最新刊期
卷 ， 期 12 ， 2015
- 摘要：Lignin,surpassed only by cellulose,is the second most abundant renewable biomass.It is also a kind of environmentally friendly organic polymer materials.Atom transfer radical polymerization (ATRP) is a kind of living/controlled free radical polymerization technology which has been developed rapidly in recent years with important applications.The latest research progress of ATRP in grafting copolymerization of lignin was summarized.The surface modification of lignin via ATRP is proposed to give lignin various functionalities,such as thermosensitive,ionic-responsive,gas-switchability and gene delivery by grafting copolymerization of different functional monomers onto the surface of lignin.At last,the application of AGET ATRP (activators generated by electron transfer ATRP) in the grafting copolymerization of lignin is introduced.关键词：Lignin;Grafting copolymerization;Modification;Atom transfer radical polymerization (ATRP)
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发布时间：2021-03-19
Reviews
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The Curing Mechanism of Epoxy Resin/Liquid Nitrile Rubber System by Sulfur and Its Network Structure
摘要：The curing reaction mechanism of epoxide groups and C/C double bonds was investigated by using sulfur (S) as curing agent,and liquid nitrile butadiene rubber (NBR),phenyl glycidyl glycerol ether (GPE) and allyl phenyl glycidyl ether (APE) as model compounds.Differential scanning calorimetry (DSC),Fourier transform infrared spectroscopy (FTIR),X-ray photoelectron spectroscopy (XPS) and dynamic mechanical thermal analysis (DMA) were used to detect the variations of curing enthalpy,double bonds and the epoxy groups with reaction time.The experimental results showed that the chemical reactions between the nitrile rubber and epoxy model compounds were verified,and the curing reaction in NBR-Sulfur system is a one step reaction,and in that rubber/epoxy compounds/sulfur system is a two step reaction.Comparatively,the cured NBR-S shows the lowest glass transition temperature and the highest energy storage modulus and crosslinking density,while,NBR-APE-S presents the highest glass transition temperature and the lowest energy storage modulus and crosslinking density.Furthermore,the curing mechanism of the liquid rubber and epoxy compound is suggested as:sulfur can cleavage into sulfur radicals,which initiate the addition reaction of rubber double bonds to form mercapto groups.Finally,the resultant mercapto groups react further with epoxy groups through ring-opening reaction.Meanwhile,coupling reactions between different radicals occur.关键词：Allyl phenyl glycidyl ether;Phenyl glycidyl ether;Liquid nitrile rubber;Epoxy resin;Sulfur;Curing mechanism- 48
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发布时间：2021-03-19 - 摘要：The fractionation of trans-1,4-poly(butadiene-co-isoprene) copolymer rubbers (TBIR) was carried out by stepwise isothermal crystallization fractionation method,and the structure and composition of the TBIR fractions were studied.It was found that TBIR-20 was a semi-crystalline copolymer with long trans-1,4-polyisoprene (TPI) blocks and butadiene units randomly distributed in the molecular chain.While TBIR-40 was a copolymer containing TPI blocks and trans-1,4-polybutadiene (TPB) blocks.The application of TBIR as hump strip stocks in passenger car radical (PCR) tires was investigated.The NR/BR/TBIR compounds showed improved green strength,crystallinity and shore A hardness,as well as accelerated curing rate.For NR/BR/TBIR vulcanizates,physical and mechanical properties,such as tensile strength,tear strength,modulus and resilience stand in a high level,outstanding properties including decreased heat built- up,improved abrasion resistance and ageing- resistant performance,and excellent flexing fatigue properties were observed with the incorporation of TBIR.DMA tests showed that NR has a better compatibility with TBIR compared with BR.TEM results showed a good dispersion of carbon black in NR/BR/TBIR vulcanizates.So NR/BR/TBIR vulcanizates with about 20 phr TBIR showed satisfied mechanical properties,improved abrasion and ageing resistance,especially excellent dynamic properties like low heat built- up and very high flexing fatigue-resistance.关键词：Trans-1;4-;Butadiene;Isoprene;Copolymer;Tire;Hump strip
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发布时间：2021-03-19 - 摘要：A new kind of mixed matrix membranes (MMMs) with cellulose acetate butyrate (CAB) as matrix and multi-walled carbon nanotubes (MWCNTs) as fillers was prepared by solvent mixing-solution casting method.The morphology,structure and mechanical properties of CAB/MWCNTs MMMs were characterized using scanning electron microscopy (SEM),transmission electron microscopy (TEM) and tensile testing.The results showed that MWCNTs and CAB matrix had good interfacial adhesion.No obvious defect was observed on the fracture surface of CAB/MWCNTs MMMs.The obtained CAB/MWCNTs MMMs exhibited good mechanical properties.Furthermore,gas separation properties of the CAB/MWCNTs MMMs for O2,N2,CH4,CO and CO2 were investigated.It was found that,with the increase of MWCNTs content,the permeability coefficients of CAB/MWCNTs MMMs for all test gases (O2,N2,CH4,CO,CO2) were significantly improved,especially for quicker gasO2 and CO2.When the content of MWCNTs was 30 wt%,the permeability of MMMs for O2 and CO2 reached 40.24 and 180.20 Barrer,which compared with neat CAB membrane,increased by 300% and 260%,respectively.Moreover,the CAB/MWCNTs MMMs showed excellent separation property for some gas pairs,such as CO2/N2,CO2/CH4,CO2/CO and O2/N2.The selectivity of CO2/N2,CO2/CH4 and CO2/CO was not sacrificed with the increase of CO2 permeability.More interestingly,with the increase of O2 permeability,the selectivity of O2/N2 also increased from 3.2 to 4.0,an increase of 25% compared with neat CAB membranes.Therefore,the present work provides a facile and effective method to prepare new kind of cellulose based MMMs with improved gas separation properties.关键词：Cellulose acetate butyrate;Multi-walled carbon nanotubes;Gas separation;Mixed matrix membranes
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发布时间：2021-03-19 - 摘要：A series of reduced graphene oxide/polyimide (rGO/PI) nanocomposites are prepared via in situ random co-polycondensation of chemically modified reduced graphene oxide (rGO-NH2) and commercial ODA,ODPA,BPADA,as well as subsequently casting on glasses and thermal imidization.The chemical structure and composition,as well as the microstructure are employed to confirm that GO is chemically modified and further reduced successfully for rGO-NH2.It was found that with the incorporation of rGO-NH2 at 2 wt%,Tg,T5% in N2 and air of the resulting rGO/PI nanocomposites were increased by 17.9 K,32.7 K and 46.7 K,respectively,as well as the tensile strength,modulus and elongation at break increased by 40.6%,16.7%,187.8% in turn compared with neat PI.In addition,water surface contact angle (SCA) of the rGO/PI nanocomposite films reached up to 103.8 with 2 wt% of rGO-NH2.All of these effects of the content of rGO-NH2 are explained to correlate the micromorphology of the resulting nanocomposites.This facile and effective approach provides a possibility for developing homogeneously dispersed,high performance PI composites based on graphene for advanced engineering or functional materials.关键词：In situ random co-polycondensation;Graphene;Polyimide;Nanocomposites
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发布时间：2021-03-19 - 摘要：The sodium lignosulphonate polyethenoxy ether (SL-PEG) was prepared by electrophilic substitution reaction using sodium lignosulphonate (SL) and polyethylene glycol (PEG600).The chemical structure of SL-PEG was characterized and the weight-average molecular weight of SL-PEG was up to 32900,because of the grafting of many polyethenoxy ether units.The grafting reaction was found to occur at phenolic hydroxy of SL,thus the phenolic hydroxy contents of SL-PEG reduced from 1.17 to 0.30 mmolg-1.Subsequently,the lignin-based cationic-anionic surfactant (CA-SL) was prepared via electrostatic self-assembled method combining SL-PEG with cetyl trimethyl ammonium bromide (CTAB).The surface activity and aqueous solution behaviour of CA-SL was studied,the result showed that the CA-SL aqueous solution presents far lower surface tension (minimum to 38.75 mNm-1) and critical aggregation concentration (0.0050~0.0065 gL-1) than SL.In order to investigate the dispersing and stabilizing properties of CA-SL,the CA-SL was used as dispersants to prepare imidacloprid and dimethomorph suspension concentrates.The results indicated that the CA-SL has good grinding and dispersion effect,and these two suspension concentrates exhibit good stability during the heat storage process,owing to its excellent ability to restrain the creaming and particle coarsening effectively.关键词：Sodium lignosulphonate polyethenoxy ether;Cationic-anionic surfactant;Electrostatic self-assembly;Dispersant;Creaming
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发布时间：2021-03-19 - 摘要：Hydrophobic and cross-linked poly[cyclotriphosphazene-co-(4,4'-9-(fluorenylidene)diphenol)](PZHF)microspheres were facilely prepared by a one-step precipitation copolymerization of hexachlorocyclotriphosphazene and 4,4'-9-(fluorenylidene)diphenol with triethylamine as deacid reagent and acetonitrile as solvent.The chemical structure and morphology of the microspheres were characterized by Fourier transform infrared (FTIR)spectroscopy,X-ray photoelectron spectroscopy (XPS)and scanning electron microscopy (SEM),respectively.Then the microspheres were employed to stabilize air-water interface to form liquid marbles.The static stability of the resultant liquid marble and the interfacial packing of the PZHF microspheres was investigated by digital camera and optical microscope,respectively.In addition,the vapor or gas permeability of the liquid marble was also studied.The results showed that the PZHF microspheres owned highly cross-linked and organic-inorganic hybrid structure,and the average particle size was 1.3 m.The microspheres possessed a rather rough surface and thus hydrophobicity.The microspheres could encapsulate liquid to form stable liquid marbles.The loose packing of the microspheres at the air-water interface endowed the liquid marble with unique vapor or gas permeability.The outside gas could diffuse into the liquid marble easily without destroying its architecture.关键词：Polyphosphazene microspheres;Cross-linked;Stabilizer;Liquid marble;Air-Liquid interface
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发布时间：2021-03-19 - 摘要：Polybutadiene rubber with the fluorescence and thermo-responsive properties was synthesized by macromolecular design.Firstly,the block copolymer polybutadiene-b-poly(-caprolactone)(HTBCP) was synthesized via the ring-opening polymerization of -caprolactone in presence of a hydroxyl-terminated polybutadiene(HTBP),which was catalyzed by stannous octanoate[Sn(Oct)2].With the help of -caprolactone,polybutadiene rubber was improved in molecular weight and heat resistance,which was also terminated by hydroxyl (-OH).Then the macro-monomer of carboxyl- terminated poly(N-isopropyl acrylamide)(PNIPAm-COOH) was synthesized via the free radical polymerization in presence of mercaptoacetic acid(MAA).Finally the copolymer of polybutadiene rubber(HTBCP-b-PNIPAm) with moderate molecular weights (Mn=8000~15000) was synthesized from polybutadiene-b-poly(-caprolactone) and the macro-monomer of carboxyl- terminated poly(N-isopropyl acrylamide) by the condensation reaction,which was catalyzed by dichloroacety chloride(DCC).The polymer of polybutadiene-b-poly(-caprolactone)(HTBCP),poly(N-isopropyl acrylamide) (PNIPAm-COOH) and polybutadiene rubber (HTBCP-b-PNIPAm) were characterized by Fourier transform infrared spectroscopy (FTIR),nuclear magnetic resonance (NMR),gel permeation chromatography (GPC),X-ray photoelectron spectroscopy (XPS),UV-Visible spectroscopy (UV-Vis),fluorescence spectroscopy etc.The results suggested that the copolymer of polybutadiene rubber was fluorescent having UV absorption at 274 nm and fluorescence excitation at 304 nm; besides the copolymer of polybutadiene rubber showed a critical phase transition temperature (LCST) at 30℃,at temperatures higher than 30℃,the copolymer HTBCP-b-PNIPAm has hydrophobic/hydrophobic chain segments,on the other hand it has hydrophobic/hydrophilic chain segments.The polybutadiene rubber with the fluorescence and thermo-responsive properties will make contribution in the field of luminescent or separating material.关键词：Poly-butadiene rubber;Poly(N-isopropyl acrylamide);Fluorescent;Thermo-responsive
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发布时间：2021-03-19 - 摘要：The self-assemble morphologies of amphiphilic diblock copolymers in dilute selective solutions confined in circular tubes and horizontal slits were investigated by self-consistent field theory (SCFT),which were affected by the confinements,the hydrophilc-lipophilic properties of the walls and the spacing between substrates.In neutral circular tubes,with the increase of the repulsion interaction between solvent and hydrophobic blocks and the attraction interaction between solvent and hydrophilic blocks,the copolymer adsorbed on the walls assembling as mushroom shapes.The more intense the two interactions,the easier the adsorption phenomena of the amphiphilic diblock copolymers.In hydrophilic tubes,the adsorption phenomena eased,and the spherical micelles arranged regularly near the walls with the increase of the interaction between walls and hydrophilic segments of the copolymer.When the differences between the hydrophobic chain and hydrophilic chain interactions with the solvent were very large,the adsorption phenomena of the copolymers could not be eliminated,even though the adsorption interaction between the wall and the hydrophilic blocks was enhanced.In neutral horizontal substrates,as the substrate spacing was increased,amphiphilic diblock copolymers sequentially appeared as spherical micelles-mushroom-like micelles-single spherical micelles-polymer brush-double spherical micelles-symmetrical polymer brushes near the substrates.关键词：Amphiphilic diblock copolymers;Dilute solution;Adsorption behavior;Self-consistent field theory;Self-assembly;Circular pores;Horizontal substrates
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发布时间：2021-03-19 - 摘要：Polyurethane/graphene (PU/RGO) nanocomposites were prepared by in situ polymerization of the residual hydroxyl or carboxyl groups on graphene with the castor oil-based polyurethane prepolymer,and their molecular structures were characterized by FTIR and Raman spectroscopy.In addition,the thermal stability and morphological structure and resistivity-temperature behavior of PU/RGO nanocomposites were investigated by thermogravimetric analyzer (TGA),X-ray diffraction (XRD),scanning electron microscope (SEM) and ZC36 high resistance meter,respectively.The results indicated that the addition of the graphene led to the increase in the cross-linked network owing to the reaction of more-NCO groups of PU with graphenes,and the enhancement in physical crosslink amongst the polyurethane-based composites owing to the effect of the relative free graphene residual.As a result,the PU/RGO composites showed a slight increase in room-temperature resistivity due to the combined effect of crosslink network and physical crosslink reaction on the conductive network.When the temperature value reached a critical temperature,the rapid expansion of the volume of PU-based polymer destroyed the significant reductive network of graphene,resulting in the remarkable enhancement in the resistivity-temperature behavior of PU/RGO composites.Especially,at the loading of 3 wt% graphene hybrid filler in PU matrix,PTCR behavior of the composites was observed with resistivity increase of nearly 3 orders of magnitude.Therefore,it is expected that the PU-based composites with a few contents of graphene might be the promising PTCR materials.关键词：Graphene;Polyurethane;PTC;In situ polymerization
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发布时间：2021-03-19 - 摘要：High internal water phase double emulsions were used as the templates to prepare interconnecting porous poly(styrene-divinyl benzene-ethylene glycol dimethacrylate) microspheres which were applied in the load of catalysts and the adsorption of heavy metal ions.First,high internal water phase double emulsions were prepared via phase inversion of water-in-oil high internal phase emulsions (W/O HIPEs) stabilized solely by 12-acryloxy-9-octadecenoic acid (AOA) through increasing the content of water phase.The polymerization of these emulsions was then initiated by either -ray irradiation or chemical initiators.Scanning electrical microscopy (SEM) images showed that interconnecting porous microspheres were reached by using -ray irradiation,while only hollow microspheres were obtained by using chemical initiators.After hydrolysis,interconnecting porous microspheres prepared by -ray irradiation were modified with carboxyl groups,which were used to adsorb Cu2+ ions.It was found that the adsorption capacity of Cu2+ first increased and then decreased with the increasing of pH,and the maximum adsorption capacity was 175 mg/g at pH=5.In addition,using in situ reduction,interconnecting porous microspheres were loaded with Pd nanoparticles which were used to catalyze the hydrogenation of cinnamaldehyde.Thermogravimetric analysis and TEM results showed that Pd@hydrolyzed porous microspheres had higher catalytic efficiency due to the higher load of uniform dispersed Pd nanoparticles,while Pd@unhydrolyzed porous microspheres had lower catalytic efficiency owing to the lower load of aggregated Pd particles.关键词：Double emulsions;Porous microspheres;Catalytic hydrogenation;Absorption of heavy metal ions
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发布时间：2021-03-19 - 摘要：A series of waterborne cationic-nonionic polyurethanes surfactants (CPUS) was prepared through prepolymerization method and their structures were investigated by FTIR and 1H-NMR.The effects of N-methyldiethanolamine (MDEA) concentration on the surface tension,critical micelle concentration,rheology property,micelle size,micropolarity and aggregation behaviors of CPUS were studied by DLS,surface tension analysis,steady state rheological analysis and fluorescence analysis.TEM results showed that CPUS micelles displayed as core-shell spheres.It was also found that average micelle particle size and polydispersity index of CPUS solutions decreased with increasing MDEA concentration.While the surface tension and critical micelle concentration (CMC) decreased first and then increased,the lowest of which were 1.99 g/L and 39.54 mN/m.When the CPUS concentration was lower than CMC,the light scattering intensity was very low and changed slowly with CPUS concentration.However,the light scattering intensity displayed a gradually increasing tendency when the CPUS concentration was greater than CMC.Meanwhile,the aggregation number of CPUS micelles increased greatly.The viscosity of CPUS solution increased with increasing MDEA concentration,as well as the interactions among micelles increased,while the pseudoplastic behavior was enhanced.In addition,fluorescence spectrometry showed that I1/I3 values decreased from 1.8 to 1.3 and I338/I334 increased from 0.5 to 1.7,suggesting that the hydrophobic groups tended to aggregate and form hydrophobic microdomains,and pyrene molecules transfered from the aqueous polar phase to micellar interphase.Furthermore,the micelle micropolarity and the difficulty with micelle formation decreased first and then increased as increasing MDEA concentration.关键词：Waterborne cationic polyurethane;Critical micelle concentration;Solution properties;Micelle;Aggregation behaviors
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发布时间：2021-03-19 - 摘要：This study has focused on preparing an OFET-structured memory device based on poly(3-hexylthiophene)/poly(ethylene oxide) doped with ethyl viologen diperchlorate (P3HT/(PEO+EV)) bilayer solid membranes and investigating the electrical response of this system.The obtained data revealed that the conductivity of the system can be reversibly switched between high and low conductance states with write and erase bias at +3 and-3 V,respectively,and readout bias at 0.5 V.The system showed good resistive bistable memory characteristics with the ON/OFF current ratio up to 105.Although the ON current decayed with the retention time,the write/erase action remained robust after 2800 s readout operation,indicating the reliability of the switching characteristics.To better understand the memory mechanism,confocal laser scanning microscopy (CLSM) was used to monitor the fluorescence fluctuations during the write and erase pulses.The obtained results showed that fluorescence from P3HT layer quenched gradually when the switching-ON pulse was applied,indicating polarons formed at the source electrode and then propagated from the source to the drain electrode with a rate of around 120 m/s.However,fluorescence recovered immediately when the switching-OFF pulse was applied,demonstrating P3HT polarons were reduced to neutral state.关键词：Poly(3-hexylthiophene);Ethyl viologen diperchlorate;Polyelectrolyte;Electrical memory;Confocal laser scanning microscopy
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发布时间：2021-03-19 - 摘要：Chitosan-doxorubicin prodrug with the linkage of hydrazone bond (Chitosan-hz-DOX) was employed as the carrier ofcamptothecin (CPT) to develop a dual-drugdelivery system (CPT-CS-DOX).UV-Vis,DLS,and TEM analyses were conducted to investigate the diameter,morphology,drug loading and releasebehaviors of the system.With the increase in the grafting content of DOX on chitosan,the resultant Chitosan-hz-DOX prodrug showed an enhanced loading capacity of CPT.The optimal addition amount of CPT to prepare CPT-CS-DOX was determined to be 20%.After loading CPT,the Chitosan-hz-DOX nanoparticles still remained the spherical morphology but their diameters were increased.In addition,the diameter of CPT-CS-DOX was decreased gradually with the DOX content of Chitosan-hz-DOXbecause of the strong hydrophobic interactions.The premature releases of DOX and CPT at pH=7.4 were effectively inhibited from the delivery system,that is,their cumulative releases were 10% and 20%,respectively.Compared with that,in particular,their release rates were remarkably increased at acidic conditions,showing a highly pH-dependent drug release behavior.Furthermore,Peppas equation was employed to analyze the release mechanism of DOX and CPT at different environment conditions.Their release process can be divided into two stages.Thereleases of DOX and CPT at the first stagefollowedthe Fick-diffusion controlled and swelling controlled mechanisms at neutral condition,while at acidic conditions,the release mechanism of CPT remained unchanged but that of DOX was changed.At the second stage,the releases of both drugs obeyedtheFick-diffusion controlledmechanism.关键词：Chitosan-doxorubicin prodrug;Camptothecin;pH-Responsive;Dual-drug delivery
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发布时间：2021-03-19 - 摘要：The cyclomatrix-type polyphosphazene fluorescent nanofibers(PZS-NFs)were prepared by one-step precipitation polymerization of hexachlorocyclotriphosphazene and 4,4'-sulfonyldiphenol with trimethylamine as acid-accepter and a mixture of toluene and acetone(8:1 by volume)as solvent.The chemical structure,morphology,thermal stability,and fluorescent property of PZS-NFs, were characterized by Fourier transform infrared spectroscopy,X-ray photoelectron spectroscopy,scanning electron microscopy,transmission electron microscopy,thermal gravity analysis,and fluorescence spectroscopy,respectively.Then PZS-NFs were served as a fluorescent chemical sensor for the detection of PA in solution phase by a spectrofluorometric titration method using a spectrofluorometer.The selective detection performance was investigated,and the corresponding detection mechanism was also discussed.The results showed that the mean diameter of the nanofibers was 80 nm.The highly cross-linked and organic-inorganic hybrid structure endowed the nanofibers with excellent thermal stability.The initial thermal decomposition temperature was as high as 520℃ in nitrogen atmosphere.The nanofibers exhibited an intrinsically fluorescent emission at 433 nm when excited at 369 nm,and showed the fluorescence quenching response towards PA with high sensitivity,efficiency,and selectivity over a number of other analytes including 2,4,6-trinitrotoluene,2,4-dinitrotoluene,1,3-dinitrobenzene,4-nitrophenol,nitrobenzene,4-benzoquinone,chlorobenzene,and nitromethane in methanol.The quenching constant and detection limit for PA were 1.81104 M-1 and 80 g/L,respectively.The specific recognition of PA by PZS-NFs might be attributed to the effective enrichment of PA from solution to the surface of PZS-NFs realized by the acid-base interaction between the acidic phenolic hydroxyl groups of PA molecules and the electron-rich nitrogen atoms of the cyclotriphosphazene units in PZS-NFs,facilitating the formation of a ground-state non-fluorescent complex of the nanofibers and PA as well as the excited-state energy transfer from the nanofibers to PA.Considering the simple preparation and high selectivity,PZS-NFs have a great potential to serve as a fluorescence chemical sensor for the detection of PA in practice.关键词：Polyphosphazene;Nanofibers;Fluorescence;Picric acid;Selective detection
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发布时间：2021-03-19 - 摘要：A series of cobalt dicholoride complexes (1~4) bearing[2-(4,5-diphenylimidazolyl)phenylimino]phenol ligands ([N^N^O] tridentate ligands) have been synthesized and characterized by FTIR spectra and elemental analysis.These cobalt complexes were applied in the stereospecific polymerization of 1,3-butadiene under various reaction parameters.The type of cocatalyst,Al/Co molar ratio,reaction temperature and ligand structure of cobalt complexes were investigated in order to verify their influences on the catalytic activity and the properties of resulting polymers.Among the Al-based cocatalysts,ethylaluminum sesquichloride (EASC) was proven to be the best cocatalyst,yielding higher conversion of butadiene and cis-1,4 content of polybutadienes.The increase of Al/Co molar ratio enhanced the conversion of butadiene and slightly affected the molecular weight and microstructure of polymers.The catalytic systems displayed good thermal stability in the temperature range of 25~90℃; however,the higher temperature led to the lower molecular weight and broader molecular weight distribution,and the decrease in the cis-1,4 content and the increase in the trans-1,4 and 1,2 content.Upon activation with EASC,all the cobalt complexes displayed high catalytic activity for the polymerization of 1,3-butadiene, and high cis-1,4 contents in the resulting polymers were obtained.关键词：Cobalt;EASC;Butadiene;Polymerization;Cis-1,4 content
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发布时间：2021-03-19
Research Article
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