanofibers is about 145 nm and the BET specific surface area is 73.45 m2/g.Electrospun polyindole nanofibers show good adsorption properties for Cd(Ⅱ) ions from aqueous solution.The equilibrium adsorption capacity is about 140.36 mg/g reached at pH 6 after 50 min.The adsorption isotherm data fit well the Freundlich isothermal model.The kinetic process of Cd(Ⅱ) adsorption by polyindole nanofiber is found to fit the pseudo-second order rate equation.Desorption results show that the adsorption capacity can retain 100.67 mg/g (up to 71%) after 10 times usage,which indicates that the polyindole nanofibers could be suitable for potential applications in water treatment for the removal of Cd(Ⅱ) ion as a nano-adsorbent.
摘要:Poly(3,4-ethlenedioxythiophene)/lignosulfonic acid (PEDOT/LS) conductive compounds was synthesized chemically,using LS not only as a dispersant but also a dopant for PEDOT.The structure and performance were investigated by ultraviolet-visible spectroscopy (UV-Vis),Fourier transform infrared spectroscopy (FTIR),zeta potential and particle size analysis,the atomic force microscopy (AFM),X-ray photoelectron spectroscopy (XPS),X-ray diffraction (XRD),four point probes meter,electrophoresis and surface resistivity tests.It showed that PEDOT was successfully polymerized in LS aqueous solution,resulting in water-dispersive PEDOT/LS conductive particles.For the structure of PEDOT/LS particles,the stoichiometric PEDOT/LS complex stays in the inner core and the excess of hydrophilic LS covered on the surface.The interaction between PEDOT and LS is so strong that they can not be separated under electrophoresis.This complex is amorphous according to XRD.When the weight ratio of LS to EDOT increased from 0.7:1 to 3.0:1,the particle size dropped from 673 nm to 348 nm,and the surface resistivity of PEDOT/LS rose to 87.2 k/sq from 1.9 k/sq.Also,the PEDOT /LS film became smoother.The coating made by PEDOT/LS could make the surface resistance of a sheet glass decreased to 107 /sq from 1012 /sq.
摘要:Polypyrrole/nano-SiO2 composite (PPy/nSiO2) was prepared by chemical oxidative polymerization and characterized by SEM and FTIR techniques.It was used for oxidative degradation of hydroquinone.The results showed that polypyrrole was loaded on the surface of nano-SiO2 evenly.With nSiO2 used as the carrier,agglomeration phenomenon of polypyrrole could be effectively inhibited.As compared with PPy,PPy/nSiO2 exhibited high oxidative property for hydroquinone in weak acid solutions,and the degradation process was in line with the rule of the apparent first-order kinetics within 2 h.The results of UV-Visible spectroscopy showed that hydroquinone was oxidized to be benzoquinone by the polypyrrole reactive intermediates,which was formed between hydroquinone and polypyrrole by hydrogen bond interactions.After recovery treatment of PPy/nSiO2,oxidation removal of hydroquinone on PPy/nSiO2 within 120 min was 84.1% under the same conditions.Polypyrrole had a dual function both as the catalyst and the oxidant for oxidative degradation of hydroquinone.
摘要:Sodium 2,2'-methylene-bis(4-6-di-t-butylphenyl) phosphate (NA-1) and sodium 2,2'-methylene-bis(4-t-butylphenyl) phosphate (NA-2) were synthesized from 2,4-di-t-butyl phenol.The differences of nucleated effectiveness which the ortho-substituted groups of aromatic heterocyclic phosphate salts resulted in were studied.The structures of molecule,condensed state,character of surface and thermal parameters were characterized by Fourier transform infrared spectrometry (FTIR),nuclear magnetic resonance (NMR),X-ray diffraction (XRD) and scanning electronic microscopy (SEM),thermo gravimetric analysis (TGA) and differential scanning calorimetry (DSC).The structure of crystal,crystallization behavior and optical properties of the NA-1/iPP and NA-2/iPP composites were analyzed by polarizing optical microscopy (POM),analysis of the fractured surface,DSC,photo electricity opacimetry (PEOM).The results showed that NA-1 could induce iPP's spheruletes finer,peak temperature of crystallization (Tcp) higher 5.1 ℃,haze lower 7.4% and transmittance higher 4.3% than NA-2 when the content of two kinds of nucleates in iPP is 0.2%.The results of fractured surface SEM analysis of iPP and nucleated iPP composites showed that the uniformity of NA-1 and NA-2 in the base material was fine and their mean particle sizes were 0.79 m and 0.82 m.Their curves of Frequency distributions by particle size were similar.The differences of uniformity and distributions were indistinctive,so the Effects of nucleating effectiveness of Aromatic Heterocyclic Phosphate Salts were induced by the ortho-substituted groups of molecular structures.
摘要:A new blue chain extender,1-(1,1-bis(hydroxymethyl)) ethyl amino-4-methylamino anthraquinone (HMEMAQ) was synthesized using 1-methylamino-4-bromo-anthraquinone and 2-amino-2-methyl-1,3-propanediol as raw materials by substitution reaction,and then the polyurethane prepolymer was prepared using HMEMAQ and N,N-bis(2-hydroxyethyl) acrylamideas chain extenders.After that,the covalently blue polyurethane-acrylate copolymer (PUA) emulsion was fabricated through the copolymerization of polyurethane prepolymer with methyl methacrylate and butyl acrylate.The chemical structure of HMEMAQ and the properties of PUA emulsions and their latex films were characterized by 1H-NMR,FTIR,UV-Vis spectra,size and zeta potential analysis,xenon arc aging testing and so on.Results showed that,under nitrogen atmosphere,the color fading of emulsions could be avoided when AIBN was used as initiator during the fabrication of PUA emulsions.When the AIBN amount was equal to 2 wt% based on the unsaturated monomers,the conversion of unsaturated monomers reached 99.9%.The unsaturated monomer conversion and the colloidal properties had no obvious change with the increase of the HMEMAQ amount.The max value of the PUA film and HMEMAQ was the same at 640.8 nm,indicating the same color of them.Comparing with the non-covalently blue PUA film which had the same chromophore,the covalently blue PUA film exhibited obvious improvements both in light fastness and solvent fastness.